CN105153447B - A kind of preparation method of sandwich structure flexible copper clad functional particles conducting film - Google Patents
A kind of preparation method of sandwich structure flexible copper clad functional particles conducting film Download PDFInfo
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- CN105153447B CN105153447B CN201510655697.0A CN201510655697A CN105153447B CN 105153447 B CN105153447 B CN 105153447B CN 201510655697 A CN201510655697 A CN 201510655697A CN 105153447 B CN105153447 B CN 105153447B
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Abstract
The present invention relates to flexible conducting material field, specifically a kind of preparation method of sandwich structure flexible copper clad functional particles conducting film, its step is：（1）The preparation of bottom pure silicon glued membrane,（2）The preparation of flexible copper conducting film.The present invention plates layer of metal copper respectively using chemical plating method on the surface of glass microballoon and glass fibre, the performances such as the high conductivity of copper and low-density, the corrosion-resistant and high mechanical properties of glass microballoon or glass fibre are combined, the features such as preparing with low-density, low cost and good dispersion and the excellent functional particles of electric conductivity, then it is filled into as conductive filler and the thick sandwich structure flexible copper clad functional particles conducting films of 0.4~1 mm is prepared in liquid silastic, its specific insulation is up to 10‑2Ω cm, and with preferable weatherability and inoxidizability, in stretching（Maximum tension strain is 100%）The change of its electric conductivity is little after up to a hundred times.
Description
Technical field
The present invention relates to flexible conducting material field, specifically a kind of sandwich structure flexible copper clad functional particles conducting film
Preparation method.
Background technology
In recent years, with the development of compliant conductive functional material, conventional metals powder is due to the shortcomings of density is big, cost is high
The demand of contemporary scientific technology development can not be met, and the material preparation process such as new CNT, graphene is complicated, cost
It is expensive and do not highlight its excellent high conduction performance in industrialized development, therefore, research and development lightweight, it is highly conductive, low into
This and be adapted to produce in enormous quantities conductive filler be industrial development active demand.The main component of glass microballoon and glass fibre
It is silica, aluminum oxide, calcium oxide, boron oxide, magnesia and sodium oxide molybdena etc., is the inorganic non-metallic material of excellent performance,
There is excellent small density, good insulating, heat resistance, good corrosion resistance, high mechanical strength, be typically used as in composite
Reinforcing material, electrically insulating material and heat-insulating material, circuit substrate etc..
Chemical plating is a kind of wider method of simple and easy to apply, with low cost, practicality.In recent years, using chemical plating method
The research that metal is plated on the matrixes such as metal, polymer and inorganic powder is more, either sheet material, bar, complex-shaped different
Section bar or dusty material, can obtain the smooth and fine and close composite of coating.M.Jagannatham etc.
[M.Jagannatham,et al.,Mat.Sci.Eng.A,2015,638:197-207.] method of electroless copper is used to carbon
Nanotube surface is metallized, and successfully prepares a kind of shell-core structure composite, discharge plasma sintering is passed through with aluminium powder
The aluminum matrix composite with higher compression intensity is obtained.H.Zhao etc. [H.Zhao, et al., Fiber.Polym.,
2015,16:593-598.] by reducing agent of sodium borohydride surface of cotton fabric success copper facing, test result show the material have
There is good electromagnet shield effect.
The content of the invention
The present invention is intended to provide a kind of stretchable, flexible and wearable sandwich structure flexible copper clad functional particles are led
The preparation method of electrolemma.
The present invention is achieved by the following technical solutions：A kind of sandwich structure flexible copper clad functional particles conducting film
Preparation method, its step is：
(1) preparation of bottom pure silicon glued membrane：
Solvent is added dropwise in liquid silastic fully to dissolve to it, curing agent is then added dropwise, by liquid silicon rubber after stirring
Sol solution flow casting molding in a mold, solidifies 20~40min, obtains the bottom pure silicon glued membrane of the micro- solidification in surface at room temperature；
(2) preparation of flexible copper clad functional particles conducting film：
Solvent is added dropwise in liquid silastic fully to dissolve to it, curing agent is then added dropwise, copper facing glass is stirring evenly and then adding into
Glass microballon or copper facing glass fibre functional particles are simultaneously mixed, and the flow casting molding on bottom pure silicon glued membrane solidifies 24h at room temperature；Gu
During change, copper facing glass microballoon or copper facing glass fibre functional particles are gradually deposited down, be held on above and below two layers of pellosil
Between, form the thick sandwich structure flexible copper clad functional particles conducting films of 0.4~1mm；
The mass ratio of the bottom pure silicon glued membrane and liquid silastic in the pellosil of upper strata is 3~5:6, in the pellosil of upper strata
The mass ratio of liquid silastic and copper facing glass microballoon or copper facing glass fibre functional particles is 3:1~3, the base of liquid silastic
Expect for dimethyl siloxane.
Especially, it should be noted that, if the thickness of flexible copper clad functional particles conducting film is less than 0.4mm, the liquid silicon of use
Rubber consumption is very few, and two layers of pellosil cladding is imperfect up and down；If the thickness of flexible copper clad functional particles conducting film is higher than 1mm,
Then influence the electric conductivity and tensile property of conducting film.
In addition, the use tetraethyl orthosilicate of curing agent preferably；It is preferred that, the mass ratio of liquid silastic and curing agent is
100:2~7；It is preferred that, solvent is dimethylbenzene, hexamethylene, ethyl acetate or acetone.
For the above-mentioned preparation method of further description, the invention provides the copper facing glass microballoon or copper facing glass
The preparation method of fiber functional particles：Metal salt copper sulphate and complexing agent are weighed, is added sequentially in distilled water, is stirred
After add ammoniacal liquor, then use distilled water constant volume to cause pH for 9~13, afterwards will with metal salt copper sulphate mass ratio be 3:1.5
~9 glass microballoon or glass fibre is added in the solution of above-mentioned preparation, is heated to 60~90 DEG C, is slowly dripped after stirring
Plus reducing agent hydrazine hydrate solution, persistently stir after 20~100min, washing, suction filtration, drying, obtain copper facing glass microballoon or copper facing
Glass fibre functional particles.
The copper facing glass microballoon or copper facing glass fibre functional particles obtained by above-mentioned preparation method is relative to existing skill
The functional particles that art is prepared, its specific insulation is up to 10-4Ω·cm.The complexing agent of optimization uses sodium citrate, second two
Amine tetraacethyl disodium or sodium potassium tartrate tetrahydrate.
Further, the invention provides the process for surface preparation of glass microballoon or glass fibre, (a) roughening：Glass is micro-
Pearl or glass fibre are added in coarsening solution, and 30 DEG C of constant temperature are at the uniform velocity stirred after 15min, distill water washing, standby；(b) it is sensitized：Through
Glass microballoon or glass fibre after roughening treatment are added in sensitizing solution, and 30 DEG C of constant temperature are at the uniform velocity stirred after 15min, distillation washing
Wash, it is standby；(c) activate：Glass microballoon or glass fibre after sensitized treatment is added in activating solution, 30 DEG C of constant temperature are at the uniform velocity stirred
Mix after 15min, distill water washing, obtain glass microballoon or glass fibre after surface preparation.After surface preparation
Glass microballoon or glass fibre, can assign its surface certain catalytic activity, enable to more elemental copper depositions after activation
Glass microballoon or fiberglass surfacing, reduce functional particles resistivity.
And there is provided the reagent used in above-mentioned process for surface preparation：The coarsening solution is the weight by 20~50g/L
What potassium chromate, the 50~100mL/L 98wt% concentrated sulfuric acid and distilled water were constituted；The sensitizing solution is by 10~60g/L
What stannous chloride, 10~90mL/L 37wt% hydrochloric acid and distilled water were constituted；The activating solution is the chlorine by 0.1~0.5g/L
Change what palladium, 1~5mL/L 37wt% hydrochloric acid and distilled water were constituted.
In addition, glass fibre has carried out ungrease treatment in advance before roughening treatment is carried out, it is the step of the ungrease treatment：
Glass fibre is added in NaOH solution, and 70 DEG C of constant temperature are at the uniform velocity stirred after 2h, distills water washing, is placed in constant temperature in 80 DEG C of baking ovens and is dried
Dry 4h, it is standby.
The present invention plates layer of metal copper respectively using chemical plating method on the surface of glass microballoon and glass fibre, by copper
The performance such as high conductivity and low-density, the corrosion-resistant and high mechanical properties of glass microballoon or glass fibre combine,
The features such as preparing with low-density, low cost and good dispersion and the excellent functional particles of electric conductivity, are then made
It is filled into for conductive filler and the thick sandwich structure flexible copper clad functional particles conductions of 0.4~1mm is prepared in liquid silastic
Film, its specific insulation is up to 10-2Ω cm, and with preferable weatherability and inoxidizability, in stretching, (maximum tension is strained
It is little for its electric conductivity change after 100%) up to a hundred times.The flexible copper conducting film be expected to electromagnetic shielding, flexible electronic device,
The field such as flexible sensor and health monitoring equipment is applied, and is meeting contemporary lightweight, efficient, low cost and high-volume
It is also a kind of stretchable, flexible and wearable fexible conductor while the technical requirements such as production.
Brief description of the drawings
Fig. 1 is the SEM photograph of the copper facing glass microballoon functional particles prepared by embodiment 1.
Fig. 2 is Fig. 1 partial enlarged drawing.
Fig. 3 is the SEM photograph of the copper facing glass microballoon functional particles prepared by embodiment 2.
Fig. 4 is Fig. 3 partial enlarged drawing.
Fig. 5 is the XRD spectrum of the copper facing glass microballoon functional particles prepared by embodiment 2.
Fig. 6 is the SEM photograph of the copper facing glass microballoon functional particles prepared by embodiment 3.
Fig. 7 is Fig. 6 partial enlarged drawing.
Fig. 8 is the SEM photograph of the copper facing glass fibre functional particles prepared by embodiment 4.
Fig. 9 is Fig. 8 partial enlarged drawing.
Figure 10 is the SEM photograph of the copper facing glass fibre functional particles prepared by embodiment 5.
Figure 11 is Figure 10 partial enlarged drawing.
Figure 12 is the SEM photograph of the copper facing glass fibre functional particles prepared by embodiment 6.
Figure 13 is Figure 12 partial enlarged drawing.
Figure 14 is the SEM photograph of the sandwich structure flexible copper clad functional particles conducting film prepared by embodiment 2.
Figure 15 is the SEM photograph of the sandwich structure flexible copper clad functional particles conducting film prepared by embodiment 5.
Embodiment
Embodiment 1
(1) glass microballoon surface preparation
Weigh 6g glass microballoons and be added to 30 DEG C of constant temperature in 100mL coarsening solutions, at the uniform velocity stir 15min, suction filtration uses distilled water
30 DEG C of constant temperature in 100mL sensitizing solutions are added to after washing 2 times, 15min is at the uniform velocity stirred, suction filtration, with being added after distillation water washing 2 times
30 DEG C of constant temperature into 100mL activating solutions, are at the uniform velocity stirred after 15min, suction filtration, standby with distillation water washing.Wherein, coarsening solution, quick
The composition and process for preparation for changing liquid and activating solution are as follows：
Coarsening solution：Weigh 30g potassium bichromates to be added in the large beaker equipped with 1000mL distilled water, then measure
The 60mL98wt% concentrated sulfuric acid is slowly added thereto while stirring, and coarsening solution is produced after graininess potassium bichromate is completely dissolved.
Sensitizing solution：Weigh 2gSnCl2Put into the beaker equipped with 100mL distilled water, be added dropwise 1mL37wt%'s thereto
Dense HCl, stirring are until solution clarification, as sensitizing solution.
Activating solution：Weigh 0.1gPdCl2, it is dissolved in 1mL37wt% dense HCl, is instilled after being stirred with glass bar
In the large beaker for filling 1000mL distilled water, 2h is stored at room temperature after stirring.
(2) preparation of copper facing glass microballoon functional particles
3g copper sulphate and 20g sodium citrates are weighed, in the beaker for being added sequentially to fill a small amount of distilled water, stirring and dissolving
Afterwards, 25wt% ammoniacal liquor 24mL is added, 192mL (pH is 11) is then settled to distilled water, afterwards will be above-mentioned pre- by surface
The glass microballoon of processing is added in the solution of preparation and heated in water-bath, and mixing speed is 300r/min, when in beaker
When temperature rises to 80 DEG C, 8mL30wt% hydrazine hydrate is slowly dropped into above-mentioned solution, terminating reaction after 50min is persistently stirred,
Vacuum filtration, is successively washed 3 times, 5h is dried at room temperature, copper facing glass microballoon function is obtained respectively with distilled water and absolute ethyl alcohol
Particle.
(3) preparation of sandwich structure flexible copper clad functional particles conducting film
Mould wiped clean is dried in ventilating kitchen with distilled water, absolute ethyl alcohol in advance.Toward 3g liquid silastic (bases
Expect for dimethyl siloxane) middle dropwise addition xylene solvent 7.5g, after stirring is fully dissolved to liquid silastic, positive silicic acid second is added dropwise
Ester 0.06g, after stirring by the liquid silastic solution of above-mentioned dilution in above-mentioned mould flow casting molding, solidify at room temperature
25min, obtains the bottom pure silicon glued membrane of the micro- solidification in surface；Then on the bottom pure silicon film surface flow casting molding upper strata being molded
Hybrid films, be specially：10g xylene solvents are added dropwise into 5g liquid silastics, stirring is fully dissolved to liquid silastic, then
0.1g tetraethyl orthosilicates are added dropwise, is stirring evenly and then adding into 1.67g copper facing glass microballoon functional particles and mixes；This is well mixed
Solution directly in above-mentioned mould flow casting molding on the surface of the bottom pure silicon glued membrane of micro- solidification, solidify 24h at room temperature, produce
To sandwich structure flexible copper clad functional particles conducting film.
Embodiment 2
(1) glass microballoon surface preparation
Weigh 6g glass microballoons and be added to 30 DEG C of constant temperature in 100mL coarsening solutions, at the uniform velocity stir 15min, suction filtration uses distilled water
30 DEG C of constant temperature in 100mL sensitizing solutions are added to after washing 2 times, 15min is at the uniform velocity stirred, suction filtration, with being added after distillation water washing 2 times
30 DEG C of constant temperature into 100mL activating solutions, are at the uniform velocity stirred after 15min, suction filtration, standby with distillation water washing.Wherein, coarsening solution, quick
The composition and process for preparation for changing liquid and activating solution are as follows：
Coarsening solution：Weigh 20g potassium bichromates to be added in the large beaker equipped with 1000mL distilled water, then measure
The 100mL98wt% concentrated sulfuric acid is slowly added thereto while stirring, and coarsening solution is produced after graininess potassium bichromate is completely dissolved.
Sensitizing solution：Weigh 1gSnCl2Put into the beaker equipped with 100mL distilled water, be added dropwise 9mL37wt%'s thereto
Dense HCl, stirring are until solution clarification, as sensitizing solution.
Activating solution：Weigh 0.3gPdCl2, it is dissolved in 5mL37wt% dense HCl, is instilled after being stirred with glass bar
In the large beaker for filling 1000mL distilled water, 2h is stored at room temperature after stirring.
(2) preparation of copper facing glass microballoon functional particles
5g copper sulphate and 10g disodium ethylene diamine tetraacetates are weighed, in the beaker for being added sequentially to fill a small amount of distilled water, is stirred
Mix after dissolving, add 25wt% ammoniacal liquor 20mL, 192mL (pH is 10) is then settled to distilled water, afterwards by above-mentioned processing
The glass microballoon crossed is added in the solution of preparation and heated in water-bath, and mixing speed is 300r/min, when warm in beaker
When degree rises to 70 DEG C, 8mL30wt% hydrazine hydrate is slowly dropped into above-mentioned solution, terminating reaction after 60min is persistently stirred, very
Empty suction filtration, is successively washed 3 times, 5h is dried at room temperature respectively with distilled water and absolute ethyl alcohol, obtains copper facing glass microballoon function grain
Son.
(3) preparation of sandwich structure flexible copper clad functional particles conducting film
Mould wiped clean is dried in ventilating kitchen with distilled water, absolute ethyl alcohol in advance.Dripped into 3g liquid silastics
Plus cyclohexane solvent 5g, after stirring is fully dissolved to liquid silastic, tetraethyl orthosilicate 0.09g is added dropwise, will be upper after stirring
The liquid silastic solution of the dilution flow casting molding in above-mentioned mould is stated, solidifies 20min at room temperature, obtains the bottom of the micro- solidification in surface
Layer pure silicon glued membrane；Then in the bottom pure silicon film surface flow casting molding upper strata hybrid films being molded, it is specially：Toward 5.5g liquid
7.5g cyclohexane solvents are added dropwise in silicon rubber, stirring is fully dissolved to liquid silastic, and 0.165g tetraethyl orthosilicates are then added dropwise,
It is stirring evenly and then adding into 3.67g copper facing glass microballoon functional particles and mixes；By the well mixed solution directly in above-mentioned mould
Flow casting molding solidifies 24h at room temperature on the surface of the bottom pure silicon glued membrane of micro- solidification in tool, that is, obtains sandwich structure flexibility plating
Copper functional particles conducting film.
Embodiment 3
(1) glass microballoon surface preparation
Weigh 6g glass microballoons and be added to 30 DEG C of constant temperature in 100mL coarsening solutions, at the uniform velocity stir 15min, suction filtration uses distilled water
30 DEG C of constant temperature in 100mL sensitizing solutions are added to after washing 2 times, 15min is at the uniform velocity stirred, suction filtration, with being added after distillation water washing 2 times
30 DEG C of constant temperature into 100mL activating solutions, are at the uniform velocity stirred after 15min, suction filtration, standby with distillation water washing.Wherein, coarsening solution, quick
The composition and process for preparation for changing liquid and activating solution are as follows：
Coarsening solution：Weigh 50g potassium bichromates to be added in the large beaker equipped with 1000mL distilled water, then measure
The 50mL98wt% concentrated sulfuric acid is slowly added thereto while stirring, and coarsening solution is produced after graininess potassium bichromate is completely dissolved.
Sensitizing solution：Weigh 6gSnCl2Put into the beaker equipped with 100mL distilled water, be added dropwise 5mL37wt%'s thereto
Dense HCl, stirring are until solution clarification, as sensitizing solution.
Activating solution：Weigh 0.5gPdCl2, it is dissolved in 3mL37wt% dense HCl, is instilled after being stirred with glass bar
In the large beaker for filling 1000mL distilled water, 2h is stored at room temperature after stirring.
(2) preparation of copper facing glass microballoon functional particles
14g copper sulphate and 40g sodium potassium tartrate tetrahydrates are weighed, in the beaker for being added sequentially to fill a small amount of distilled water, is stirred molten
Xie Hou, adds 25wt% ammoniacal liquor 40mL, 192mL (pH is 13) is then settled to distilled water, afterwards will be above-mentioned treated
Glass microballoon is added in the solution of preparation and heated in water-bath, and mixing speed is 300r/min, when burning cup temperature liter
During to 60 DEG C, 8mL30wt% hydrazine hydrate is slowly dropped into above-mentioned solution, terminating reaction, vacuum after 100min is persistently stirred
Suction filtration, is successively washed 3 times, 5h is dried at room temperature, copper facing glass microballoon functional particles are obtained respectively with distilled water and absolute ethyl alcohol.
(3) preparation of sandwich structure flexible copper clad functional particles conducting film
Mould wiped clean is dried in ventilating kitchen with distilled water, absolute ethyl alcohol in advance.Dripped into 3g liquid silastics
Plus ethyl acetate solvent 7.5g, after stirring is fully dissolved to liquid silastic, tetraethyl orthosilicate 0.12g is added dropwise, after stirring
By the liquid silastic solution of above-mentioned dilution in above-mentioned mould flow casting molding, solidify 40min at room temperature, obtain the micro- solidification in surface
Bottom pure silicon glued membrane；Then in the bottom pure silicon film surface flow casting molding upper strata hybrid films being molded, it is specially：Toward 6g liquid
10g ethyl acetate solvents are added dropwise in body silicon rubber, stirring is fully dissolved to liquid silastic, and the positive silicic acid second of 0.24g is then added dropwise
Ester, is stirring evenly and then adding into 6g copper facing glass microballoon functional particles and mixes；By the well mixed solution directly in above-mentioned mould
Flow casting molding solidifies 24h at room temperature on the surface of the bottom pure silicon glued membrane of micro- solidification in tool, that is, obtains sandwich structure flexibility plating
Copper functional particles conducting film.
Embodiment 4
(1) fiberglass surfacing is pre-processed
Firstly the need of ungrease treatment is carried out in the preprocessing process of glass fibre, 100g glass fibres are added to 500mL
NaOH solution (30g/L NaOH) in, be heated to 70 DEG C, constant temperature is at the uniform velocity stirred after 2h, with distillation water washing, in 80 DEG C of baking
4h is dried in case, it is standby；Then 6g degreasing glass fibres are weighed and are added to 30 DEG C of constant temperature in 100mL coarsening solutions, are at the uniform velocity stirred
15min, suction filtration with 30 DEG C of constant temperature in 100mL sensitizing solutions are added to after distillation water washing 2 times, at the uniform velocity stirs 15min, suction filtration is used
30 DEG C of constant temperature in 100mL activating solutions are added to after distillation water washing 2 times, are at the uniform velocity stirred after 15min, suction filtration, with distillation water washing,
It is standby.Wherein, the composition and process for preparation of coarsening solution, sensitizing solution and activating solution be as described in example 1 above.
(2) preparation of copper facing glass fibre functional particles
6g copper sulphate and 10g sodium citrates are weighed, in the beaker for being added sequentially to fill a small amount of distilled water, stirring and dissolving
Afterwards, 25wt% ammoniacal liquor 16mL is added, 192mL (pH is 9) is then settled to distilled water, afterwards by above-mentioned treated glass
Fiber is added in the solution of preparation and heated in water-bath, and mixing speed is 300r/min, and 70 are risen to when burning cup temperature
DEG C when, 8mL30wt% hydrazine hydrate is slowly dropped into above-mentioned solution, persistently stir 20min after terminating reaction, vacuum filtration,
Successively washed respectively with distilled water and absolute ethyl alcohol 3 times, 5h is dried at room temperature, copper facing glass fibre functional particles are obtained.
(3) preparation of sandwich structure flexible copper clad functional particles conducting film
Mould wiped clean is dried in ventilating kitchen with distilled water, absolute ethyl alcohol in advance.Dripped into 3g liquid silastics
Plus acetone solvent 6.0g, after stirring is fully dissolved to liquid silastic, tetraethyl orthosilicate 0.15g is added dropwise, will be upper after stirring
The liquid silastic solution of the dilution flow casting molding in above-mentioned mould is stated, solidifies 30min at room temperature, obtains the bottom of the micro- solidification in surface
Layer pure silicon glued membrane；Then in the bottom pure silicon film surface flow casting molding upper strata hybrid films being molded, it is specially：Toward 5.3g liquid
9.0g acetone solvents are added dropwise in silicon rubber, stirring is fully dissolved to liquid silastic, and 0.264g tetraethyl orthosilicates are then added dropwise, stir
Mix uniform rear addition 1.77g copper facing glass fibre functional particles and mix；By the well mixed solution directly in above-mentioned mould
Middle flow casting molding solidifies 24h, that is, obtains sandwich structure flexible copper clad at room temperature on the surface of the bottom pure silicon glued membrane of micro- solidification
Functional particles conducting film.
Embodiment 5
(1) fiberglass surfacing is pre-processed
Weigh 6g degreasing glass fibres and be added to 30 DEG C of constant temperature in 100mL coarsening solutions, at the uniform velocity stir 15min, suction filtration, with steaming
Distilled water is added to 30 DEG C of constant temperature in 100mL sensitizing solutions after washing 2 times, at the uniform velocity stirs 15min, suction filtration, after distillation water washing 2 times
30 DEG C of constant temperature in 100mL activating solutions are added to, are at the uniform velocity stirred after 15min, suction filtration, it is standby with distillation water washing.Wherein, it is roughened
The composition and process for preparation of liquid, sensitizing solution and activating solution are as described in example 1 above.
(2) preparation of copper facing glass fibre functional particles
8g copper sulphate and 20g sodium citrates are weighed, in the beaker for being added sequentially to fill a small amount of distilled water, stirring and dissolving
Afterwards, 25wt% ammoniacal liquor 24mL is added, 192mL (pH is 11) is then settled to distilled water, afterwards by above-mentioned treated glass
Glass fiber is added in the solution of preparation and heated in water-bath, and mixing speed is 300r/min, is risen to when burning cup temperature
At 80 DEG C, 8mL30wt% hydrazine hydrate is slowly dropped into above-mentioned solution, terminating reaction after 40min is persistently stirred, vacuum is taken out
Filter, is successively washed 3 times, 5h is dried at room temperature, copper facing glass fibre functional particles are obtained respectively with distilled water and absolute ethyl alcohol.
(3) preparation of sandwich structure flexible copper clad functional particles conducting film
Mould wiped clean is dried in ventilating kitchen with distilled water, absolute ethyl alcohol in advance.Into 3.5g liquid silastics
Xylene solvent 9.0g is added dropwise, after stirring is fully dissolved to liquid silastic, tetraethyl orthosilicate 0.18g is added dropwise, after stirring
By the liquid silastic solution of above-mentioned dilution in above-mentioned mould flow casting molding, solidify 35min at room temperature, obtain the micro- solidification in surface
Bottom pure silicon glued membrane；Then in the bottom pure silicon film surface flow casting molding upper strata hybrid films being molded, it is specially：Toward 5.7g
15g xylene solvents are added dropwise in liquid silastic, stirring is fully dissolved to liquid silastic, and the positive silicic acid second of 0.342g is then added dropwise
Ester, is stirring evenly and then adding into 3.8g copper facing glass fibre functional particles and mixes；By the well mixed solution directly above-mentioned
Flow casting molding solidifies 24h at room temperature on the surface of the bottom pure silicon glued membrane of micro- solidification in mould, that is, obtains sandwich structure flexible
Copper facing functional particles conducting film.
Embodiment 6
(1) fiberglass surfacing is pre-processed
Weigh 6g degreasing glass fibres and be added to 30 DEG C of constant temperature in 100mL coarsening solutions, at the uniform velocity stir 15min, suction filtration, with steaming
Distilled water is added to 30 DEG C of constant temperature in 100mL sensitizing solutions after washing 2 times, at the uniform velocity stirs 15min, suction filtration, after distillation water washing 2 times
30 DEG C of constant temperature in 100mL activating solutions are added to, are at the uniform velocity stirred after 15min, suction filtration, it is standby with distillation water washing.Wherein, it is roughened
The composition and process for preparation of liquid, sensitizing solution and activating solution are as described in example 1 above.
(2) preparation of copper facing glass fibre functional particles
18g copper sulphate and 32g sodium citrates are weighed, in the beaker for being added sequentially to fill a small amount of distilled water, stirring and dissolving
Afterwards, 25wt% ammoniacal liquor 32mL is added, 192mL (pH is 12) is then settled to distilled water, afterwards by above-mentioned treated glass
Glass fiber is added in the solution of preparation and heated in water-bath, and mixing speed is 300r/min, is risen to when burning cup temperature
At 90 DEG C, 8mL30wt% hydrazine hydrate is slowly dropped into above-mentioned solution, terminating reaction after 70min is persistently stirred, vacuum is taken out
Filter, is successively washed 3 times, 5h is dried at room temperature, copper facing glass fibre functional particles are obtained respectively with distilled water and absolute ethyl alcohol.
(3) preparation of sandwich structure flexible copper clad functional particles conducting film
Mould wiped clean is dried in ventilating kitchen with distilled water, absolute ethyl alcohol in advance.Toward 4.85g liquid silastics
Middle dropwise addition xylene solvent 20.0g, after stirring is fully dissolved to liquid silastic, is added dropwise tetraethyl orthosilicate 0.21g, stirs
Afterwards by the liquid silastic solution of above-mentioned dilution in above-mentioned mould flow casting molding, solidify 40min at room temperature, obtain surface micro- solid
The bottom pure silicon glued membrane of change；Then in the bottom pure silicon film surface flow casting molding upper strata hybrid films being molded, it is specially：It is past
13.0g xylene solvents are added dropwise in 5.8g liquid silastics, stirring is fully dissolved to liquid silastic, and 0.406g then is being added dropwise just
Silester, is stirring evenly and then adding into 5.8g copper facing glass fibre functional particles and mixes；The well mixed solution is direct
Flow casting molding solidifies 24h, that is, obtains sandwich knot at room temperature on the surface of the bottom pure silicon glued membrane of micro- solidification in above-mentioned mould
Structure flexible copper clad functional particles conducting film.
The specific insulation contrast of functional particles and conducting film in the various embodiments described above of table 1
Claims (9)
1. a kind of preparation method of sandwich structure flexible copper clad functional particles conducting film, it is characterised in that its step is：
（1）The preparation of bottom pure silicon glued membrane：
Solvent is added dropwise in liquid silastic fully to dissolve to it, curing agent is then added dropwise, it is after stirring that liquid silastic is molten
Liquid flow casting molding in a mold, solidifies 20~40min, obtains the bottom pure silicon glued membrane of the micro- solidification in surface at room temperature；
（2）The preparation of flexible copper clad functional particles conducting film：
Solvent is added dropwise in liquid silastic fully to dissolve to it, curing agent is then added dropwise, copper facing glass is stirring evenly and then adding into micro-
Pearl or copper facing glass fibre functional particles are simultaneously mixed, and the flow casting molding on bottom pure silicon glued membrane solidifies 24h at room temperature；Solidified
Cheng Zhong, copper facing glass microballoon or copper facing glass fibre functional particles are gradually deposited down, be held on above and below between two layers of pellosil,
Form the thick sandwich structure flexible copper clad functional particles conducting films of 0.4~1 mm；
The mass ratio for preparing liquid silastic of the liquid silastic of bottom pure silicon glued membrane with preparing upper strata pellosil is 3 ~ 5:6,
The mass ratio of liquid silastic and copper facing glass microballoon or copper facing glass fibre functional particles is 3 in the pellosil of upper strata:1 ~ 3, liquid
The base-material of body silicon rubber is dimethyl siloxane.
2. a kind of preparation method of sandwich structure flexible copper clad functional particles conducting film according to claim 1, it is special
Levy and be, the curing agent is tetraethyl orthosilicate.
3. a kind of preparation method of sandwich structure flexible copper clad functional particles conducting film according to claim 2, it is special
Levy and be, the mass ratio of the liquid silastic and curing agent is 100:2~7.
4. a kind of preparation side of sandwich structure flexible copper clad functional particles conducting film according to claim 1 or 2 or 3
Method, it is characterised in that the solvent is dimethylbenzene, hexamethylene, ethyl acetate or acetone.
5. a kind of preparation method of sandwich structure flexible copper clad functional particles conducting film according to claim 4, it is special
Levy and be, the preparation method of the copper facing glass microballoon or copper facing glass fibre functional particles is：Weigh metal salt copper sulphate with
And complexing agent, be added sequentially to after distilled water, be stirring evenly and then adding into ammoniacal liquor, then use distilled water constant volume cause pH for 9~
13, will be afterwards 3 with metal salt copper sulphate mass ratio:1.5~9 glass microballoon or glass fibre is added to the molten of above-mentioned preparation
In liquid, 60~90 DEG C are heated to, reducing agent hydrazine hydrate solution is slowly added dropwise after stirring, is persistently stirred after 20~100min,
Washing, suction filtration, drying, obtain copper facing glass microballoon or copper facing glass fibre functional particles.
6. a kind of preparation method of sandwich structure flexible copper clad functional particles conducting film according to claim 5, it is special
Levy and be, described complexing agent is sodium citrate, disodium ethylene diamine tetraacetate or sodium potassium tartrate tetrahydrate.
7. a kind of preparation method of sandwich structure flexible copper clad functional particles conducting film according to claim 6, it is special
Levy and be, the glass microballoon or glass fibre for preparing copper facing glass microballoon or copper facing glass fibre functional particles have carried out table in advance
Face is pre-processed, and is the step of the pretreatment：
（a）Roughening：Glass microballoon or glass fibre are added in coarsening solution, and 30 DEG C of constant temperature are at the uniform velocity stirred after 15min, distillation washing
Wash, it is standby；
（b）Sensitization：Glass microballoon or glass fibre after roughened processing are added in sensitizing solution, and 30 DEG C of constant temperature are at the uniform velocity stirred
After 15min, water washing is distilled, it is standby；
（c）Activation：Glass microballoon or glass fibre after sensitized treatment is added in activating solution, 30 DEG C of constant temperature are at the uniform velocity stirred
After 15min, water washing is distilled, glass microballoon or glass fibre after surface preparation is obtained.
8. a kind of preparation method of sandwich structure flexible copper clad functional particles conducting film according to claim 7, it is special
Levy and be, the coarsening solution is the potassium bichromate, 50~100 mL/L 98 wt% concentrated sulfuric acid and steaming by 20~50 g/L
What distilled water was constituted；The sensitizing solution is by 10~60 g/L stannous chloride, 10~90 mL/L 37 wt% hydrochloric acid and distillation
What water was constituted；The activating solution is by 0.1~0.5 g/L palladium bichloride, 1~5 mL/L 37 wt% hydrochloric acid and distilled water structure
Into.
9. a kind of preparation method of sandwich structure flexible copper clad functional particles conducting film according to claim 8, it is special
Levy and be, glass fibre has carried out ungrease treatment in advance before roughening treatment is carried out, be the step of the ungrease treatment：Glass fibers
Dimension is added in NaOH solution, and 70 DEG C of constant temperature are at the uniform velocity stirred after 2h, is distilled water washing, is placed in constant temperature drying 4h in 80 DEG C of baking ovens,
It is standby.
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| DE19751711A1 (en) * | 1997-11-21 | 1999-05-27 | Leybold Systems Gmbh | Glass coating comprises a silver layer sandwiched between two high refractive index layers |
| CN102432201A (en) * | 2011-09-16 | 2012-05-02 | 中北大学 | Preparation method for silver-plated glass fibers and conductive rubber of same |
| CN104327777A (en) * | 2014-08-27 | 2015-02-04 | 安徽丹凤电子材料股份有限公司 | Method using silver-coated glass fiber to prepare conducting resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19751711A1 (en) * | 1997-11-21 | 1999-05-27 | Leybold Systems Gmbh | Glass coating comprises a silver layer sandwiched between two high refractive index layers |
| CN102432201A (en) * | 2011-09-16 | 2012-05-02 | 中北大学 | Preparation method for silver-plated glass fibers and conductive rubber of same |
| CN104327777A (en) * | 2014-08-27 | 2015-02-04 | 安徽丹凤电子材料股份有限公司 | Method using silver-coated glass fiber to prepare conducting resin |
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