CN101431885B - All-directional conductive foam and producing method thereof - Google Patents
All-directional conductive foam and producing method thereof Download PDFInfo
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- CN101431885B CN101431885B CN2008101634136A CN200810163413A CN101431885B CN 101431885 B CN101431885 B CN 101431885B CN 2008101634136 A CN2008101634136 A CN 2008101634136A CN 200810163413 A CN200810163413 A CN 200810163413A CN 101431885 B CN101431885 B CN 101431885B
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Abstract
The present invention relates to unidirectional conductive foam and a manufacture method thereof. The technical problem to be solved through the invention is to provide unidirectional conductive foam and a manufacture method, and the conductive foam produced in the way described in the invention has excellent compressibility and softness, can guarantee good conductive contact area with excellent electromagnetic shielding performance. The technical solution is as following: unidirectional conductive foam characterized in that substrate of the conductive foam is flake high elastic foaming sponge with polyester, polyether or PET as its main components; wrap the unidirectional conductive foam with breathable mesh cloth and the thickness of wrapped foam is between 1mm to 10mm; chemical plating copper layer, electroplating nickel layer and resin protective layer are provided from inside to outside in series. The invention can be used in producing electromagnetic shielding material in housing, industrial and military device and instruments.
Description
Technical field
The present invention relates to a kind of surface metalation and handle the high polymer and the production method of sponge kind material, especially a kind of all-directional conductive foam and production method thereof with high conduction performance and shield effectiveness.Be applicable to and make family expenses, industrial and military project electromagnetic shielding material with equipment and instrument.
Background technology
High-tech electric equipment products, when offering convenience to people and enjoying, the problem that electromagnetic radiation produces is also serious day by day as mobile phone, computer and television set.Electromagnetic radiation pollution has been acknowledged as the fourth-largest public hazards after air pollution, water pollution, noise pollution.Prove that through medical research electromagnetic radiation can produce three kinds of effects to biology: thermal effect, non-thermal effect and cumulative effect, these effects all can produce in various degree harm to each organ of human body, tissue, system.Be the injury that reduces and avoid electromagnetic radiation that human body is caused, the demand of Electromagnetically shielding fabrics is with increasing.Now developed Electromagnetically shielding fabrics both at home and abroad with coating, galvanoplastic and composite spinning manufactured.
Conducting foam is to adopt to have excellent flexible foam sponge as raw material, and outsourcing material is the ventilative grid cloth structure of big grid, product tool better elastic that finally obtains and splendid shielding properties.Its compressibility is good, and flexibility is good, makes it can guarantee good conducting contact area, and has high performance price ratio.Being at present up-to-date, also is most widely used shielding material.
The foam raw material carries out suitable processing, fits with screen cloth on foam then, with the protection foam.The foam material makes it have good electrical conductivity after handling through a series of sensitization, activation, plating etc., obtains having the buffer pad (between the thickness specification 1mm-10mm) of high conduction performance and shield effectiveness.Can be applied to equipment and instrument such as electronic products such as PDP TV, LCD display, LCD TV, mobile phone, notebook, MP3, communication cabinet, Medical Instruments and military project, space industry.
But also exist some defectives at the conducting foam that is commercially available at present, relatively poor as elasticity, be difficult to after the compression restore to the original state.
Summary of the invention
The technical problem to be solved in the present invention is: provide one for all-directional conductive foam and production method thereof, be intended to that its compressibility of conducting foam of producing with the present invention is good, flexibility good, can guarantee good conducting contact area, and have good capability of electromagnetic shielding and high conduction performance.
The technical solution adopted in the present invention is: all-directional conductive foam; the base material that it is characterized in that this conducting foam be sheet elastomeric be the foaming sponge of main component with polyester, polyethers or PET; the outsourcing grid cloth of breathing freely; the foam thickness that posts is between 1-10mm, and the surface of conducting foam has chemical plating copper layer, electroless nickel layer and resin protective layer from inside to outside successively.
The production method of all-directional conductive foam of the present invention may further comprise the steps:
1) raw material is prepared, and will be that the foaming sponge of main component is cut into sheet with polyester, polyethers or PET, fits with ventilative grid cloth in the outside of every foam, and the foam thickness that posts is between 1-10mm;
2) cleaning is removed dust and foreign material;
3) sensitization and activation, palladium bichloride or palladium and aqueous polyurethane or acroleic acid resin matching surface activating agent are mixed with the catalysis slurries, with step 2) foam be placed in the described catalysis slurries and pad, under temperature 100-200 ℃, baked 10-20 minute, and made foam surface formation metal catalytic layer as thin as a wafer;
4) strengthen, it is that the formalin of 35-45% is soaked that the foam of step 3) is put into concentration, strengthens the foam surface layer structure;
5) electroless copper, first preparation chemical bronze plating liquid, with following raw material:
Copper sulphate 5~100g/L
Sodium tartrate 10~50g/L
Ethylenediamine tetra-acetic acid 10~50g/L
Alkaline agent 2~20g/L
Concentration is 37~40% formaldehyde, 10~30g/L
Nickel chloride 0~10g/L
Copper stabilizer 2~100mg/L
Potassium cyanide 1~15mg/L
Bleeding agent 0~10g/L
The raw material of above-mentioned prescription is mixed stirring down at 40-70 ℃, adjusts the pH value, obtain chemical bronze plating liquid to 10-13,
The foam of step 4) is put into chemical bronze plating liquid soaked 10-20 minute, obtain the conducting foam of copper metallization;
6) electronickelling is adopted sulfur-bearing nickel anode or carbon containing nickel anode or is contained the oxygen nickel anode, then with following raw material preparation electronickelling solution:
Nickel salt solution, ammonium nickel sulfate or nickel sulfamic acid 100~500g/L
Anode activator 7~20g/L
Buffer 25~40g/L
Magnesium sulfate 30~50g/L
Anti-pinhole agent 0.01~2g/L
With above-mentioned raw materials at 10~66 ℃ of temperature, cathode current 0.5~5A/dm
2Under the environment, regulate pH value and reach 3~6, adding entry, to be made into total concentration be 5~40% electronickelling solution, the conducting foam that plating is obtained by step 5) in 10~50 ℃ of scopes;
7) armor coated, with the conducting foam that step 6) obtains, dip-coating PU or PE coating adhesive, roll dried, the oven dry after obtain the all-directional conductive foam finished product.
Described alkaline agent is NaOH or sodium carbonate.
Described copper stabilizer is α, α '-2 bipyridine or 2-sulfurio benzo thiazole.
Described nickel salt solution is nickelous sulfate or nickel chloride.
Described anode activator is sodium chloride or nickel chloride.
Described buffer is boric acid or ammonium chloride.
Described anti-pinhole agent is hydrogen peroxide or dodecyl sodium sulfate.
The invention has the beneficial effects as follows: this conducting foam since the foaming sponge etc. that adopts the elasticity excellence as raw material, therefore the and ventilative grid cloth of outsourcing has excellent elasticity and flexibility, can guarantee good conducting contact area; After the foam material is handled through a series of sensitization, activation, plating etc., characteristic with metal, possesses simultaneously the unexistent character of common metal again, be a kind of resilient " metal ", so have good electrical conductivity and shield effectiveness, the Z of conducting foam of the present invention is very low to resistance, below 0.1 Ω, reaches as high as the shield effectiveness of 100dB below the frequency of 2G; In addition, this conducting foam also has high performance price ratio, does not add environmentally harmful material in metallized production process, and the very big electro-coppering of environmental pollution has been avoided in its technological process, meets the fundamental state policy of protecting environment.
Embodiment
Embodiment 1,
The base material of this routine conducting foam is the elastomeric foaming sponge based on PU of sheet, the outsourcing grid cloth of breathing freely, and the foam thickness that posts is 5mm, the surface of conducting foam has chemical plating copper layer, electroless nickel layer and resin protective layer from inside to outside successively.
The production method of this routine all-directional conductive foam may further comprise the steps:
1) raw material is prepared, and is that main foaming sponge is cut into sheet with PU, fits with ventilative grid cloth in the outside of every foam, and the foam thickness that posts is 5mm;
2) cleaning is removed dust and foreign material;
3) sensitization and activation are mixed with the catalysis slurries with palladium bichloride and aqueous polyurethane matching surface activating agent JFC, with step 2) foam be placed in the described catalysis slurries and pad, under 150 ℃ of temperature, baked 15 minutes, make the foam surface form as thin as a wafer metal catalytic layer;
4) strengthen, it is that 40% formalin is soaked that the foam of step 3) is put into concentration, strengthens the foam surface layer structure;
5) electroless copper, first preparation chemical bronze plating liquid, with following raw material:
Copper sulphate 50g/L
Sodium tartrate 30g/L
Ethylenediamine tetra-acetic acid 30g/L
NaOH 10g/L
Concentration is 38% formaldehyde 20g/L
Nickel chloride 5g/L
α, α '-2 bipyridine 50mg/L
Potassium cyanide 8mg/L
JFC 5g/L
The raw material of above-mentioned prescription is mixed stirring down at 55 ℃, adjusts pH value to 12, obtain chemical bronze plating liquid,
The foam of step 4) is put into chemical bronze plating liquid soaked 15 minutes, obtain the conducting foam of copper metallization;
6) electronickelling is adopted sulfur-bearing nickel anode or carbon containing nickel anode or is contained the oxygen nickel anode, then with following raw material preparation electronickelling solution:
Nickelous sulfate 300g/L
Sodium chloride 13g/L
Boric acid 32g/L
Magnesium sulfate 40g/L
Hydrogen peroxide 1g/L
With above-mentioned raw materials at 38 ℃ of temperature, cathode current 3A/dm
2Under the environment, regulate pH value and reach 4, adding entry, to be made into total concentration be 22% electronickelling solution, the conducting foam that plating is obtained by step 5) in 30 ℃ of scopes;
7) armor coated, with the conducting foam that step 6) obtains, dip-coating PU coating adhesive, roll dried, the oven dry after obtain the all-directional conductive foam finished product.
Embodiment 2,
The base material of this routine conducting foam is selected elastomeric sponge based on polyethers, and its production method may further comprise the steps:
1) raw material is prepared, and the base material sponge is cut into sheet, fits with ventilative grid cloth in the outside of every foam, and the foam thickness that posts is 1mm;
2) cleaning is removed dust and foreign material;
3) sensitization and activation are mixed with the catalysis slurries with palladium and acroleic acid resin matching surface activating agent JFC, with step 2) foam be placed in the described catalysis slurries and pad, under 100 ℃ of temperature, baked 10 minutes, make the foam surface form as thin as a wafer metal catalytic layer;
4) strengthen, it is that 35% formalin is soaked that the foam of step 3) is put into concentration, strengthens the foam surface layer structure;
5) electroless copper, first preparation chemical bronze plating liquid, with following raw material:
Copper sulphate 5g/L
Sodium tartrate 10g/L
Ethylenediamine tetra-acetic acid 10g/L
Sodium carbonate 2g/L
Concentration is 37% formaldehyde 10g/L
Nickel chloride 1g/L
2-sulfurio benzo thiazole 2mg/L
Potassium cyanide 1mg/L
JFC 1g/L
The raw material of above-mentioned prescription is mixed stirring down at 40 ℃, adjusts pH value to 10, obtain chemical bronze plating liquid,
The foam of step 4) is put into chemical bronze plating liquid soaked 10 minutes, obtain the conducting foam of copper metallization;
6) electronickelling is adopted sulfur-bearing nickel anode or carbon containing nickel anode or is contained the oxygen nickel anode, then with following raw material preparation electronickelling solution:
Ammonium nickel sulfate 100g/L
Nickel chloride 7g/L
Ammonium chloride 25g/L
Magnesium sulfate 30g/L
Dodecyl sodium sulfate 0.01g/L
With above-mentioned raw materials at 10 ℃ of temperature, cathode current 0.5A/dm
2Under the environment, regulate pH value and reach 3, adding entry, to be made into total concentration be 5% electronickelling solution, the conducting foam that plating is obtained by step 5) in 10 ℃ of scopes;
7) armor coated, with the conducting foam that step 6) obtains, dip-coating PE coating adhesive, roll dried, the oven dry after obtain the all-directional conductive foam finished product.
Embodiment 3,
The base material of this routine conducting foam is selected the foaming sponge based on PPG and polyurethane, and its production method may further comprise the steps:
1) raw material is prepared, and base material is cut into sheet based on the foaming sponge of PPG and polyurethane, and the outside of every foam is with ventilative grid cloth applying, and the foam thickness that posts is 10mm;
2) cleaning is removed dust and foreign material;
3) sensitization and activation are mixed with the catalysis slurries with palladium bichloride and aqueous polyurethane matching surface activating agent JFC, with step 2) foam be placed in the described catalysis slurries and pad, under 200 ℃ of temperature, baked 20 minutes, make the foam surface form as thin as a wafer metal catalytic layer;
4) strengthen, it is that 45% formalin is soaked that the foam of step 3) is put into concentration, strengthens the foam surface layer structure;
5) electroless copper, first preparation chemical bronze plating liquid, with following raw material:
Copper sulphate 100g/L
Sodium tartrate 50g/L
Ethylenediamine tetra-acetic acid 50g/L
NaOH 20g/L
Concentration is 40% formaldehyde 30g/L
Nickel chloride 10g/L
α, α '-2 bipyridine 100mg/L
Potassium cyanide 15mg/L
JFC 10g/L
The raw material of above-mentioned prescription is mixed stirring down at 70 ℃, adjusts pH value to 13, obtain chemical bronze plating liquid,
The foam of step 4) is put into chemical bronze plating liquid soaked 20 minutes, obtain the conducting foam of copper metallization;
6) electronickelling is adopted sulfur-bearing nickel anode or carbon containing nickel anode or is contained the oxygen nickel anode, then with following raw material preparation electronickelling solution:
Nickel sulfamic acid 500g/L
Sodium chloride 20g/L
Boric acid 40g/L
Magnesium sulfate 50g/L
Hydrogen peroxide 2g/L
With above-mentioned raw materials at 66 ℃ of temperature, cathode current 5A/dm
2Under the environment, regulate pH value and reach 6, adding entry, to be made into total concentration be 40% electronickelling solution, the conducting foam that plating is obtained by step 5) in 50 ℃ of scopes;
7) armor coated, with the conducting foam that step 6) obtains, dip-coating PU coating adhesive, roll dried, the oven dry after obtain the all-directional conductive foam finished product.
What use in the foregoing description all is outsourcing from the market with polyester, polyethers or PET as the foaming sponge of main component, except being the main component with polyester, polyethers or PET, also be added with in the prescription: one or more in toluene di-isocyanate(TDI), PPG, dicyanomethane, inferior tin octoate, triethylene diamine, the silicone oil etc., concrete prescription is grasped by manufacturer, and the present invention only need choose and get final product.
Claims (7)
1. the production method of an all-directional conductive foam may further comprise the steps:
1) raw material is prepared, and will be the foaming sponge of main component with polyester or polyethers, fits with ventilative grid cloth in the outside of every foam, and the foam thickness that posts is between 1-10mm;
2) cleaning is removed dust and foreign material;
3) sensitization and activation, palladium bichloride or palladium and aqueous polyurethane or acroleic acid resin matching surface activating agent are mixed with the catalysis slurries, with step 2) foam be placed in the described catalysis slurries and pad, under temperature 100-200 ℃, baked 10-20 minute, and made foam surface formation metal catalytic layer as thin as a wafer;
4) strengthen, it is that the formalin of 35-45% is soaked that the foam of step 3) is put into concentration, strengthens the foam surface layer structure;
5) electroless copper, first preparation chemical bronze plating liquid, with following raw material:
Copper sulphate 5~100g/L
Sodium tartrate 10~50g/L
Ethylenediamine tetra-acetic acid 10~50g/L
Alkaline agent 2~20g/L
Concentration is 37~40% formaldehyde, 10~30g/L
Nickel chloride 0~10g/L
Copper stabilizer 2~100mg/L
Potassium cyanide 1~15mg/L
Bleeding agent 0~10g/L
The raw material of above-mentioned prescription is mixed stirring down at 40-70 ℃, adjusts the pH value, obtain chemical bronze plating liquid to 10-13,
The foam of step 4) is put into chemical bronze plating liquid soaked 10-20 minute, obtain the conducting foam of copper metallization;
6) electronickelling is adopted sulfur-bearing nickel anode or carbon containing nickel anode or is contained the oxygen nickel anode, then with following raw material preparation electronickelling solution:
Nickel salt solution, ammonium nickel sulfate or nickel sulfamic acid 100~500g/L
Anode activator 7~20g/L
Buffer 25~40g/L
Magnesium sulfate 30~50g/L
Anti-pinhole agent 0.01~2g/L
With above-mentioned raw materials at 10~66 ℃ of temperature, cathode current 0.5~5A/d m
2Under the environment, regulate pH value and reach 3~6, adding entry, to be made into total concentration be 5~40% electronickelling solution, the conducting foam that plating is obtained by step 5) in 10~50 ℃ of scopes;
7) armor coated, with the conducting foam that step 6) obtains, dip-coating PU or PE coating adhesive, roll dried, the oven dry after obtain the all-directional conductive foam finished product.
2. the production method of all-directional conductive foam according to claim 1, it is characterized in that: described alkaline agent is NaOH or sodium carbonate.
3. the production method of all-directional conductive foam according to claim 1, it is characterized in that: described copper stabilizer is α, α '-2 bipyridine or 2-sulfurio benzo thiazole.
4. the production method of all-directional conductive foam according to claim 1, it is characterized in that: described nickel salt solution is nickelous sulfate or nickel chloride.
5. the production method of all-directional conductive foam according to claim 1, it is characterized in that: described anode activator is sodium chloride or nickel chloride.
6. the production method of all-directional conductive foam according to claim 1, it is characterized in that: described buffer is boric acid or ammonium chloride.
7. the production method of all-directional conductive foam according to claim 1, it is characterized in that: described anti-pinhole agent is hydrogen peroxide or dodecyl sodium sulfate.
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Families Citing this family (9)
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CN103215590A (en) * | 2013-04-11 | 2013-07-24 | 梧州三和新材料科技有限公司 | Preparation method of conductive sponges |
CN104608437A (en) * | 2015-02-05 | 2015-05-13 | 吴江市金桥纺织品有限公司 | Soft nano-shielding film and production method thereof |
CN107452433B (en) * | 2016-06-01 | 2023-06-02 | 益阳市菲美特新材料有限公司 | Omnibearing conductive sponge and preparation method thereof |
CN106009578A (en) * | 2016-07-02 | 2016-10-12 | 郭迎庆 | Preparation method for acetylated lignin-modified unsaturated polyester conductive foam |
CN106965509A (en) * | 2017-05-02 | 2017-07-21 | 益阳市菲美特新材料有限公司 | A kind of composite conducting sponge and preparation method thereof |
CN107723756A (en) * | 2017-08-29 | 2018-02-23 | 无锡鼎亚电子材料有限公司 | Sulfamic acid type impacts the preparation method of nickel |
CN108315762B (en) * | 2018-02-08 | 2020-06-09 | 华南师范大学 | Synthesis method of Ni-Mo-Co hydrogen evolution catalyst with high activity in acidic environment |
CN108998778A (en) * | 2018-06-05 | 2018-12-14 | 胡海 | A kind of preparation method and conductive sponge of conductive sponge |
CN108716010B (en) * | 2018-06-06 | 2020-11-03 | 华南师范大学 | Preparation method of multistage nano nickel-based microcolumn |
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CN2640204Y (en) * | 2003-09-08 | 2004-09-08 | 孙爱祥 | Omnibearing conductive foamed cotton |
CN2673052Y (en) * | 2003-12-30 | 2005-01-19 | 孙爱祥 | Conductive foamed cotton |
CN1706991A (en) * | 2004-06-07 | 2005-12-14 | 比亚迪股份有限公司 | Foam nickel preparing process |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN2640204Y (en) * | 2003-09-08 | 2004-09-08 | 孙爱祥 | Omnibearing conductive foamed cotton |
CN2673052Y (en) * | 2003-12-30 | 2005-01-19 | 孙爱祥 | Conductive foamed cotton |
CN1706991A (en) * | 2004-06-07 | 2005-12-14 | 比亚迪股份有限公司 | Foam nickel preparing process |
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