CN116063723A - Resistive wave-absorbing film and preparation method and application thereof - Google Patents
Resistive wave-absorbing film and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
- 239000002002 slurry Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000003822 epoxy resin Substances 0.000 claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 16
- 238000007650 screen-printing Methods 0.000 claims abstract description 16
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 32
- 239000006229 carbon black Substances 0.000 claims description 19
- 239000010439 graphite Substances 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000011358 absorbing material Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
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- 238000003756 stirring Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 238000007790 scraping Methods 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical group CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 4
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
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- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 2
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 238000010409 ironing Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
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- 229920000642 polymer Polymers 0.000 claims description 2
- 238000009736 wetting Methods 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
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- 238000009472 formulation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
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- SOOZEQGBHHIHEF-UHFFFAOYSA-N methyltetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21C SOOZEQGBHHIHEF-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
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- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
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Abstract
The invention provides a resistance type wave-absorbing film which is mainly prepared from mixed carbon slurry and a film carrier, wherein the mixed carbon slurry comprises the following components in parts by weight: 10 to 15 parts of benzoxazine resin, 25 to 40 parts of epoxy resin, 0.1 to 5 parts of auxiliary agent, 10 to 15 parts of solvent, 15 to 35 parts of anhydride curing agent and 10 to 35 parts of conductive powder, and also provides a preparation method of the resistive wave-absorbing film, which comprises the following steps: and heating and uniformly mixing the benzoxazine resin and the epoxy resin, cooling, adding a solvent, an anhydride curing agent and an auxiliary agent, uniformly mixing, adding conductive powder, dispersing and grinding to obtain mixed carbon paste, screen-printing the mixed carbon paste on a film carrier, and curing to obtain the resistive wave-absorbing film. The carbon paste is coated on the film to form a conductive layer, wherein the conductive layer is resistant to the high temperature of more than 180 ℃, the substrate is also resistant to the high temperature, and the formed resistance type wave-absorbing film has high temperature resistance.
Description
Technical Field
The invention belongs to the technical field of wave-absorbing materials, and particularly relates to a resistive wave-absorbing film, a preparation method and application thereof.
Background
Along with the rapid development of the target detection technology, the current requirements on the wave-absorbing material are higher and higher, and the requirements on the light weight, the thin thickness, the wave-absorbing frequency bandwidth, the strong absorption peak and the like of the material are met. Wave-absorbing materials can be largely classified into resistive, dielectric and magnetic media according to electromagnetic loss mechanisms. The current common method for preparing the wave-absorbing material is as follows: dispersing the absorbent in the material to form a corrugated or pyramid structure, but the application is limited in many fields due to the thickness or weight of the wave-absorbing material; the mixed carbon paste is silk-screened on a carrier to prepare the wave-absorbing material by adopting a smearing and silk-screen mode, but the problems of insufficient high temperature resistance, low tensile strength and peeling strength, poor corrosion resistance and the like easily occur, the resistance value change is very large after other materials are adhered and compounded, the wave-absorbing effect is unstable, the performance requirement cannot be met, and the application of the wave-absorbing material is limited to a certain extent, so that the wave-absorbing material with high temperature resistance, controllable resistance and excellent performance is urgently needed.
Disclosure of Invention
The invention aims to solve the technical problems and overcome the defects and shortcomings in the background art, and provides a high-temperature-resistant, controllable-resistance and excellent-performance resistance type wave-absorbing film, and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the resistive wave-absorbing film is mainly prepared from mixed carbon slurry and a film carrier, wherein the mixed carbon slurry comprises the following components in parts by weight: 10 to 15 parts of benzoxazine resin, 25 to 40 parts of epoxy resin, 0.1 to 5 parts of auxiliary agent, 10 to 15 parts of solvent, 15 to 35 parts of anhydride curing agent and 10 to 35 parts of conductive powder.
Preferably, the epoxy resin is bisphenol a epoxy resin; the solvent comprises one or more of ethylene glycol butyl ether acetate, dimethyl glutarate and dimethyl succinate; the anhydride curing agent comprises one or a combination of more of liquid methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and methyl nadic anhydride. The solvent is selected from high boiling point solvents, the volatilization is slower at normal temperature, and the viscosity of the sizing agent in the printing process can be ensured to be more stable.
The epoxy resin and a sufficient amount of anhydride are cured under the action of an auxiliary agent, and after the epoxy resin is completely cured, the benzoxazine is subjected to ring-opening polymerization under the action of high temperature, so that an interpenetrating network structure is formed, and the mechanical and impact resistance, thermal performance, wet heat aging performance and the like of the epoxy resin crosslinking anhydride curing agent are further effectively improved.
Because the benzoxazine resin (BEP) has the characteristics of heat resistance, flame retardance, low shrinkage and good mechanical property, the epoxy resin has the characteristics of high bonding strength and cohesive strength, excellent corrosion resistance and dielectric property, the anhydride curing agent has the characteristics of small curing shrinkage, high curing heat deformation temperature and excellent mechanical and electrical properties, the curing agent is very slow to cure at normal temperature and can be stored for a long time, and the three components cooperate with each other to improve the heat resistance, corrosion resistance and other properties of the wave-absorbing film.
Preferably, the auxiliary agent comprises one or more of a dispersant, a defoamer and an accelerator; the dispersing agent is BYK polymer wetting dispersing agent, and the weight part of the dispersing agent is 1-4; the defoaming agent is tributyl phosphate, and the weight part of the defoaming agent is 0.1-0.5 part; the accelerator is an imidazole accelerator, the imidazole accelerator comprises one or a combination of more of 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole, and the weight part of the accelerator is 0.1-0.5 part.
Preferably, the conductive powder is a mixture of carbon black particles and graphite particles, and the carbon black particles are high-conductivity carbon black particles with the radius of 0.5-8 mu m; the radius of the graphite particles is 0.5-5 mu m, and the mixing mass ratio of the carbon black particles to the graphite particles is 1:1-8. More preferably, the mixing mass ratio of carbon black particles to graphite particles is 1:4.
Preferably, the film carrier is one of an FR4 film and a PI film, the thickness of the film carrier is less than or equal to 0.1mm, and the areal density is less than or equal to 100g/m 2 . The electromagnetic wave energy-eliminating material is light, thin and high temperature resistant material as carrier and has the functions of attenuating electromagnetic wave energy and eliminating electromagnetic wave energy effectively, and when electromagnetic wave is incident in space, inducing current is produced on the surface and the current is blocked inside the material to produce internal energy, so that the electromagnetic wave is converted into heat energy and electromagnetic wave is producedThe wave attenuation and elimination are realized, the carrier materials are all high temperature resistant film materials, the high temperature resistance of the electronic wave absorbing film can be effectively improved, and the light and thin carrier can further ensure that the whole thickness of the wave absorbing film is small, so that the stability of the resistor is facilitated.
Based on the general inventive concept, the invention also provides a preparation method of the resistive wave-absorbing film, which comprises the following steps: and heating and uniformly mixing the benzoxazine resin and the epoxy resin, cooling, adding a solvent, an anhydride curing agent and an auxiliary agent, uniformly mixing, adding conductive powder, dispersing and grinding to obtain mixed carbon paste, screen-printing the mixed carbon paste on a film carrier, and curing to obtain the resistive wave-absorbing film. The carbon paste is coated on the film to form a conductive layer, wherein the conductive layer is resistant to the high temperature of more than 180 ℃, the substrate is also resistant to the high temperature, and the formed resistance type wave-absorbing film has high temperature resistance.
Preferably, the heating and mixing are carried out by stirring at a temperature of 70 ℃ or lower; the cooling is to cool to room temperature; the dispersion is carried out by a dispersing machine, and the rotating speed of the dispersing machine is 600-1200 r/min; the grinding is carried out for 2-3 times by adopting a three-roller grinder.
Preferably, the ambient temperature of the silk screen printing is 18-28 ℃, the silk screen printing adopts a silk screen printer, and the parameters of the silk screen printer are as follows: the hardness of the doctor blade is 65-80 degrees, the pressure of the doctor blade is 40-50N, the silk screen plate is any one of a steel wire screen plate and a polyester screen plate, and the mesh number is 200-300 meshes; the moving speed of the ink scraping knife is 80-200 mm/s, and the moving speed of the ink returning knife is 240mm/s. The screen printer comprises a doctor blade, a screen plate and a scraping plate, wherein the scraping plate applies certain pressure to conductive paste on the screen plate, meanwhile, the scraping plate moves at a constant speed towards the other end of the screen plate, and the conductive paste is extruded onto a carrier from a mesh by the scraping plate in the moving process, so that a wave-absorbing film is formed. Too low a doctor blade pressure hardness affects printing accuracy and the service life is too short. The most suitable mesh number is 200-300 meshes, the mesh number is too small, the mesh size is large, the sizing agent easily penetrates through the silk screen, the mesh number is too large, and powder particles are difficult to scratch through the silk screen by a doctor blade.
Preferably, the curing process is as follows: and (3) carrying out adhesive ironing for 3-5 min at 80-90 ℃ and curing for 0.5-3 h at 150-160 ℃. The high-temperature paste at 80-90 ℃ can volatilize most of the solvent, and the high-temperature curing at 150-160 ℃ ensures complete curing.
Based on the general inventive concept, the invention also provides application of the resistive wave-absorbing film, wherein the resistive wave-absorbing film is attached to polyurethane foam or polymethacrylimide foam to prepare the composite functional wave-absorbing material or stealth material.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the resistive wave-absorbing film provided by the invention, the ultrathin high-temperature-resistant film is adopted as a carrier, the high-temperature-resistant anhydride substance is adopted as a curing agent, the benzoxazine resin is adopted as a modifier, and the epoxy resin cross-linked anhydride curing agent is modified, and the three are mutually cooperated, so that on one hand, the glass transition temperature and the impact strength of a cross-linked product of the epoxy resin and the anhydride curing agent can be improved, the defects of brittleness and inadequacy of impact resistance of the epoxy resin are overcome, and further, the mechanical and impact resistance, the thermal performance, the humid heat aging performance and the electrical insulation performance of the epoxy resin cross-linked anhydride curing agent are effectively improved, and on the other hand, the prepared wave-absorbing film has the advantages of high-temperature resistance, good impact resistance, good bonding performance, stable resistance and the like, and the flat pull strength of the prepared wave-absorbing film is more than 1.5MPa, and the high-temperature resistance is more than 180 ℃.
2. According to the invention, the mixed carbon paste is screen printed on an ultrathin carrier for solidification and molding, and meanwhile, an ultrathin high-temperature-resistant base material is adopted as the carrier, so that the performances of light weight, high temperature resistance, corrosion resistance, high bonding strength and the like of the wave-absorbing film are realized, the wave-absorbing film can be bonded and compounded with a wave-transmitting material to prepare a structural wave-absorbing material, the mixed carbon paste with different resistance values can be prepared by controlling the proportion of high-temperature-resistant conductive powder, the mixed carbon paste is screen printed on the ultrathin high-temperature-resistant carrier to prepare the resistance-type wave-absorbing film with different resistance values, the resistance can be adjusted, the performances of high temperature resistance, tensile strength and the like of the wave-absorbing film are improved, and the wave-absorbing film has the characteristics of small area density, high mechanical strength, solvent resistance, high and low temperature resistance, wear resistance, excellent adhesive force and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a resistive wave-absorbing film prepared according to the present invention.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
a resistive wave-absorbing film is prepared by coating a film carrier with a mixed carbon slurry and curing the mixed carbon slurry, wherein the mixed carbon slurry is prepared by the raw materials according to the mass ratio shown in a table 1. The selected high-conductivity carbon black particles are CaBOT carbon black VXC-72R.
The preparation method of the resistive wave-absorbing film comprises the following steps:
1. adding benzoxazine resin and bisphenol A epoxy resin into a flask according to a proportion, heating to 70 ℃, uniformly stirring to obtain a mixed solution in which the resin is completely dissolved, and then cooling to room temperature for standby;
2. adding a solvent, an anhydride curing agent and an auxiliary agent in fixed proportions into a stainless steel iron tank according to the table, adjusting the rotating speed to 600-1200 r/min, and uniformly dispersing;
3. the resin mixture prepared in step 1 was added to the mixture prepared in step 2 in the following ratio of table 1, and then conductive powder (a mixture of carbon black particles and graphite particles) was added thereto, stirred at high speed for 3 hours, and transferred to a three-roll mill for 3 times to prepare a mixed carbon slurry to be used.
Table 1: raw material formulation of example 1
| Component (A) | Parts by mass |
| Highly conductive carbon black particles (2 um) | 63g |
| Graphite particles (1.7 um) | 232g |
| Benzoxazine resin BEP | 110g |
| Bisphenol A epoxy resin | 250g |
| Methyl tetrahydrophthalic anhydride MTHPA | 185g |
| 2-ethyl-4-methylimidazole 2E4MZ | 2g |
| BYK-163 (Bi Kepai) | 20g |
| Tributyl phosphate | 3g |
| Glutaric acid dimethyl ester | 135g |
4. Screen printing the mixed carbon slurry to an areal density of 80g/m 2 And (3) on a 0.05mmFR4 film, wherein the environment temperature of silk screen printing is 23 ℃, the hardness of a doctor blade is 80 ℃, the pressure of the doctor blade is 40N, the mesh number of steel wires is 200 meshes, the moving speed of the doctor blade is 150mm/s, the moving speed of an ink returning knife is 240mm/s, finally, the carrier subjected to silk screen printing is stuck and scalded on a metal plate at 85 ℃ for 4min, most of solvent is volatilized, and then, the carrier is heated in an oven at 150 ℃ for 2h, so that the resistive wave-absorbing film is obtained. The high temperature resistance of the resistance type wave absorbing film is more than 180 ℃, the flat pull strength is more than 1.5MPa, the resistance change is 1.0-1.1, and the areal density is 92g/m 2 . As shown in fig. 1.
The resistance type wave-absorbing film is attached to polyurethane foam or polymethacrylimide foam, and can be made into a composite functional wave-absorbing material or a stealth material.
Example 2:
a resistive wave-absorbing film is prepared by coating a film carrier with a mixed carbon slurry and curing the mixed carbon slurry, wherein the raw materials of the mixed carbon slurry are prepared according to the mass ratio shown in a table 2. The selected high-conductivity carbon black particles are CaBOT carbon black VXC-72R.
The preparation method of the resistive wave-absorbing film comprises the following steps:
1. adding benzoxazine resin and bisphenol A epoxy resin into a flask according to a proportion, heating to 70 ℃, uniformly stirring to obtain a mixed solution in which the resin is completely dissolved, and then cooling to room temperature for substitution;
2. adding a solvent, an anhydride curing agent and an auxiliary agent in fixed proportions into a stainless steel iron tank according to the table, stirring and dispersing uniformly, and dispersing by using a dispersing machine with the rotating speed of 600-1200 r/min;
3. and (2) adding the resin mixed solution prepared in the step (1) into the mixed solution prepared in the step (2) according to the proportion shown in the table (4), adding carbon black particles and graphite particles with fixed proportions, stirring at a high speed for 3 hours, and transferring to a three-roller grinder for grinding for 3 times to prepare the ready-to-use mixed carbon slurry. Raw material ratios are added as shown in table 2:
table 2: raw material formulation of example 2
| Component (A) | Parts by mass |
| Highly conductive carbon black particles (2 um) | 58g |
| Graphite particles (1.7 um) | 142g |
| Benzoxazine resin BEP | 110g |
| Bisphenol A epoxy resin | 310g |
| Methyl tetrahydrophthalic anhydride MTHPA | 252g |
| 2-ethyl-4-methylimidazole 2E4MZ | 2g |
| BYK-163 (Bi Kepai) | 20g |
| Tributyl phosphate | 3g |
| Glutaric acid dimethyl ester | 103g |
4. Screen printing the mixed carbon slurry to an areal density of 81g/m 2 0.05 mmFR4: wherein the ambient temperature of screen printing is 23 ℃, the hardness of a doctor blade is 80 ℃, the pressure of the doctor blade is 40N, the mesh number of steel wires is 200 meshes, the moving speed of the doctor blade is 150mm/s, and the moving speed of an ink returning blade is 240mm/s. And finally, sticking and scalding the support subjected to silk screen printing on a metal plate at 85 ℃ for 4min to volatilize most of the solvent, and then heating the support in a baking oven at 150 ℃ for 2h to obtain the resistive wave-absorbing film. The high temperature resistance of the resistance type wave-absorbing film is more than 180 ℃, the flat pull strength is more than 1.5MPa, and the resistance change is 1.0-1.1.
Example 3:
a resistive wave-absorbing film is prepared by coating a film carrier with a mixed carbon slurry and curing the mixed carbon slurry, wherein the raw materials of the mixed carbon slurry are prepared according to the mass ratio shown in a table 3. The selected high-conductivity carbon black particles are CaBOT carbon black VXC-72R.
The preparation method of the resistive wave-absorbing film comprises the following steps:
1. adding benzoxazine resin and epoxy resin into a flask according to a certain proportion, heating to 70 ℃, uniformly stirring to obtain a mixed solution in which the resin is completely dissolved, and then cooling to room temperature for substitution;
2. adding a solvent, an anhydride curing agent and an auxiliary agent in fixed proportions into a stainless steel iron tank according to the table, stirring and dispersing uniformly, and dispersing by using a dispersing machine with the rotating speed of 600-1200 r/min;
3. and (3) adding the resin mixed solution prepared in the step (1) into the mixed solution prepared in the step (2) according to the proportion shown in the table (3), adding carbon black particles and graphite particles with fixed proportions, stirring at a high speed for 3 hours, and transferring to a three-roller grinder for grinding for 3 times to prepare the ready-to-use mixed carbon slurry. The proportion of the added raw materials is as follows:
table 3: example 3 raw material formulation
| Component (A) | Parts by mass |
| Highly conductive carbon black particles (2 um) | 58g |
| Graphite particles (1.7 um) | 142g |
| BEP | 110g |
| Bisphenol A epoxy resin | 310g |
| Methyl hexahydrophthalic anhydride MHHPA | 252g |
| 2-methylimidazole 2MZ | 2g |
| BYK-163 (Bi Kepai) | 20g |
| Tributyl phosphate | 3g |
| Glutaric acid dimethyl ester | 103g |
4. Screen printing the mixed carbon slurry to an areal density of 80g/m 2 0.05mm PI filmAnd (3) the following steps: wherein the ambient temperature of silk screen printing is 23 ℃, the hardness of a doctor blade is 80 ℃, the pressure of the doctor blade is 40 newtons, the mesh number of steel wires is 200 meshes, the moving speed of the doctor blade is 150mm/s, and the moving speed of an ink returning blade is 240mm/s. And finally, sticking and scalding the support subjected to silk screen printing on a metal plate at 85 ℃ for 4min to volatilize most of the solvent, and then heating the support in a baking oven at 150 ℃ for 2h to obtain the resistive wave-absorbing film. The high temperature resistance of the resistance type wave-absorbing film is more than 180 ℃, the flat pull strength is more than 1.5MPa, and the resistance change is 1.0-1.1.
Comparative example 1:
the steps and the raw material proportions of the resistive wave-absorbing film are the same as those of the preparation method of the embodiment 1, except that in the comparative example, carbon black is not added in the conductive carbon powder, and all the conductive carbon powder is graphite.
The proportion of each component in the comparative example 1 is as follows:
table 4: raw material ratio of comparative example 1
The wave-absorbing film of comparative example 1 has a flat pull strength of < 1.0MPa, and the adhesive property of the prepared wave-absorbing film is remarkably reduced compared with that of example 1.
The resistive type wave-absorbing films of comparative example 1, examples 1 to 3 were subjected to performance test, and the test results were as follows:
table 5: performance test of the wave-absorbing films prepared in examples 1 to 3
Table 6: test of reflectivity of the wave-absorbing films prepared in examples and comparative examples
| Wave absorbing effect | L | S | C | X | Ku | Ka |
| Example 1 | -0.45 | -2.88 | -16.84 | -13.74 | -10.34 | -8.99 |
| Example 2 | -0.15 | -0.97 | -4.90 | -4.41 | -4.73 | -7.37 |
| Example 3 | -0.16 | -1.09 | -5.71 | -5.05 | -5.52 | -7.63 |
| Comparative example 1 | -0.09 | -0.13 | -1.62 | -2.32 | -1.64 | -2.12 |
As can be seen from tables 5 and 6, the wave-absorbing film prepared without adding carbon black has a small flat pull strength and a small reflectance.
Claims (10)
1. The resistive wave-absorbing film is characterized by being prepared from mixed carbon slurry and a film carrier, wherein the mixed carbon slurry comprises the following components in parts by weight: 10 to 15 parts of benzoxazine resin, 25 to 40 parts of epoxy resin, 0.1 to 5 parts of auxiliary agent, 10 to 15 parts of solvent, 15 to 35 parts of anhydride curing agent and 10 to 35 parts of conductive powder.
2. The resistive wave-absorbing film of claim 1, wherein the epoxy is bisphenol a epoxy; the solvent comprises one or more of ethylene glycol butyl ether acetate, dimethyl glutarate and dimethyl succinate; the anhydride curing agent comprises one or a combination of more of liquid methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and methyl nadic anhydride.
3. The resistive wave-absorbing film according to claim 1, wherein the auxiliary agent comprises one or more of a combination of dispersants, defoamers, accelerators; the dispersing agent is BYK polymer wetting dispersing agent, and the weight part of the dispersing agent is 1-4; the defoaming agent is tributyl phosphate, and the weight part of the defoaming agent is 0.1-0.5 part; the accelerator is an imidazole accelerator, the imidazole accelerator comprises one or a combination of more of 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole, and the weight part of the accelerator is 0.1-0.5 part.
4. The resistive wave-absorbing film according to claim 1, wherein the conductive powder is a mixture of carbon black particles and graphite particles, the carbon black particles being highly conductive carbon black particles having a radius of 0.5 μm to 8 μm; the radius of the graphite particles is 0.5-5 mu m, and the mixing mass ratio of the carbon black particles to the graphite particles is 1:1-8.
5. The resistive wave-absorbing film according to claim 1, wherein the film carrier is one of an FR4 film and a PI film, and the film carrier has a thickness of 0.1mm or less and an areal density of 100g/m or less 2 。
6. A method for producing the resistive wave-absorbing film according to any one of claims 1 to 5, comprising the steps of: and heating and mixing the benzoxazine resin and the epoxy resin uniformly, cooling, adding the mixture of the solvent, the anhydride curing agent and the auxiliary agent, uniformly mixing, adding the conductive powder, dispersing and grinding to obtain mixed carbon paste, silk-screen printing the mixed carbon paste on a film carrier, and curing to obtain the resistive wave-absorbing film.
7. The method of claim 6, wherein the heating and mixing is carried out by stirring at 65-80 ℃; the cooling is to cool to room temperature; the dispersion is carried out by a dispersing machine, and the rotating speed of the dispersing machine is 600-1200 r/min; the grinding is carried out for 2-3 times by adopting a three-roller grinder.
8. The method according to claim 6, wherein the ambient temperature of the screen printing is 18-28 ℃, the screen printing is performed by a screen printer, and parameters of the screen printer are as follows: the hardness of the doctor blade is 65-80 degrees, the pressure of the doctor blade is 40-50N, the silk screen plate is any one of a steel wire screen plate and a polyester screen plate, and the mesh number is 200-300 meshes; the moving speed of the ink scraping knife is 80-200 mm/s, and the moving speed of the ink returning knife is 240mm/s.
9. The method of claim 6, wherein the curing process is: and (3) carrying out adhesive ironing for 3-5 min at 80-90 ℃ and curing for 0.5-3 h at 150-160 ℃.
10. Use of a resistive wave-absorbing film according to any one of claims 1 to 5 or a resistive wave-absorbing film produced by a method according to any one of claims 6 to 9, wherein the resistive wave-absorbing film is attached to polyurethane foam or polymethacrylimide foam to produce a composite functional wave-absorbing material or stealth material.
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