CN111019285A - High-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties - Google Patents

High-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties Download PDF

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Publication number
CN111019285A
CN111019285A CN201911233580.8A CN201911233580A CN111019285A CN 111019285 A CN111019285 A CN 111019285A CN 201911233580 A CN201911233580 A CN 201911233580A CN 111019285 A CN111019285 A CN 111019285A
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absorbing material
frequency
volume ratio
flame
retardant
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周成
向小玲
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Wuxi Ruisui Electronic Material Technology Co ltd
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Wuxi Ruisui Electronic Material Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04Ingredients characterised by their shape and organic or inorganic ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477Six-membered rings
    • C08K5/3492Triazines
    • C08K5/34928Salts
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/06Elements
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/16Solid spheres
    • C08K7/18Solid spheres inorganic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2217Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224Magnesium hydroxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)

Abstract

The invention belongs to the technical field of wave-absorbing materials, and particularly relates to a high-frequency-band wave-absorbing material with flame retardant and oxidation resistance. The high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties comprises the following raw materials in volume ratio: the volume ratio of the fibrous conductive carbon fiber is 2.5-12%, the volume ratio of carbonyl iron powder is 45-70%, the volume ratio of resin is 20-22%, and the volume ratio of the flame retardant is 5-8%. The beneficial effects are as follows: the flexible wave-absorbing material has excellent absorption effect and inhibition effect on some reflected waves, can effectively solve the problem of the reduction of the absorption performance of electromagnetic waves caused by bending or folding, is suitable for manufacturing flexible wave-absorbing materials with the thickness of less than 100 mu m, and has the absorption capacity of 10 percent in a 0.5GHz frequency band and the absorption capacity of more than 40 percent in a 3GHz frequency band, and the emission capacity can reach less than-5 dB in the 0.1GHz-3GHz frequency band.

Description

High-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties
Technical Field
The invention belongs to the technical field of wave-absorbing materials, and particularly relates to a high-frequency-band wave-absorbing material with flame retardant and oxidation resistance.
Background
In recent years, the update speed of electronic products is fast, and the development of miniaturization, weight reduction and multi-functionalization is progressing, and particularly, the development of smart phones is more and more advanced, and with the miniaturization of electronic devices and the higher operating frequency, in electronic devices with high-density packaged sub-devices, the suppression of electromagnetic interference becomes more and more important, and a flexible magnetic material for suppressing electromagnetic interference is provided, which can have the function of suppressing electromagnetic interference in a wide frequency band from low frequency to high frequency.
Disclosure of Invention
The invention provides a high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties, aiming at making up for the defects of the prior art.
The invention is realized by the following technical scheme:
a high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties comprises the following raw materials in volume ratio: the volume ratio of the fibrous conductive carbon fiber is 2.5-12%, the volume ratio of carbonyl iron powder is 45-70%, the volume ratio of resin is 20-22%, and the volume ratio of the flame retardant is 5-8%.
Further, the flame retardant includes melamine polyphosphate, magnesium hydroxide, hydrotalcite, and preferably magnesium hydroxide and melamine polyphosphate are used.
Further, the carbonyl iron powder is spherical, and the average grain diameter is 1-10 um.
The fibrous conductive carbon is obtained by processing carbon fibers, and is preferably a chopped fiber having a fiber length of 3 to 24mm or a ground fiber having a fiber length of 30 to 150 μm.
Further, the resin is a styrene elastomer, an olefin elastomer, a polyester elastomer, a polyamide elastomer, a polyurethane elastomer, or a silicone elastomer.
Further, examples of the styrene elastomer include SEBS styrene ethylene butylene styrene block copolymer, and elastomers that can be used by mixing acrylic resin, epoxy resin, polyolefin resin.
Further, the high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties contains an antioxidant, the volume ratio of the antioxidant is 0.5-3%, the antioxidant comprises 2', 3-bis [3- [3, 5-tert-butyl-4-hydroxyphenyl ] acrylic ester ] propionohydrazide, the antioxidant of the resin comprises tetracyanoyl [ trimethylene-3- (3 ', 5' -butyl-4 ' -hydroxyphenyl) propionate ], tris- (3, 5-butyl-4-hydroxybenzyl) -isocyanurate and N, N ' -hexamethylene bis (3, 5-butyl-4-hydroxy 10-amide), and the antioxidant is preferably one compatible with the resin.
The invention has the beneficial effects that: the flexible wave-absorbing material has excellent absorption effect and inhibition effect on some reflected waves, can effectively solve the problem of the reduction of the absorption performance of electromagnetic waves caused by bending or folding, is suitable for manufacturing flexible wave-absorbing materials with the thickness of less than 100 mu m, and has the absorption capacity of 10 percent in a 0.5GHz frequency band and the absorption capacity of more than 40 percent in a 3GHz frequency band, and the emission capacity can reach less than-5 dB in the 0.1GHz-3GHz frequency band.
Detailed Description
The high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties of the invention is further described in the following by combining the examples.
A high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties comprises the following raw materials in volume ratio: the volume ratio of the fibrous conductive carbon fiber is 2.5-12%, the volume ratio of carbonyl iron powder is 45-70%, the volume ratio of resin is 20-22%, and the volume ratio of the flame retardant is 5-8%.
Further, the flame retardant includes melamine polyphosphate, magnesium hydroxide, hydrotalcite, and preferably magnesium hydroxide and melamine polyphosphate are used.
Further, the carbonyl iron powder is spherical, and the average grain diameter is 1-10 um.
The fibrous conductive carbon is obtained by processing carbon fibers, and is preferably a chopped fiber having a fiber length of 3 to 24mm or a ground fiber having a fiber length of 30 to 150 μm.
Further, the resin is a styrene elastomer, an olefin elastomer, a polyester elastomer, a polyamide elastomer, a polyurethane elastomer, or a silicone elastomer.
Further, examples of the styrene elastomer include SEBS styrene ethylene butylene styrene block copolymer, and elastomers that can be used by mixing acrylic resin, epoxy resin, polyolefin resin.
Further, the high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties contains an antioxidant, the volume ratio of the antioxidant is 0.5-3%, the antioxidant comprises 2', 3-bis [3- [3, 5-tert-butyl-4-hydroxyphenyl ] acrylic ester ] propionohydrazide, the antioxidant of the resin comprises tetracyanoyl [ trimethylene-3- (3 ', 5' -butyl-4 ' -hydroxyphenyl) propionate ], tris- (3, 5-butyl-4-hydroxybenzyl) -isocyanurate and N, N ' -hexamethylene bis (3, 5-butyl-4-hydroxy 10-amide), and the antioxidant is preferably one compatible with the resin.
Example 1
The invention relates to a high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties, which adopts fibrous conductive carbon fibers with the length of 6mm, the fiber diameter of 1 mu m and the density of 1.5g/cm3The volume ratio is 4 percent, the particle diameter of the carbonyl iron powder is 6.2 mu m, and the density is 7.8g/cm335 percent by volume and 21 percent by volume of the styrene elastomer, taking melamine polyphosphate as a flame retardant, carrying out thin film stress on the sample by taking the magnesium hydroxide as a flame retardant, carrying out thin.
Example 2
The invention relates to a high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties, which adopts fibrous conductive carbon fibers with the length of 6mm, the fiber diameter of 1 mu m and the density of 1.5g/cm3The volume ratio is 4 percent, the particle diameter of the carbonyl iron powder is 6.2 mu m, and the density is 7.8g/cm355 percent by volume, 21 percent by volume of the styrene elastomer, 1.8g/cm in density and 8 percent by volume when melamine polyphosphate is used as the flame retardant, 2.4g/cm in density and 8 percent by volume when magnesium hydroxide is used as the flame retardant, and the sample of the wave-absorbing material with the thickness of 50um is prepared.
Example 3
The invention relates to a high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties, which adopts fibrous conductive carbon fibers with the length of 6mm, the fiber diameter of 1 mu m and the density of 1.5g/cm3The volume ratio is 4 percent, the particle diameter of the carbonyl iron powder is 6.2 mu m, and the density is 7.8g/cm355 percent by volume of styrene elastomer, 21 percent by volume of melamineAnd (3) carrying out high-speed high-.
Example 4
The invention relates to a high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties, which adopts fibrous conductive carbon fibers with the length of 6mm, the fiber diameter of 1 mu m and the density of 1.5g/cm3) The volume ratio is 6 percent, the particle diameter of the carbonyl iron powder is 6.2 mu m, and the density is 7.6g/cm355 percent by volume and 21 percent by volume of the styrene elastomer, taking melamine polyphosphate as a flame retardant, carrying out bulk transferring at a density of 1.8g/cm and 8 percent by volume, taking magnesium hydroxide as a flame retardant, carrying out bulk transferring at a density of 2.4g/cm and carrying out bulk transferring at a volume ratio of 8 percent, and preparing the wave-absorbing material sample with the thickness of 100 um.
Example 5
The invention relates to a high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties, which adopts fibrous conductive carbon fibers with the length of 6mm, the fiber diameter of 1 mu m and the density of 1.5g/cm3The volume ratio is 3 percent, the particle diameter of the carbonyl iron powder is 6.2 mu m, and the density is 7.8g/cm365% in volume ratio, 21% in volume ratio of the styrene elastomer, 1.8g/cm in density and 7% in volume ratio when melamine polyphosphate is used as the flame retardant, 2.4g/cm in density and 7% in volume ratio when magnesium hydroxide is used as the flame retardant, and the sample of the wave-absorbing material with the thickness of 50um is prepared.
Example 6
The invention relates to a high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties, which adopts fibrous conductive carbon fibers with the length of 6mm, the fiber diameter of 1 mu m and the density of 1.5g/cm3The volume ratio is 2 percent, the particle diameter of the carbonyl iron powder is 6.2 mu m, and the density is 7.8g/cm3The volume ratio is 60 percent, the volume ratio of the styrene elastomer is 21 percent, and a 50um wave-absorbing material sample is prepared.
The high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant performances in the embodiments are subjected to the measurement of the electromagnetic wave absorption capacity and the emission capacity, and the specific tests are as follows:
1. using a microstrip line test method, wherein the jig is a substrate with the length of 100mm, the width of 2.3mm, the thickness of 35 microns and the impedance of 50 ohms, and the flexible wave-absorbing material is made into the size of 40mm x 50 mm;
2. and (3) testing the bending wave-absorbing performance: the wave-absorbing material is made into a sample with the size of 50mm x 40mm, the sample is placed under a plastic plate with the thickness of 3mm and an oblique angle edge of 70 degrees, then the sample is bent along the oblique angle, the short edge (40 mm) of the sample is parallel to the oblique edge of the plastic plate, a test piece is pulled in the direction vertical to the side surface, the test piece is in close contact with the edge and the oblique surface, meanwhile, the plastic plate is lightly held along the pulling direction, the whole test piece is uniformly folded as much as possible, after the operation is carried out for 10 times through the actions, the absorption and reflection quantity of electromagnetic waves are immediately measured by using a line strip method, and the characteristic change is confirmed, wherein two groups of comparison groups are as follows:
comparative group 1: flattening FE-SI-AL, carrying out thin-film dry distillation with the density of 6.9g/cm, carrying out grain diameter of 50um, volume ratio of 47 percent and volume ratio of 53 percent on the styrene elastomer, and preparing a 100um wave-absorbing material sample;
comparative group 2: the grain diameter of the carbonyl iron powder is 6.2 mu m, and the density is 7.8g/cm3The volume ratio is 60 percent, the volume ratio of the styrene elastomer is 21 percent, and a 50um wave-absorbing material sample is prepared.
Electromagnetic wave absorption amount measurement data:
contrast item Thickness of Absorption% @0.5GHz Absorption% @3GHz Reflection dB 100MHz-3GHz
Example 1 45um 21 49 -14
Example 2 50um 50 30 70
Example 3 100um 32 90 -7
Example 4 100um 22 88 -8
Example 5 50um 27 68 -8
Example 6 50um 4 26 -20
Comparative group 1 100um 10 43 -10
Comparative group 2 50um 20 75 -9
Bending test data:
Figure DEST_PATH_IMAGE002
the present invention is not limited to the above embodiments, and any technical solutions similar or identical to the present invention, which are made in the light of the present invention, are within the scope of the present invention.
The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.

Claims (7)

1. A high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties is characterized by comprising the following raw materials in percentage by volume: the volume ratio of the fibrous conductive carbon fiber is 2.5-12%, the volume ratio of carbonyl iron powder is 45-70%, the volume ratio of resin is 20-22%, and the volume ratio of the flame retardant is 5-8%.
2. The high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties according to claim 1, wherein the flame retardant comprises melamine polyphosphate, magnesium hydroxide and hydrotalcite, preferably magnesium hydroxide and melamine polyphosphate.
3. The high-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties according to claim 1, wherein the carbonyl iron powder is spherical and has an average particle size of 1-10 um.
4. The high-frequency-band wave-absorbing material with flame retardance and oxidation resistance according to claim 1, wherein the fibrous conductive carbon is fibrous carbon obtained by processing carbon fibers, preferably chopped fibers with the fiber length of 3-24 mm or ground fibers with the fiber length of 30-150 μm.
5. The material of claim 1, wherein the resin is a styrene elastomer, an olefin elastomer, a polyester elastomer, a polyamide elastomer, a polyurethane elastomer, or a silicone elastomer.
6. The high-frequency band wave-absorbing material with flame-retardant and oxidation-resistant properties as claimed in claim 1, wherein the styrene elastomer includes SEBS styrene ethylene butylene styrene block copolymer, which can be used by mixing acrylic resin, epoxy resin, polyolefin resin.
7. The high-frequency-band wave-absorbing material with flame retardant and oxidation resistance of claim 1, wherein the high-frequency-band wave-absorbing material with flame retardant and oxidation resistance contains an antioxidant, the volume ratio of the antioxidant is 0.5-3%, the antioxidant comprises 2', 3-bis [3- [3, 5-tert-butyl-4-hydroxyphenyl ] acrylate ] propionohydrazide, the antioxidant of the resin comprises tetracyanoyl [ trimethylene-3- (3 ', 5' -butyl-4 ' -hydroxyphenyl) propionate ], tris- (3, 5-butyl-4-hydroxybenzyl) -isocyanurate, N, N ' -hexamethylene bis (3, 5-butyl-4-hydroxy 10-amide), the one compatible with the resin is preferred.
CN201911233580.8A 2019-12-05 2019-12-05 High-frequency-band wave-absorbing material with flame-retardant and oxidation-resistant properties Pending CN111019285A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000021618A (en) * 1998-07-03 2000-01-21 Tokin Corp Powder magnetic core
JP2007129179A (en) * 2005-10-03 2007-05-24 Toda Kogyo Corp Conductive/magnetic filler, electromagnetic wave interference controlling sheet, flat cable for high frequency signal, flexible printed circuit board and method for manufacturing the sheet

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000021618A (en) * 1998-07-03 2000-01-21 Tokin Corp Powder magnetic core
JP2007129179A (en) * 2005-10-03 2007-05-24 Toda Kogyo Corp Conductive/magnetic filler, electromagnetic wave interference controlling sheet, flat cable for high frequency signal, flexible printed circuit board and method for manufacturing the sheet
TW200840467A (en) * 2005-10-03 2008-10-01 Toda Kogyo Corp Conductive/magnetic filler, electromagnetic wave interference controlling sheet using the same and usage thereof, and method for manufacturing the sheet

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