CN114773975A - Water-based infrared stealth coating and preparation method and application thereof - Google Patents

Water-based infrared stealth coating and preparation method and application thereof Download PDF

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CN114773975A
CN114773975A CN202210215872.4A CN202210215872A CN114773975A CN 114773975 A CN114773975 A CN 114773975A CN 202210215872 A CN202210215872 A CN 202210215872A CN 114773975 A CN114773975 A CN 114773975A
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infrared stealth
water
infrared
coating
phase
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CN114773975B (en
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何文龙
王书传
潘伟超
王诗榕
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Quanzhou Xinhe Graphene Research Institute Co ltd
XINHE NEW MATERIAL CO Ltd
Xinhe New Material Suzhou Co ltd
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XINHE NEW MATERIAL CO Ltd
Xinhe New Material Suzhou Co ltd
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Abstract

The invention discloses a water-based infrared stealth coating and a preparation method and application thereof, wherein the water-based infrared stealth coating is prepared from the following raw materials in percentage by weight: 0.1-1.0% of wetting dispersant, 0.05-0.5% of defoamer, 0-20% of nano cesium tungsten bronze powder, 0-20% of nano indium tin oxide powder, 10-30% of aqueous aluminum silver paste, 30-50% of PU emulsion, 0.1-1% of bactericide, 0.1-1% of thickener, 2-6% of phase change microcapsule, 1-4% of hollow glass microsphere and the balance of deionized water. The problem that most of the existing infrared stealth coatings are solvent-based and do not meet the environmental protection requirement is solved. The coating prepared by the invention is applied to a wearable electrothermal film, so that the electrothermal film has cold-proof and warm-keeping functions by infrared electric heating and has infrared stealth capability.

Description

Water-based infrared stealth coating and preparation method and application thereof
Technical Field
The invention relates to the technical field of chemical coatings, in particular to a water-based infrared stealth coating and a preparation method and application thereof.
Background
In winter in severe cold environment, the temperature of the body periphery and exposed parts of individual soldiers often decreases during work (such as guard standing, patrol, latency, camping and the like), and if the individual soldiers do not effectively cold-proof protection in time, cold damage is easy to occur, the working capacity and efficiency are obviously affected, and serious persons even endanger life. Products manufactured by processing wearable electric heating films, such as infrared electric heating clothes, hats, scarves, insoles and the like, can enable vast officers and soldiers to feel warm experience brought by light and thin clothes in winter.
All objects on the earth emit infrared radiation all the time, and the infrared detection technology realizes the detection of targets by capturing infrared radiation energy. The infrared detection technology is an essential means for military reconnaissance and plays an indispensable role in modern military wars. With the intellectualization and the continuous improvement of the accuracy of the infrared detector, the survival of military targets on a battlefield faces huge threats, and the realization of the infrared stealth means of the heat source target is very important. Infrared stealth is the process of making the infrared radiation of a target close to or consistent with the surrounding environment, so that an enemy infrared detector cannot easily or cannot detect and identify the target object.
The method for realizing the infrared stealth technology mainly comprises the following steps: and the infrared radiation characteristic of the target is changed, the infrared radiation energy signal of the target is reduced, and the infrared radiation propagation path is adjusted. Among them, reducing the infrared radiation energy signal of a target is a main stealth means. The general method is to coat infrared stealth paint on the surface of a target, and the low infrared emissivity means of the coating is utilized to obviously reduce and change the heat radiation characteristic of the target, thereby greatly reducing the probability of the target being discovered by an infrared detecting instrument and achieving the purpose of infrared stealth. Patent No. CN 109867805A discloses a preparation method of a film material with infrared stealth function, which comprises the following steps: s1, dispersing and mixing the nano extinction material and the solvent resin, adding a certain amount of nano dielectric material, and uniformly mixing, wherein the solid content ratio of the nano extinction material, the resin and the nano dielectric material is (1-100) to (1-100); s2, uniformly coating the product obtained in the step S1 on a flexible substrate in a coating mode, soaking the flexible substrate in a poor solvent of resin for a period of time, and finally drying to obtain the porous film material with the infrared stealth function. The infrared radiation rate of the target can be obviously reduced, the possibility of detection by an infrared detector is effectively reduced, and the infrared radiation rate is low, the compatibility is good, the process is simple, the repeatability is good, the equipment requirement is low, and the like.
Most of the traditional infrared stealth coating is solvent type, a large amount of organic solvent is used in production, resources are wasted, the environment is polluted, and the volatilization of some toxic solvents in the construction process can generate adverse effects on human health and the environment. At present, relatively few reports of waterborne system infrared stealth coatings exist, for example, patent No. CN 102925050A discloses a preparation method of a waterborne infrared-laser composite stealth coating, which comprises the following steps: (1) preparing an adhesive, (2) preparing a filler, and (3) adding an anti-precipitation agent, a dispersing agent, a leveling agent, an anti-aging agent, a defoaming agent, a thickening agent and the like into the adhesive and the filler, and preparing the aqueous infrared-laser composite stealth coating through the processes of high-speed dispersion, grinding, sieving, coating, drying and the like. The adhesive and the auxiliary agent used in the invention are water-soluble, and are mixed with the filler which is uniformly dispersed to prepare the coating, uniform and stable slurry can be obtained, and the coating is coated on a carrier, so that a target object has the infrared and laser compound stealth capability, and the purpose of infrared-laser compound stealth is achieved.
Disclosure of Invention
Therefore, aiming at the content, the invention provides the water-based infrared stealth coating and the preparation method and the application thereof, and solves the problem that the existing infrared stealth coating is mostly solvent-based and does not meet the environmental protection requirement.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the water-based infrared stealth coating comprises the following raw materials in percentage by weight:
Figure BDA0003534611170000031
the further improvement is that: the wetting dispersant is an acrylic block copolymer containing pigment affinity groups.
The further improvement is that: the defoaming agent is a mixture of any one or more than two of organic silicon defoaming agent, non-silicone organic ester hydrocarbon and mineral oil defoaming agent containing hydrophobic particles mixed in any ratio.
The further improvement is that: the nano cesium tungsten bronze powder has the appearance: blue-black powder, content: not less than 99.9%, primary particle size: 30 to 100 nm.
The further improvement is that: the nano indium tin oxide powder has the appearance: blue-gray powder, content: not less than 99.99%, primary particle size: 20-80 nm.
The further improvement is that: the PU emulsion has the solid content of 40 +/-1%, the pH value of 7.0-9.0, the tensile strength of 20MPa and the elongation of 700%.
The further improvement is that: the active ingredient of the bactericide is isothiazolinone.
The further improvement is that: the thickener is a mixture of one or two of polyurethane thickener or modified polyurea thickener mixed in any ratio.
The further improvement is that: the phase change microcapsule is prepared by the following steps:
(1) dissolving diisocyanate, polyether polyol and stannous octoate in an organic solvent, and reacting for 90-150 min at 65-75 ℃ to generate a prepolymer with an end isocyanate group, wherein the mass ratio of the diisocyanate to the polyether polyol to the stannous octoate is 15-30: 32-64: 0.1-0.3;
(2) dissolving C12-C18 straight-chain alkane and prepolymer in a toluene solvent to form an oil phase;
(3) dissolving sodium dodecyl sulfate in deionized water to form a water phase;
(4) mixing the water phase and the oil phase, shearing and emulsifying to obtain emulsion, adding ethylene glycol and 1, 3-xylyl diamine, reacting for 1-2 hours at 64-72 ℃, and filtering, washing and drying after the reaction is finished to obtain the phase-change microcapsule.
The further improvement is that: the mass ratio of the C12-C18 straight-chain alkane, the prepolymer, the deionized water, the sodium dodecyl sulfate, the ethylene glycol and the 1, 3-xylyl diamine is 1: 0.6-1: 5-10: 0.08-0.18: 0.05-0.1: 0.01-0.02.
The further improvement is that: the particle size of the hollow glass beads is 25-40 mu m.
The invention also provides a preparation method of the water-based infrared stealth coating, which comprises the following steps:
s1, weighing the raw material components in proportion for later use;
s2, sequentially adding deionized water, a wetting dispersant, a defoaming agent, a phase change microcapsule, hollow glass beads, nano cesium tungsten bronze powder and nano indium tin oxide powder into a stirring cylinder, stirring and dispersing uniformly at a rotating speed of 800-1000 r/min, then transferring into a grinding machine, fully grinding until the fineness is less than 5 microns, then reducing the rotating speed to 200-400 r/min, adding aqueous aluminum paste, PU emulsion, a bactericide and a thickening agent to obtain the aqueous infrared stealth coating, detecting the obtained product, filtering after the product is qualified, and packaging.
The invention also provides application of the water-based infrared stealth coating or the water-based infrared stealth coating obtained by the preparation method in a wearable electrothermal film. The specific application mode is as follows: coating the water-based infrared stealth coating on the outer surface of the wearable electric heating film in a screen printing, brush coating or spraying manner, and drying by utilizing a natural air drying or infrared heating drying manner, wherein the infrared drying temperature is 80 ℃ and the time is 15 min.
The Stepan-Boltzmann law is an important law in thermodynamics, and the main contents are as follows: the total energy E emitted per unit area of the black body surface per unit time (called the radiation intensity of the object) is proportional to the fourth power of the absolute temperature T of the black body itself, i.e. E ∈ σ T4. In the formula: ε is the emissivity and σ is the Spandella-Boltzmann constant.
By adopting the technical scheme, the invention has the beneficial effects that:
the application takes the water-based PU emulsion as a film forming substance, and overcomes the defects of the solvent-based infrared stealth coating. The waterborne polyurethane coating is convenient to construct, and the cured coating has excellent acid and alkali resistance and adhesive force, but has higher infrared reflectivity. According to the preparation method, the waterborne aluminum paste, the nano cesium tungsten bronze powder and the nano indium tin oxide powder are used as fillers and added into a formula system, so that the waterborne aluminum paste has an excellent infrared radiation prevention function and can greatly reduce the infrared emissivity of a coating; compare in waterborne aluminum paste, the infrared emission rate of nanometer cesium tungsten bronze powder, nanometer indium oxide tin powder is high, but nanometer cesium tungsten bronze powder, nanometer indium oxide tin powder have the characteristic of absorbing infrared ray, through the shared proportion of the different fillers of reasonable adjustment, can allocate the coating of different infrared emission rates.
According to the Stepan-Boltzmann law, in order to reduce the infrared radiation intensity of the target and achieve the purpose of stealth, measures for reducing the infrared emissivity of the target can be taken, and the infrared emissivity can be realized by controlling the surface temperature of the target. The single control temperature or the infrared emissivity of the changed target has certain limitation, and the more ideal infrared stealth effect can be realized through the cooperation of the single control temperature and the infrared emissivity. For this reason, the following improvements are made in the present application: firstly, a phase-change material is added into a formula, the phase-change material has the characteristic of changing the physical state within a certain temperature range, and the purpose of regulating and controlling the temperature by utilizing the characteristic can be achieved. In addition, the phase-change microcapsule is prepared by taking the phase-change material as a core material and polyurethane as a wall material through interfacial polymerization and added into a formula system, so that the purpose of providing a stable phase-change space is achieved, the use efficiency of the phase-change material is improved, the compatibility of the microcapsule and the aqueous PU emulsion can be improved by taking the polyurethane as the wall material, and the phase-change microcapsule is uniformly dispersed in the system. Secondly, hollow glass beads are added into the formula. The hollow glass beads are hollow, spherical and light inorganic functional particles, have the advantages of low density, low thermal conductivity, easy dispersion, good chemical stability and the like, can improve the mechanical property of the coating when added into a coating system, can effectively block heat flow transfer, weaken the temperature characteristic of the surface of a target, and finally weaken the infrared radiation intensity of the target. The reason why the particle size is 25-40 μm is that the hollow glass beads are found to have low compressive strength due to a thin shell and a large cavity volume in the test process, and are easy to crack in the use process, and the particles with too large or too small particle sizes are easy to crush in the preparation process and cannot play the due role.
The working principle of the infrared thermal imaging detector is that a target object is distinguished from a background environment by using the radiation intensity difference of the target and the background in two wave bands of 3-5 micrometers and 8-14 micrometers. The water-based infrared stealth coating prepared by the invention is coated on the outer surface of the electric heating film, and the infrared radiation intensity of the outer surface of the electric heating film can be obviously reduced, so that the probability of being discovered by an infrared detecting instrument is greatly reduced, and the electric heating film has the function of cold protection and warm keeping while having the infrared stealth capability through infrared electric heating.
Detailed Description
The following detailed description will be given with reference to specific embodiments, so that how to apply the technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Unless otherwise indicated, the techniques employed in the examples are conventional and well known to those skilled in the art, and the reagents and products employed are also commercially available. The source, trade name and if necessary the constituents of the reagents used are indicated at the first appearance.
Example 1
A water-based infrared stealth coating is composed of the following raw materials in percentage by weight:
Figure BDA0003534611170000071
the nano cesium tungsten bronze powder has the appearance: blue-black powder, content: not less than 99.9%, primary particle size: 100 nm. The PU emulsion has the solid content of 40 +/-1%, the pH value of 7.0-9.0, the tensile strength of 20MPa and the elongation of 700%. The active ingredient of the bactericide is isothiazolinone. The particle size of the hollow glass bead is 25 μm.
The phase change microcapsule is prepared by the following steps:
(1) dissolving diisocyanate, polyether polyol and stannous octoate in an organic solvent, reacting for 150min at 65 ℃ to generate a prepolymer with a terminal isocyanate group, wherein the mass ratio of the diisocyanate to the polyether polyol to the stannous octoate is 15:32:0.1, the polyether polyol is polyoxypropylene polyol with the hydroxyl value of 368mgKOH/g,
(2) dissolving dodecane and the prepolymer in a toluene solvent to form an oil phase;
(3) dissolving sodium dodecyl sulfate in deionized water to form a water phase;
(4) mixing the water phase and the oil phase, shearing and emulsifying to obtain emulsion, adding ethylene glycol and 1, 3-xylyl diamine, reacting for 2h at 64 ℃, filtering, washing and drying after the reaction is finished to obtain the phase-change microcapsule. The mass ratio of the dodecane, the prepolymer, the deionized water, the sodium dodecyl sulfate, the ethylene glycol and the 1, 3-xylyl diamine is 1:0.6:5:0.08:0.05: 0.01.
The preparation method of the water-based infrared stealth coating comprises the following steps:
s1, weighing the raw material components in proportion for later use;
s2, sequentially adding deionized water, a wetting dispersant, a defoaming agent, a phase change microcapsule, hollow glass beads and nano cesium tungsten bronze powder into a stirring cylinder, stirring and dispersing uniformly at the rotating speed of 800r/min, then transferring into a grinding machine, fully grinding until the fineness is less than 5 microns, then reducing the rotating speed to 200r/min, adding aqueous aluminum silver paste, PU emulsion, a bactericide and a thickening agent to obtain the aqueous infrared stealth coating, detecting the obtained product, filtering and packaging after the detection is qualified.
Example 2
A water-based infrared stealth coating is composed of the following raw materials in percentage by weight:
Figure BDA0003534611170000081
the wetting dispersant is produced by German Vockel company and has the model number of
Figure BDA0003534611170000082
Disper 9171 wets the dispersant. The defoaming agent is a mineral oil defoaming agent which is produced by Germany and modest and has the model of DefomoW-086 containing hydrophobic particles. The nano indium tin oxide powder has the appearance: blue-gray powder, content: not less than 99.99%, primary particle size: 50 nm. The particle size of the hollow glass bead is 40 μm.
The phase change microcapsule is prepared by the following steps:
(1) dissolving diisocyanate, polyether polyol and stannous octoate in an organic solvent, and reacting at 70 ℃ for 120min to generate a prepolymer with a terminal isocyanate group, wherein the mass ratio of the diisocyanate to the polyether polyol to the stannous octoate is 24:50:0.2, and the polyether polyol is polytetrahydrofuran polyether polyol with a hydroxyl value of 374 mgKOH/g;
(2) dissolving hexadecane and the prepolymer in a toluene solvent to form an oil phase;
(3) dissolving sodium dodecyl sulfate in deionized water to form a water phase;
(4) mixing the water phase and the oil phase, shearing and emulsifying to obtain emulsion, adding ethylene glycol and 1, 3-xylyl diamine, reacting at 68 ℃ for 1.5h, and filtering, washing and drying after the reaction is finished to obtain the phase-change microcapsule. The mass ratio of the hexadecane to the prepolymer to the deionized water to the sodium dodecyl sulfate to the ethylene glycol to the 1, 3-xylyl diamine is 1:0.8:8:0.13:0.08: 0.015.
The preparation method of the water-based infrared stealth coating comprises the following steps:
s1, weighing the raw material components in proportion for later use;
s2, sequentially adding deionized water, a wetting dispersant, a defoaming agent, a phase change microcapsule, hollow glass beads and nano indium tin oxide powder into a stirring cylinder, stirring and dispersing uniformly at the rotating speed of 900r/min, then transferring into a grinding machine, fully grinding until the fineness is less than 5 mu m, reducing the rotating speed to 300r/min, adding aqueous aluminum paste, PU emulsion, a bactericide and a thickening agent to obtain the aqueous infrared stealth coating, detecting the obtained product, filtering after the detection is qualified, and packaging.
Example 3
The water-based infrared stealth coating comprises the following raw materials in percentage by weight:
Figure BDA0003534611170000091
Figure BDA0003534611170000101
the nano cesium tungsten bronze powder has the appearance: blue-black powder, content: not less than 99.9%, primary particle size: 30 nm. The nano indium tin oxide powder has the appearance: blue-gray powder, content: not less than 99.99%, primary particle size: 20 nm. The particle size of the hollow glass bead is 35 μm.
The phase change microcapsule is prepared by the following steps:
(1) dissolving diisocyanate, polyether polyol and stannous octoate in an organic solvent, and reacting for 90min at 75 ℃ to generate a prepolymer with a terminal isocyanate group, wherein the mass ratio of the diisocyanate to the polyether polyol to the stannous octoate is 30:64:0.3, and the polyether polyol is polyoxypropylene polyol with a hydroxyl value of 353 mgKOH/g;
(2) dissolving tetradecane and prepolymer in a toluene solvent to form an oil phase;
(3) dissolving sodium dodecyl sulfate in deionized water to form a water phase;
(4) mixing the water phase and the oil phase, shearing and emulsifying to obtain emulsion, adding ethylene glycol and 1, 3-xylyl diamine, reacting for 1 hour at 72 ℃, and filtering, washing and drying after the reaction is finished to obtain the phase-change microcapsule. The mass ratio of tetradecane to prepolymer to deionized water to sodium dodecyl sulfate to ethylene glycol to 1, 3-xylyl diamine is 1:1:10:0.18:0.1: 0.02.
The invention also provides a preparation method of the water-based infrared stealth coating, which comprises the following steps:
s1, weighing the raw material components in proportion for later use;
s2, sequentially adding deionized water, a wetting dispersant, a defoaming agent, a phase change microcapsule, hollow glass beads, nano cesium tungsten bronze powder and nano indium tin oxide powder into a stirring cylinder, uniformly stirring and dispersing at the rotating speed of 1000r/min, transferring into a grinding machine, fully grinding until the fineness is less than 5 microns, reducing the rotating speed to 400r/min, adding aqueous aluminum paste, PU emulsion, a bactericide and a thickening agent to obtain the aqueous infrared stealth coating, detecting the obtained product, filtering and packaging after the product is qualified.
Performance test
The aliphatic isocyanate curing agent is added into the water-based infrared stealth coating prepared in the embodiment 1-3, the mixture is dispersed at a high speed and uniformly mixed, then the mixture is respectively sprayed on clean tinplate by a spray gun, and after the surface of the coating is dried, the coating is placed in an oven to be dried for 6 hours at the temperature of 60-80 ℃ to form the coating. The properties of the coating, as measured by national standards, are shown in the following table:
Figure BDA0003534611170000111
the above table shows that the coating prepared by the invention has low infrared emissivity in the wavelength ranges of 3-5 μm and 8-14 μm, has good water resistance, alkali resistance and resistivity, is a low infrared emissivity coating with good comprehensive performance, and can meet the requirement of practicability.
It should be understood that the above description is only an example of the technical disclosure, and any modifications and variations made by those skilled in the art can be covered by the present disclosure, and not limited by the embodiments disclosed in the present disclosure.

Claims (10)

1. A water-based infrared stealth paint is characterized in that: the composite material consists of the following raw materials in percentage by weight:
Figure FDA0003534611160000011
2. the aqueous infrared stealth paint of claim 1, characterized in that: the wetting dispersant is an acrylic block copolymer containing pigment affinity groups.
3. The aqueous infrared stealth paint of claim 1, characterized in that: the defoaming agent is any one or a mixture of more than two of organic silicon defoaming agent, non-silicone organic ester hydrocarbon and mineral oil defoaming agent containing hydrophobic particles mixed in any ratio.
4. The aqueous infrared stealth paint of claim 1, characterized in that: the nano cesium tungsten bronze powder has the appearance: blue-black powder, content: not less than 99.9%, primary particle size: 30 to 100 nm.
5. The aqueous infrared stealth paint of claim 1, characterized in that: the nano indium tin oxide powder has the appearance: blue-gray powder, content: not less than 99.99%, primary particle size: 20-80 nm.
6. The aqueous infrared stealth paint of claim 1, characterized in that: the PU emulsion has the solid content of 40 +/-1%, the pH value of 7.0-9.0, the tensile strength of 20MPa and the elongation of 700%.
7. The aqueous infrared stealth paint of claim 1, characterized in that: the active ingredient of the bactericide is isothiazolinone.
8. The aqueous infrared stealth paint of claim 1, characterized in that: the thickener is a mixture of one or two of polyurethane thickener or modified polyurea thickener mixed in any ratio.
9. The aqueous infrared stealth paint of claim 1, characterized in that: the phase change microcapsule is prepared by the following steps:
(1) dissolving diisocyanate, polyether polyol and stannous octoate in an organic solvent, and reacting for 90-150 min at 65-75 ℃ to generate a prepolymer with an end isocyanate group, wherein the mass ratio of the diisocyanate to the polyether polyol to the stannous octoate is 15-30: 32-64: 0.1-0.3;
(2) dissolving C12-C18 straight-chain alkane and prepolymer in a toluene solvent to form an oil phase;
(3) dissolving sodium dodecyl sulfate in deionized water to form a water phase;
(4) mixing the water phase and the oil phase, shearing and emulsifying to obtain emulsion, adding ethylene glycol and 1, 3-xylyl diamine, reacting for 1-2 h at 64-72 ℃, filtering, washing and drying after the reaction is finished to obtain the phase-change microcapsule.
10. The aqueous infrared stealth paint of claim 9, wherein: the mass ratio of the C12-C18 straight chain alkane, the prepolymer, the deionized water, the sodium dodecyl sulfate, the ethylene glycol and the 1, 3-xylyl diamine is 1: 0.6-1: 5-10: 0.08-0.18: 0.05-0.1: 0.01-0.02.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104060474A (en) * 2014-06-05 2014-09-24 常州大学 Preparation method of stealth fabric with radar stealth and infrared stealth functions
CN104762809A (en) * 2015-04-10 2015-07-08 南通科尔纺织服饰有限公司 Nano-stealth material and application thereof in infrared camouflage fabric
CN105040469A (en) * 2015-06-30 2015-11-11 浙江捷凯实业有限公司 Military invisible fabric
CN105316945A (en) * 2015-06-26 2016-02-10 浙江盛发纺织印染有限公司 Double-side coating fabric
CN106582463A (en) * 2016-12-15 2017-04-26 上海雅运纺织助剂有限公司 Polyurethane microcapsule dispersing agent preparation method and product thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104060474A (en) * 2014-06-05 2014-09-24 常州大学 Preparation method of stealth fabric with radar stealth and infrared stealth functions
CN104762809A (en) * 2015-04-10 2015-07-08 南通科尔纺织服饰有限公司 Nano-stealth material and application thereof in infrared camouflage fabric
CN105316945A (en) * 2015-06-26 2016-02-10 浙江盛发纺织印染有限公司 Double-side coating fabric
CN105040469A (en) * 2015-06-30 2015-11-11 浙江捷凯实业有限公司 Military invisible fabric
CN106582463A (en) * 2016-12-15 2017-04-26 上海雅运纺织助剂有限公司 Polyurethane microcapsule dispersing agent preparation method and product thereof

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