CN104674542B - Laser direct structured flexible fabric - Google Patents
Laser direct structured flexible fabric Download PDFInfo
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- CN104674542B CN104674542B CN201410820945.8A CN201410820945A CN104674542B CN 104674542 B CN104674542 B CN 104674542B CN 201410820945 A CN201410820945 A CN 201410820945A CN 104674542 B CN104674542 B CN 104674542B
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- laser direct
- direct organization
- flexible fabric
- coupling agent
- laser
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Abstract
The invention discloses a laser direct structured flexible fabric which is prepared from the following raw materials in percentage by weight: 90-94% of a polyacrylonitrile matrix material, 3-7.5% of a laser direct structured additive, 1-1.5% of graphene, 0.9-1.2% of a coupling agent and 0.3-0.6% of a lubricant. The fabric is prepared by the following steps: mixing the raw materials; drying and spinning the raw materials to prepare a flexible fabric; carrying out laser-induction to form a circuit template; and finally depositing on the circuit template through chemical plating and electroplating to form a metal circuit. The fabric disclosed by the invention can be used for laser direct structured treatment and the original performances of the polyacrylonitrile fabric can be maintained. The laser direct structured flexible fabric is likely applied to the fields of intelligent garments, flexible medical apparatuses and instruments, wearable communication equipment, flexible circuit boards and the like.
Description
Technical field
The present invention relates to a kind of flexible fabric, particularly to a kind of laser direct organization flexible fabric.
Background technology
Printed conductor injection-moulding device (molded injection devices, mid) can by mask means, plating (or change
Learn plating) process builds circuit on three dimensional mold part.The custom circuit plate phase made with plastics by glass fiber reinforcement etc.
Instead, the three dimensional structure of the mid assembly prepared by this way is so as to not only have the precision architecture of printed circuit board (PCB), simultaneously institute
Purchasing the wiring that the circuit built can substitute in electrical equipment or electronic equipment, thus saving space, electronic equipment manufacturing can be obtained
Less, and reduce manufacturing cost by reducing package count and contact procedure.These mid equipment are largely used to mobile phone, integrated
Circuit, computer are sponsored in the production application of other electronic equipments together.
Stamped metal (stamp metal), installation flexible printed circuit board (fpcb) and two sections of molding methods (two-shot
Molding method) it is three kinds of existing technology preparing mid.But, the method for molding and installation fpcb is in pattern geometry
In there is limitation, and mould is expensive, needs more mold exchange when producing the different pattern requiring thus taking time and effort.And two sections of moulds
Though molding process has been used for producing the mid equipment with three dimensional structure, environment can be produced larger in its production process
Pollution.
Therefore, the new mid technology of exploitation becomes the fashion trend of the outer relevant industries of Now Domestic.Wherein, laser straight
Connect the extensive pass that structuring (laser directly structuring, lds) technology receives research worker and developer
Note.In lds method, the laser beam of computer controls can move thus leaving preinstalled circuit in frosting on mid
Trace, this trace can process (including plating and chemical plating method etc.) required circuit of formation through the later stage.Lds method can obtain
Obtain 150 microns or less of conductive path width.Additionally, the interval between conductive path can also be 150 microns or more
Little, therefore, the mid being formed by the method can reduce the volume and weight of electronic equipment.Additionally, lds also has additive method
Not available motility and convenience；Only by control laser reprogramming can access new circuit pattern and
Circuit design.
But, current the method is applied only for structure and the production of the surface circuit of the rigid materials such as plastics, pottery.And
In some special application aspect, these materials far can not meet and are actually needed, such as intelligent clothing, flexible medical device
The fields such as tool, wearable communication apparatus, flexible PCB.Therefore, it is necessary to a kind of flexible textile material of exploitation is so as to energy
Enough designed by lds method and build electronic circuit.
Content of the invention
It is an object of the invention to provide a kind of laser direct organization flexible fabric, can be used in laser direct organization
Process, and the original properties of polyacrylonitril fabrics can be kept, the flexible fabric of this laser direct organization intends application
In fields such as intelligent clothing, flexible medical device, wearable communication apparatus, flexible PCBs.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of laser direct organization flexible fabric, described laser direct organization flexible fabric is by following weight percent
Raw material than meter:
Polyacrylonitrile matrix material 90-94%, laser direct organization additive 3-7.5%, Graphene 1-1.5%, even
Connection agent 0.9-1.2%, lubricant 0.3-0.6%；
Mixing, after being dried, spinning, make flexible fabric, form circuit masterplate through induced with laser, finally by chemical plating and
Plating deposits metal in formation metallic circuit on circuit masterplate and forms.
The core of the present invention is using specific laser direct organization additive, polyacrylonitrile matrix material to be changed
Property, so that material has induced with laser metallic characteristic, after machine-shaping, material surface irradiates the table of (induction) through laser
Facial branch forms metallized particles, just can form electronic circuit, easy and simple to handle, the time after directly adopting chemical plating (plating)
Short, low cost.Just different electronic circuit blanks can be adjusted by controlling the irradiation route of laser, through chemical plating (plating) processing
Become electronic circuit, easy to adjust, flexible.After induced with laser metallization, the material surface roughness through inducing moiety improves, so
Coating is good with the adhesion of base material afterwards for chemical plating (plating), eliminates before chemical plating (plating) to science and engineering at the additional surface of base material
Sequence.
The present invention carries out induced with laser, laser direct organization additive from specific laser direct organization additive
For the tin ash of non-copper system, light color, the color and luster controllable of achievable moulded products, such laser direct organizationization interpolation in addition
Under laser irradiation, chemical bonding structure is easier to be subjected to destruction, and metal ion is released formation metal core, can be effective for agent
Improve the deposition of metal efficiency in chemical metallization processing.The present invention select specific laser direct organization additive its with
After material other component cooperation, induced with laser Metallization effects are good, and chemical plating (plating) adhesive force on base material for the metal afterwards
Good moreover it is possible to improve the high temperature resistant, heat conduction of material and fire resistance.
Nanoscale laser direct organization additive (nanoscale stannic oxide particle) has skin effect, small-size effect
And macro quanta tunnel effect, there is very high specific surface area, therefore in granule, each particle composed atom is few, at surface
In metastable condition so as to lattice surface vibrations amplitude is larger, it is easier to lead to electronic shell transition under high energy laser excites,
Form metal active centres, shorten induction duration；Additionally due to less particle size, will be formed in unit area and more cause
Close, more spike, can reduce the addition of whole nanoscale laser direct organization additive.
The present invention is by the micron-sized laser direct organization additive (micron order tin ash) of specific dimensions and specific chi
Very little nanoscale laser direct organization additive (nanoscale tin ash) is combined, and defines very strong dimensional effect, permissible
Substantially reduce consumption and cost.The proportioning of control micron order tin ash and nanoscale tin ash and size, such material
The metallized particles roughness that the surface portion that (induction) is irradiated through laser in material surface is formed is good, and after chemical plating, metal is in base material
On adhesive force good, difficult for drop-off.Although although can be improved after chemical plating using pure nanoscale laser direct organization additive
Adhesive force on base material for the metal and anti-flammability, but plating rate of overflowing is larger, by specific control micron order tin ash and nanometer
Level tin ash cooperation, after can guarantee that chemical plating, metal, on the basis of the adhesive force on base material and anti-flammability, solves plating rate of overflowing
Larger problem.
The addition of Graphene can increase the absorbability to laser energy for the fabric, thus effectively improving induced with laser laser straight
Connect the effect of structuring additive.
Preferably, described coupling agent by phosphate coupling agent and silane coupler according to 1:1-2 weight than mixing
Become.
Preferably, the concretely comprising the following steps of described raw material mixing: phosphate coupling agent and dehydrated alcohol are mixed to form matter
Amount concentration is the phosphate coupling agent solution of 20%-40%, then adds phosphate ester to be coupled laser direct organization additive
In agent solution, stirring mixing 10-15min, it is subsequently added into silane coupler, stirring mixing 60-80min, be eventually adding polypropylene
Nitrile matrix material, Graphene and lubricant, are uniformly mixed.
Inventor's research finds, first passes through and carries out a table using phosphate coupling agent to laser direct organization additive
Face is processed, and after phosphate coupling agent is mixed into laser direct organization additive, can effectively penetrate into laser direct organization additive
Gap between granule, makes to be relatively isolated between laser direct organization additive granules, can effectively improve laser direct organization
Change the dispersibility between additive granules, then pass through again to add silane coupler to the laser direct organization additive processing
Carry out secondary surface treatment, the problem that so energy effectively solving laser direct organization additive is reunited, so that silane coupler is had
The parcel laser direct organization additive granules of effect, further prevent the group of laser direct organization additive granules
Poly-, add for follow-up polyacrylonitrile and carried out effective place mat effect, thus improve laser direct organization additive
Availability.
Preferably, described drying is vacuum dried 3-5 hour at being 50-60 DEG C.Vacuum drying can remove unnecessary moisture
And fall ethanol exclusion.
Preferably, described laser direct organization additive is by micron order stannic oxide particle and nanoscale tin ash
Granule forms, and the percentage by weight that nanoscale stannic oxide particle accounts for laser direct organization additive is 25-35%.
Preferably, described micron order stannic oxide particle particle diameter is in 5-30 micron, described nanoscale stannic oxide particle
Particle diameter is in 10-200 nanometer.
Preferably, described lubricant is ethylene bis stearamide.
The invention has the beneficial effects as follows: can be used in laser direct organizationization and process, and polyacrylonitrile can be kept to knit
The original properties of thing, the flexible fabric of this laser direct organization is intended being applied to intelligent clothing, flexible medical device, can wearing
Wear the fields such as formula communication apparatus, flexible PCB.
Specific embodiment
Below by specific embodiment, technical scheme is described in further detail.
In the present invention, if not refering in particular to, the raw material being adopted and equipment etc. are all commercially available or commonly used in the art.
Method in following embodiments, if no special instructions, is the conventional method of this area.
The polyacrylonitrile powder body (commercially available) that polyacrylonitrile matrix material is 1300000 for molecular weight.
Embodiment 1:
A kind of laser direct organization flexible fabric, composition of raw materials is:
Polyacrylonitrile matrix material 90kg, laser direct organization additive 7.5kg, Graphene 1kg, coupling agent 1.2kg,
Lubricant (ethylene bis stearamide) 0.3kg, wherein laser direct organization additive by micron order stannic oxide particle with receive
Meter level stannic oxide particle forms, and the percentage by weight that nanoscale stannic oxide particle accounts for laser direct organization additive is
25%；Coupling agent by phosphate coupling agent (commercially available) and silane coupler (kh550, commercially available) according to 1:1 weight than mixing
Become.Raw material mixes: phosphate coupling agent and dehydrated alcohol are mixed to form the phosphate coupling agent solution that mass concentration is 20%,
Then laser direct organization additive is added in phosphate coupling agent solution, stirring mixing 10min, it is subsequently added into silane even
Connection agent, stirring mixing 60min, it is eventually adding polyacrylonitrile matrix material, Graphene and lubricant, be uniformly mixed.
Then the raw material mixing is vacuum dried 5 hours at 50 DEG C, dried material dissolution is in dimethyl formyl
Amine (material concentration is 245 g/l), and pass sequentially through dimethylformamide/distilled water (volume ratio is 6:4), dimethyl formyl
Amine/distilled water (volume ratio is 2:8) and the coagulating bath of distilled water carry out spinning, and spinning drawing speed is 4 meter per seconds.
The fiber that spinning obtains obtains polyacrylonitril fabrics using tricot machine after follow-up 1.4 times of drawing-offs.
Using the blue-violet laser that wavelength is 405 nanometers, fabric is performed etching, wherein, laser power is 3.4w, laser frequency
Rate is 60khz, and etching speed is 3.0 meter per seconds.
Then, (wherein, silver ammino solution is by the silver nitrate solution of 2wt% and 2% to immerse the mixed solution of silver-colored ammonia/formaldehyde
Weak ammonia is constituted, and the concentration of formalin is 3%；The ratio of silver ammino solution and formalin mixes for 1:1), in 70 DEG C of chemistry
Plating 30 minutes, fabric drying is tested its resistivity and is: 1.2 × 10-2ω/m；Then, using the fabric of chemical plating as anode,
Copper sheet as negative electrode, electroplated formation copper circuit, applied voltage be 12v, electroplating time be 20 minutes；The resistance of circuit after drying
Rate drops to 2.7 × 10-5ω/m.
Embodiment 2:
A kind of laser direct organization flexible fabric, composition of raw materials is:
Polyacrylonitrile matrix material 94kg, laser direct organization additive 3kg, Graphene 1.5kg, coupling agent 0.9kg,
Lubricant (ethylene bis stearamide) 0.6kg, wherein laser direct organization additive by micron order stannic oxide particle with receive
Meter level stannic oxide particle forms, and the percentage by weight that nanoscale stannic oxide particle accounts for laser direct organization additive is
35%；Coupling agent by phosphate coupling agent (commercially available) and silane coupler (kh570, commercially available) according to 1:2 weight than mixing
Become.Raw material mixes: phosphate coupling agent and dehydrated alcohol are mixed to form the phosphate coupling agent solution that mass concentration is 40%,
Then laser direct organization additive is added in phosphate coupling agent solution, stirring mixing 15min, it is subsequently added into silane even
Connection agent, stirring mixing 80min, it is eventually adding polyacrylonitrile matrix material, Graphene and lubricant, be uniformly mixed.
Then the raw material mixing is vacuum dried 3 hours at 60 DEG C, dried material dissolution is in dimethyl formyl
Amine (material concentration is 245 g/l), and pass sequentially through dimethylformamide/distilled water (volume ratio is 6:4), dimethyl formyl
Amine/distilled water (volume ratio is 2:8) and the coagulating bath of distilled water carry out spinning, and spinning drawing speed is 4 meter per seconds.
The fiber that spinning obtains obtains polyacrylonitril fabrics using tricot machine after follow-up 1.4 times of drawing-offs.
Using the blue-violet laser that wavelength is 405 nanometers, fabric is performed etching, wherein, laser power is 3.4w, laser frequency
Rate is 60khz, and etching speed is 3.0 meter per seconds.
Then, (wherein, silver ammino solution is by the silver nitrate solution of 2wt% and 2% to immerse the mixed solution of silver-colored ammonia/formaldehyde
Weak ammonia is constituted, and the concentration of formalin is 3%, and the ratio of silver ammino solution and formalin mixes for 1:1), in 70 DEG C of chemistry
Plating 30 minutes, fabric drying is tested its resistivity and is: 2.7 × 10-2ω/m；Then, using the fabric of chemical plating as anode,
Copper sheet as negative electrode, electroplated formation copper circuit, applied voltage be 12v, electroplating time be 20 minutes；The resistance of circuit after drying
Rate drops to 4.2 × 10-5ω/m.
Embodiment 3:
A kind of laser direct organization flexible fabric, composition of raw materials is:
Polyacrylonitrile matrix material 92kg, laser direct organization additive 5.3kg, Graphene 1.2kg, coupling agent 1kg,
Lubricant (ethylene bis stearamide) 0.5kg, wherein laser direct organization additive by micron order stannic oxide particle with receive
Meter level stannic oxide particle forms, and the percentage by weight that nanoscale stannic oxide particle accounts for laser direct organization additive is
30%；Coupling agent is mixed according to the weight ratio of 1:1.5 with silane coupler (kh560, commercially available) by phosphate coupling agent (commercially available)
Form.Raw material mixes: phosphate coupling agent and dehydrated alcohol is mixed to form the phosphate coupling agent that mass concentration is 30% molten
Then laser direct organization additive is added in phosphate coupling agent solution by liquid, stirring mixing 12min, is subsequently added into silicon
Alkane coupling agent, stirring mixing 70min, it is eventually adding polyacrylonitrile matrix material, Graphene and lubricant, be uniformly mixed.
Then the raw material mixing is vacuum dried 4 hours at 55 DEG C, dried material dissolution is in dimethyl formyl
Amine (material concentration is 245 g/l), and pass sequentially through dimethylformamide/distilled water (volume ratio is 6:4), dimethyl formyl
Amine/distilled water (volume ratio is 2:8) and the coagulating bath of distilled water carry out spinning, and spinning drawing speed is 4 meter per seconds.
The fiber that spinning obtains obtains polyacrylonitril fabrics using tricot machine after follow-up 1.4 times of drawing-offs.
Using the blue-violet laser that wavelength is 405 nanometers, fabric is performed etching, wherein, laser power is 3.4w, laser frequency
Rate is 60khz, and etching speed is 3.0 meter per seconds.
Then, (wherein, silver ammino solution is by the silver nitrate solution of 2wt% and 2% to immerse the mixed solution of silver-colored ammonia/formaldehyde
Weak ammonia is constituted, and the concentration of formalin is 3%, and the ratio of silver ammino solution and formalin mixes for 1:1), in 70 DEG C of chemistry
Plating 30 minutes, fabric drying is tested its resistivity and is: 3.6 × 10-2ω/m；Then, using the fabric of chemical plating as anode,
Copper sheet as negative electrode, electroplated formation copper circuit, applied voltage be 12v, electroplating time be 20 minutes；The resistance of circuit after drying
Rate drops to 5.8 × 10-5ω/m.
Embodiment described above is one kind preferably scheme of the present invention, not the present invention is made any pro forma
Limit, also have other variants and remodeling on the premise of without departing from the technical scheme described in claim.
Claims (5)
1. a kind of laser direct organization flexible fabric it is characterised in that described laser direct organization flexible fabric be by with
The raw material of lower percentage by weight meter:
Polyacrylonitrile matrix material 90-94%, laser direct organization additive 3-7.5%, Graphene 1-1.5%, coupling agent 0.9-
1.2%, lubricant 0.3-0.6%；Described laser direct organization additive is by micron order stannic oxide particle and nanoscale dioxy
Change tin particles composition, the percentage by weight that nanoscale stannic oxide particle accounts for laser direct organization additive is 25-35%；Institute
State micron order stannic oxide particle particle diameter in 5-30 micron, described nanoscale stannic oxide particle particle diameter is in 10-200 nanometer；
Mixing, after being dried, spinning, make flexible fabric, form circuit masterplate through induced with laser, finally by chemical plating and plating
Deposit metal in formation metallic circuit on circuit masterplate to form.
2. a kind of laser direct organization flexible fabric according to claim 1 it is characterised in that: described coupling agent is by phosphorus
Acid esters coupling agent is mixed according to the weight ratio of 1:1-2 with silane coupler.
3. a kind of laser direct organization flexible fabric according to claim 2 it is characterised in that: the mixing of described raw material
Concretely comprise the following steps: phosphate coupling agent and dehydrated alcohol are mixed to form the phosphate coupling agent that mass concentration is 20%-40% molten
Then laser direct organization additive is added in phosphate coupling agent solution by liquid, stirring mixing 10-15min, is subsequently added into
Silane coupler, stirring mixing 60-80min, it is eventually adding polyacrylonitrile matrix material, Graphene and lubricant, stirring mixing
Uniformly.
4. a kind of laser direct organization flexible fabric according to claim 1 or 2 or 3 it is characterised in that: described drying
For being vacuum dried 3-5 hour at 50-60 DEG C.
5. a kind of laser direct organization flexible fabric according to claim 1 or 2 or 3 it is characterised in that: described lubrication
Agent is ethylene bis stearamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410820945.8A CN104674542B (en) | 2014-12-22 | 2014-12-22 | Laser direct structured flexible fabric |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410820945.8A CN104674542B (en) | 2014-12-22 | 2014-12-22 | Laser direct structured flexible fabric |
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| Publication Number | Publication Date |
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| CN104674542A CN104674542A (en) | 2015-06-03 |
| CN104674542B true CN104674542B (en) | 2017-01-25 |
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| CN201410820945.8A Expired - Fee Related CN104674542B (en) | 2014-12-22 | 2014-12-22 | Laser direct structured flexible fabric |
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| CN108243575B (en) * | 2016-12-27 | 2020-04-17 | Bgt材料有限公司 | Method for manufacturing polymer printed circuit board |
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| CN101684200B (en) * | 2008-09-25 | 2011-12-07 | 比亚迪股份有限公司 | Plastic blending material, preparation method thereof and surface metalized plastic part |
| CN103450654B (en) * | 2013-09-04 | 2016-03-30 | 上海锦湖日丽塑料有限公司 | A kind of can the resin and preparation method thereof of laser direct forming |
| CN103747635A (en) * | 2013-12-30 | 2014-04-23 | 金发科技股份有限公司 | Method for selective deposition of metals through interfacial adsorption and application thereof |
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