RU2779210C1 - Composite material with closed pores, heat-insulating material, soundproof material and their manufacturing method - Google Patents

Abstract

FIELD: composite materials.

SUBSTANCE: present invention relates to composite material with closed pores, heat-insulating material, soundproof material, and a method for their manufacture. The method for the manufacture of composite material with closed pores includes: obtaining a mixture containing 30-70 parts by weight of resin dispersed in water, 10-300 parts by weight of non-expanded heat-expanding microspheres, 100-550 parts by weight of water, mixing of the mixture, preparation of a carrier, application of a layer of the resulting mixture to the carrier, heating of the mixture layer and the carrier for a certain time, during which non-expanded heat-expanding microspheres are expanded, to obtain composite material with closed pores, containing multilayer coating of the mixture. At the same time, non-expanded heat-expanding microspheres are hollow spherical or pseudo-spherical, with walls containing thermoplastic or heat-curing polymer materials, and the resulting composite material with closed pores contains a set of closed cavities and polymer walls, which separate closed cavities from each other. Moreover, the range of sizes of closed cavities is from 20 mcm to 800 mcm, and the ratio of the total volume of closed cavities and the total volume of polymer walls is more than 16. Heat- insulating material, according to the invention, is significantly superior to traditional heat-insulating materials in passage of as much air as possible and prevention of the circulation of air carried by material with the outside air, and therefore it can be used not only for heat preservation and heat insulation, but can also be widely used in other areas, such as sound insulation and sound absorption.

EFFECT: obtaining composite material with closed pores, heat-insulating material, and soundproof material.

26 cl, 6 tbl, 17 dwg

Description

FIELD OF TECHNOLOGY TO WHICH THE INVENTION RELATES

The present invention relates to a closed-cell composite material, a heat-insulating material, a noise-insulating material and a method for their manufacture.

BACKGROUND OF THE INVENTION

"Food, clothing, housing and transport" are issues of paramount importance that human civilization has faced and solved since its inception. People are puzzled by the problem of protection from the cold in winter, except for people living in the tropics and Greece. With the development of technology, people have learned to use animal fur, cotton, down and other materials to make clothes that can protect from the cold, and with the use of the above clothes, people can stay outside for a long time even in cold winter. However, all of the above clothing is bulky and heavy. On the one hand, heavy clothing hinders the movements of the body, on the other hand, it does not meet the aesthetic needs of a person. The last drawback is especially noteworthy for women who want to show off their attractive curves in the cold winter. Imagine this fascinating picture: if the “innovative thermal insulation material” is widely used to make winter clothes, when walking in a cold area covered with snow, men can walk in a fashionable jacket, and women can wear a beautiful dress made of “innovative thermal insulation material”.

DISCLOSURE OF THE INVENTION

According to one embodiment of the present invention, a method for manufacturing a closed cell composite material is provided, the method comprising:

1) obtaining a mixture, wherein the mixture contains 30-70 parts by weight of water-dispersible resin, 10-300 parts by weight of non-expanded thermally expandable microspheres, 100-550 parts by weight of water, and stirring the mixture;

2) media preparation;

3) applying a layer of the mixture obtained in step 1) onto a support;

4) heating the layer of the mixture and the carrier for a certain time, during which the non-expanded thermally expanding microspheres expand;

5) repeating steps 3) - 4) several times to obtain a composite material with closed pores containing a multilayer coating of the mixture.

According to one embodiment of the present invention, for example, the mixture from step 1) contains 40-60 parts by weight of water-dispersible resin, 10-50 parts by weight of non-expanded thermally expandable microspheres, 80-350 parts by weight of water.

According to one embodiment of the present invention, for example, the mixture from step 1) contains 45-55 parts by weight of water-dispersible resin, 10-30 parts by weight of non-expanded thermally expandable microspheres, 100-250 parts by weight of water.

According to one embodiment of the present invention, for example, non-expanded thermally expandable microspheres are hollow spherical or pseudo-spherical with an outer diameter of 10 μm to 40 μm and a wall thickness of 1 μm to 10 μm, the walls comprising thermoplastic or thermoset polymeric materials.

According to one embodiment of the present invention, for example, the water-dispersible resin comprises two kinds of different water-based polyurethane dispersions, one being 1-25 parts by weight and the other being 49-25 parts by weight.

According to one embodiment of the present invention, for example, two kinds of different water-based polyurethane dispersions are respectively a first anionic polyurethane dispersion based on an aliphatic polyester and a second anionic polyurethane dispersion based on an aliphatic polyester, wherein the first anionic polyurethane dispersion based on an aliphatic polyester is by weight 10-20 parts, preferably 15 parts; while the second anionic polyurethane dispersion based on aliphatic polyester is 40-30 parts by weight, preferably 35 parts.

According to one embodiment of the present invention, for example, the mixture from step 1) further comprises at least one of: an antifoam agent in an amount of 0-1 parts by weight, a curing agent in an amount of 0-10 parts by weight, a thickener in an amount of 0-10 parts by weight, mold inhibitor 0-5 parts by weight, wetting and leveling agent 0-2 parts by weight, tactile modifier 0-5 parts by weight, water-based pigment 0-20 parts by weight;

preferably the mixture from step 1) additionally contains at least one of: an antifoam agent in an amount of 0.1-1 parts by weight, a curing agent in an amount of 0.1-10 parts by weight, a thickener in an amount of 0.1-10 parts by weight , mold inhibitor 0.1-5 parts by weight, wetting and leveling agent 0.1-2 parts by weight, tactile modifier 0.1-5 parts by weight, water-based pigment in amount of 0.1-20 parts by weight.

According to one embodiment of the present invention, for example, in step 4) the carrier is heated to 100-180°C for 10-300 seconds; preferably the media is heated to 120-160°C for 60-120 seconds; preferably the media is heated to 130-150°C for 60-90 seconds; preferably the media is heated to 140-150°C for 60-80 seconds.

According to one embodiment of the present invention, for example, the water-dispersible resin comprises at least one selected from the group consisting of water-dispersible polyurethane resin, water-dispersible acrylic resin, water-dispersible polyurethane-modified acrylic resin, butyl cyanide emulsion, chloroprene latex. and polyvinyl acetate latex.

According to one embodiment of the present invention, for example, the curing agent comprises at least one selected from the group consisting of a polycarbodiimide, a polyisocyanate, a blocked polyisocyanate, an aziridine, and an amino resin; the defoamer is a silicone defoamer; the wetting and leveling agent is a silicone wetting and leveling agent; the tactile sensation enhancer comprises at least one selected from the group consisting of high molecular weight organosilicon compounds, powdered wax, wax emulsion, colloidal or precipitated silica, and a liquid for dispersing them; the mold inhibitor includes an organic or inorganic water-dispersible mold inhibitor; the thickener comprises at least one selected from the group consisting of a polyurethane associative thickener, an alkali-swellable acrylic thickener, a cellulose thickener, and an inorganic thickener.

According to one embodiment of the present invention, for example, the carrier comprises at least one selected from the group consisting of woven fabric, nonwoven fabric, leather, and elastic film.

According to one embodiment of the present invention, for example, the ratio of the size of the expanded thermally expandable microspheres in step 4) to the size of the non-expanded thermally expandable microspheres in step 1) is between 2 and 10.

According to one embodiment of the present invention, for example, the closed cell composite material comprises a plurality of closed cavities and polymeric walls that separate the closed cavities from each other; while the size range of closed cavities is from 20 µm to 800 µm, preferably the size range of closed cavities is from 50 µm to 300 µm, preferably the size range of closed cavities is from 60 µm to 200 µm, even more preferably the size range of closed cavities is from 80 microns up to 120 microns; and the ratio of the total volume of closed cavities and the total volume of the polymer walls is more than 3; preferably, the ratio of the total volume of the closed cavities and the total volume of the polymer walls is more than 3.33; preferably, the ratio of the total volume of the closed cavities and the total volume of the polymer walls is more than 16; preferably, the ratio of the total volume of the closed cavities and the total volume of the polymer walls is more than 33; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 83; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 166; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 333; preferably, the ratio of the total volume of the closed cavities and the total volume of the polymer walls is more than 417; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 556; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 833; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 1667.

According to one embodiment of the present invention, for example, the closed-cell composite material is a thermal insulation (thermal insulation) material, while the thermal insulation material contains a plurality of closed cavities and polymer walls that separate the closed cavities from each other, while if the thickness of the thermal insulation material is 1 mm, the clo value of thermal insulation material is greater than or equal to 0.20, or greater than or equal to 0.40, or greater than or equal to 0.50, or greater than or equal to 0.60, or greater than or equal to 1.0, or greater or equals 1.5.

According to one embodiment of the present invention, for example, the closed cell composite material is composed of a plurality of closed cavities and polymeric walls that separate the closed cavities from each other, wherein the size range of the closed cavities is from 20 µm to 800 µm, preferably the size range of the closed cavities is from 50 µm to 300 µm, preferably the size range of the closed cavities is from 60 µm to 200 µm, even more preferably the size range of the closed cavities is from 80 µm to 120 µm; wherein the density of the closed cell composite material is from 5 kg/m ³ to 300 kg/m ³ , preferably the density of the closed cell composite material is from 10 kg/m ³ to 200 kg/m ³ , preferably the density of the closed cell composite material is from 20 kg/m ³ to 150 kg/m ³ , preferably the density of the closed cell composite material is from 30 kg/m ³ to 100 kg/m ³ , preferably the density of the closed cell composite material is from 40 kg/m ³ to 90 kg/m ³ , preferably the density of the closed cell composite is 50 kg/m ³ to 80 kg/m ³ , preferably the density of the closed cell composite is 60 kg/m ³ to 80 kg/m ³ .

According to one embodiment of the present invention, a closed cell composite material is provided, wherein the closed cell composite material comprises a plurality of closed cavities and polymeric walls that separate the closed cavities from one another; while the size range of closed cavities is from 20 µm to 800 µm, preferably the size range of closed cavities is from 50 µm to 300 µm, preferably the size range of closed cavities is from 60 µm to 200 µm, even more preferably the size range of closed cavities is from 80 microns up to 120 microns; and the ratio of the total volume of closed cavities and the total volume of the polymer walls is more than 3; preferably, the ratio of the total volume of the closed cavities and the total volume of the polymer walls is more than 3.33; preferably, the ratio of the total volume of the closed cavities and the total volume of the polymer walls is more than 16; preferably, the ratio of the total volume of the closed cavities and the total volume of the polymer walls is more than 33; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 83; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 166; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 333; preferably, the ratio of the total volume of the closed cavities and the total volume of the polymer walls is more than 417; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 556; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 833; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 1667.

According to one embodiment of the present invention, for example, the closed cell composite material consists of a plurality of closed cavities and polymeric walls that separate the closed cavities from each other.

According to one embodiment of the present invention, for example, the polymer walls comprise a thermoplastic or thermoset polymer on the inside of the relatively closed cavities, and the polymer walls contain a water-dispersible resin on the outside of the relatively closed cavities.

According to one embodiment of the present invention, for example, the thickness of the polymer walls is from 0.02 µm to 2 µm; preferably the thickness of the polymer walls is from 0.03 μm to 1.0 μm; preferably the thickness of the polymer walls is from 0.04 µm to 0.8 µm; preferably the thickness of the polymer walls is from 0.05 µm to 0.6 µm; preferably, the thickness of the polymeric walls is between 0.1 µm and 0.5 µm.

According to one embodiment of the present invention, for example, the shape of the closed cavities includes spherical, pseudospherical, and irregular shapes.

According to one embodiment of the present invention, for example, closed cavities are formed by increasing the diameter of non-expanded thermally expandable microspheres by a factor of 2-10.

According to one embodiment of the present invention, for example, the closed cell composite material is a thermal insulation material, wherein if the thickness of the thermal insulation material is 0.2 to 3.0 mm, the clo value of the thermal insulation material is from 0.1 to 3, 0.

According to one embodiment of the present invention, for example, the polymeric walls have a three-layer structure, wherein the three-layer structure comprises two outer layers and an intermediate layer located between the two outer layers, wherein the materials of the two outer layers are the same and the materials of the two outer layers are different from material of the intermediate layer located between the two outer layers.

According to one embodiment of the present invention, for example, the carrier comprises at least one selected from the group consisting of woven fabric, nonwoven fabric, leather, and elastic film.

According to one embodiment of the present invention, for example, the closed cell composite material comprises a carrier and a thermal barrier layer attached to the carrier, wherein the thickness of the carrier is between 0.1 mm and 5.0 mm and the thickness of the thermal barrier layer is between 0.2 mm up to 10 mm.

According to one embodiment of the present invention, for example, both surfaces of the closed cell composite carrier are respectively attached to the thermal insulation layer, wherein the thickness of the carrier is between 0.1 mm and 5.0 mm, and the thickness of either thermal insulation layer is between 0.2 mm up to 10 mm.

According to one embodiment of the present invention, for example, the closed cell composite comprises two outer carriers and a thermal barrier layer sandwiched between the two carriers; wherein the thickness of any one of the two carriers is from 0.1 mm to 5.0 mm, and the thickness of the heat-insulating layer is from 0.2 mm to 10 mm.

According to one embodiment of the present invention, for example, the closed cell composite material comprises one carrier and a thermal barrier layer attached to the carrier, wherein the thermal barrier layer has a multilayer structure containing more than two layers; preferably the layer in direct contact with the carrier in the thermal insulation layer is called the base thermal insulation layer, the layer which is furthest from the carrier is called the upper thermal insulation layer, the layer(s) between the base layer and the upper layer are called(-are) intermediate(s) thermal insulation layer(s), while the content of thermally expanding microspheres in the base layer is greater than the content of thermally expanding microspheres in the upper layer and in the intermediate layer.

According to one embodiment of the present invention, for example, the base thermal barrier layer contains one kind of water-dispersible resin, and the top thermal insulation layer contains at least two different kinds of water-dispersible resin.

According to one embodiment of the present invention, for example, the non-expanded thermally expandable microspheres in different thermal insulation layers may be the same or different.

According to one embodiment of the present invention, for example, a plurality of closed cell composite materials are bonded together to form a single unit by adhesives, or one or more closed cell composite materials are bonded together with other materials by adhesives, wherein the amount of adhesive required for one bonding , ranges from 10 g/m ² to 25 g/m ² ; preferably the adhesive is at least one selected from the group consisting of a moisture-curable PU adhesive, a hot melt adhesive, a water-dispersible adhesive, and a solution adhesive.

According to one embodiment of the present invention, a thermal insulating material is provided, wherein the thermal insulating material comprises a plurality of closed cavities and polymeric walls that separate the closed cavities from each other, wherein if the thickness of the thermal insulating material is 1 mm, the clo value of the thermal insulating material is greater than or equal to 0 ,20, or greater than or equal to 0.40, or greater than or equal to 0.50, or greater than or equal to 0.60, or greater than or equal to 1.0, or greater than or equal to 1.5.

According to one embodiment of the present invention, for example, the thermal insulation material consists of a plurality of closed cavities and polymeric walls that separate the closed cavities from each other.

According to one embodiment of the present invention, for example, the size range of closed cavities is from 20 µm to 800 µm, preferably the size range of closed cavities is from 50 µm to 300 µm, preferably the size range of closed cavities is from 60 µm to 200 µm, even more preferably the size range of closed cavities is from 80 µm to 120 µm.

According to one embodiment of the present invention, for example, the thickness of the polymer walls is from 0.02 µm to 2 µm; preferably the thickness of the polymer walls is from 0.03 μm to 1.0 μm; preferably the thickness of the polymer walls is from 0.04 µm to 0.8 µm; preferably the thickness of the polymer walls is from 0.05 µm to 0.6 µm; preferably, the thickness of the polymeric walls is between 0.1 µm and 0.5 µm.

According to one embodiment of the present invention, for example, the polymeric walls have a three-layer structure, in which the materials of the two outer layers are the same, while the materials of the two outer layers are different from the material of the intermediate layer located between the two outer layers.

According to one embodiment of the present invention, a closed cell composite material is provided, wherein the closed cell composite material comprises a plurality of closed cavities and polymeric walls that separate the closed cavities from one another; while the size range of closed cavities is from 20 µm to 800 µm, preferably the size range of closed cavities is from 50 µm to 300 µm, preferably the size range of closed cavities is from 60 µm to 200 µm, even more preferably the size range of closed cavities is from 80 microns up to 120 microns; and the density of the closed cell composite material is from 5 kg/m ³ to 300 kg/m ³ , preferably the density of the closed cell composite material is from 10 kg/m ³ to 200 kg/m ³ , preferably the density of the closed cell composite material is from 20 kg/m ³ to 150 kg/m ³ , preferably the density of the closed-cell composite material is from 30 kg/m ³ to 100 kg/m ³ , preferably the density of the closed-cell composite material is from 40 kg/m ³ to 90 kg/m ³ , preferably the density of the closed cell composite is 50 kg/m ³ to 80 kg/m ³ , preferably the density of the closed cell composite is 60 kg/m ³ to 80 kg/m ³ .

According to one embodiment of the present invention, for example, the closed cell composite material consists of a plurality of closed cavities and polymeric walls that separate the closed cavities from each other.

According to one embodiment of the present invention, for example, the thickness of the polymer walls is from 0.01 µm to 5 µm; preferably the thickness of the polymer walls is from 0.02 μm to 2 μm; preferably the thickness of the polymer walls is from 0.03 μm to 1.0 μm; preferably the thickness of the polymer walls is from 0.04 µm to 0.8 µm; preferably the thickness of the polymer walls is from 0.05 µm to 0.6 µm; preferably, the thickness of the polymeric walls is between 0.1 µm and 0.5 µm.

According to one embodiment of the present invention, for example, the polymeric walls have a three-layer structure, in which the materials of the two outer layers are the same, while the materials of the two outer layers are different from the material of the intermediate layer located between the two outer layers.

According to one embodiment of the present invention, for example, the thermal conductivity of the closed cell composite material is less than 0.030 W/m⋅K; preferably, the thermal conductivity of the closed cell composite material is less than 0.025 W/m⋅K; preferably, the thermal conductivity of the closed cell composite material is less than 0.020 W/m⋅K; preferably, the thermal conductivity of the closed cell composite material is less than 0.016 W/m⋅K. Thermal conductivity is determined using the method described in Embodiments 26-36 of the present disclosure.

According to one embodiment of the present invention, a sound deadening material is provided, wherein the sound deadening material comprises the closed cell composite material described above.

According to one embodiment of the present invention, a sound absorbing material is provided, wherein the sound absorbing material comprises the closed cell composite material described above.

According to one embodiment of the present invention, a garment is provided, wherein the garment comprises the closed cell composite material described above; or the garment contains a thermal insulation material as described above.

According to one embodiment of the present invention, for example, the garment further comprises a fabric and a liner, with a closed cell composite or thermal insulation material positioned between the fabric and the liner.

According to one embodiment of the present invention, a tent is provided, wherein the tent comprises the closed cell composite material described above; or the tent contains the thermal insulation material described above.

According to one embodiment of the present invention, a sleeping bag is provided, wherein the sleeping bag comprises the closed cell composite material described above; or the sleeping bag contains the thermal insulation material described above.

According to one embodiment of the present invention, footwear is provided, wherein the footwear comprises the closed cell composite material described above; or the footwear contains the thermal insulation material described above.

According to one embodiment of the present invention, a wallpaper is provided, wherein the wallpaper comprises the closed cell composite material described above; or wallpaper contains the thermal insulation material described above.

According to one embodiment of the present invention, a body is provided, wherein the body comprises the closed cell composite material described above; or the body contains the thermal insulation material described above.

According to one embodiment of the present invention, an aircraft cabin is provided, wherein the aircraft cabin comprises the closed cell composite material described above; or the cockpit of the aircraft comprises a thermally insulating material as described above.

According to one embodiment of the present invention, a refrigerator is provided, wherein the refrigerator comprises the closed cell composite material described above; or the refrigerator contains the thermal insulation material described above.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to more clearly explain the technical solution of the embodiments of the present invention, the drawings of the embodiments will now be briefly presented. Obviously, the drawings in the following description relate only to some embodiments of the present invention, and should not be construed as limiting the present invention.

Fig. 1 is an optical microscopy image showing unexpanded thermally expandable microspheres used in embodiments of the present invention.

Fig. 2 is a transmission electron microscopy (TEM) image showing one non-expanded thermally expandable microsphere used in embodiments of the present invention.

Fig. 3 is a photomicrograph of the final product obtained according to one embodiment of the present invention, it can be seen in the micrograph that the majority of the expanded thermally expandable microspheres are in a regular spherical or pseudospherical shape;

fig. 4 is a scanning electron microscopy (SEM) image of the final product obtained according to one embodiment of the present invention;

fig. 5 is a scanning electron microscopy (SEM) image of the final product obtained according to another embodiment of the present invention;

fig. 6 is a scanning electron microscopy (SEM) image of the final product obtained according to another embodiment of the present invention;

fig. 7 is a scanning electron microscopy (SEM) image of the final product obtained according to another embodiment of the present invention;

fig. 8 is a computed tomography (CT) image of the final product obtained according to another embodiment of the present invention;

fig. 9 is a computed tomography (CT) image of a cross-section of the final product obtained according to another embodiment of the present invention;

fig. 10 is a computed tomography (CT) image of a cross-section of the final product obtained according to another embodiment of the present invention;

fig. 11-17 are scanning electron microscopy (SEM) images showing microsphere wall thickness values in the final product made according to embodiments of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

In order to more clearly explain the task, the technical diagram and the advantages of the embodiments of the present invention, the technical diagram of the embodiments of the present invention will be described clearly and completely in conjunction with the drawings of the embodiments of the present invention. Obviously, the described embodiments form part, and not all, of the embodiments of the present invention. Based on the described embodiments of the present invention, all other embodiments obtained by those skilled in the art without including creative activity fall within the protection scope of the present invention.

Unless otherwise indicated, the technical terms or scientific terms used in the present invention shall have a common meaning understood by those skilled in the art to which the present invention pertains. Unless otherwise indicated, the term "part" refers to the mass part.

Man is a warm-blooded animal, while the human body itself is a heat source that constantly releases heat. The constantly generated heat must be continuously removed. In the hot summer, body heat is slowly removed, and we become hot; in cold winter, when body heat is removed quickly, we become cold. From experience, when people get cold, they usually put on extra clothes or change into thicker clothes. However, what causes warming when putting on extra clothes or changing into thicker clothes? We must consider the main ways of heat loss. In general, heat loss is due to three causes: heat conduction, heat convection and heat radiation. The definition of thermal radiation is as follows: all objects with a temperature above absolute zero continuously emit electromagnetic waves into the surrounding space. The higher the temperature, the greater the total energy emitted, and the more shortwave components. Wearing extra clothing or changing into thicker clothing mainly reduces heat conduction and heat convection to maintain heat, and has little effect on heat radiation. In the case of warm clothing, heat is transferred from the warm body to the clothing in contact with the body, and eventually the heat will be distributed to the cold atmosphere through the clothing. Heat convection involves heat exchange between the air on the surface of the human body and cold ambient air. Therefore, in order to improve the thermal insulation characteristics of clothing, on the one hand, we should strive to choose materials with low thermal conductivity for clothing; on the other hand, we must strive to reduce the likelihood of exchange between the air on the surface of the human body and the cold surrounding atmosphere.

Among known materials, still air has the lowest thermal conductivity. Therefore, fluffy thermal insulation materials such as cotton, down, etc. are usually chosen for insulated clothing. Such "airy" materials are filled with a large amount of air, so they have a better thermal insulation effect compared to other dense materials. However, the thermal insulation performance of these known thermal insulation materials is still not good enough. In order to provide protection from the cold in winter, it is necessary to make clothes thicker, which leads to the above disadvantages (restriction of body movements, lack of satisfaction of the aesthetic needs of a person).

According to the present invention, there is provided a kind of thermal insulation material in which non-conventional organic materials are mainly used as thermal insulation materials. It can greatly outperform traditional thermal insulation materials in letting as much air through as possible and preventing the air carried by the material from circulating with outside air. According to the principle of thermal insulation based on still air: with the same porosity? the larger the pore size, the higher the thermal conductivity. The thermal conductivity of interconnected pores is higher than the thermal conductivity of closed pores. The higher the proportion of closed porosity, the lower the thermal conductivity. At the same time, due to the above characteristics, this kind of material can not only be used for heat preservation and thermal insulation, but also can be widely used in other fields, such as sound insulation (noise insulation) and sound absorption.

Tents are essential equipment for outdoor sports. Thermal insulation and heat retention are the main technical difficulties that have always accompanied the global tent manufacturing companies. The successful development of the closed cell composite material of the present invention (when used for thermal insulation, it is a thermal insulation material) makes it possible to make tents light, cool in summer and warm in winter.

Due to the environment, climate and sweat, the thermal insulation performance of traditional clothing is greatly reduced. In particular, a down jacket will lose its thermal insulation ability when wet. The test of thermal insulation properties of thermal insulation materials according to the present invention in a wet state is described below. Tests and conclusions are made by a third party: Jingjian Yihe Center for Quality Control and Product Testing (Beijing). Test method: GB/T11048-2008A; test number: NB201804008. The standard samples were tested to determine the standard value in units of clo, they were weighed and the results recorded, and then the standard samples were immersed in a bowl filled with tap water for 3 minutes and completely soaked, and then the samples were taken out and placed in a dark and cool place for 30 minutes until the water stops dripping. The standard samples were wet to the touch. The moisture was determined to be 10% by weighing the samples. The clo value test was carried out again and the result was compared with the previous result, and the clo value obtained was found to be reduced by 3.6%. This result confirms that the thermal insulation material retains its thermal insulation properties when wet. If outdoor sports enthusiasts use clothing and equipment made from the insulating materials of the present invention, outdoor hiking will be safer and more confident in overcoming limitations.

Put the thermal insulation material in the freezer at -40°C for 30 minutes, then take it out for testing and comparison, while the thermal insulation material of the present invention does not show any change in thickness, feel and appearance. It can be imagined that certain equipment requires thermal insulation and heat retention when packaged and used outdoors. The protective device made from the thermally insulating material of the present invention is lighter, thinner and more effective than current materials.

When cars are parked outside for a long time, the temperature will be very high. At the moment the door is opened, a heat wave is carried out, the seat is heated, and the effective service life of the car is reduced. By applying the novel thermal insulation materials of the present invention, between the roof of the car, the surrounding decorative surface and the steel sheet of the car body, the temperature in the car can be reduced by 15-25°C compared to conventional cars. At the same time, the thermal resistance provided by the thermal insulation materials of the present invention, whether in winter or summer, can greatly reduce the use of an automobile's air conditioner and fuel consumption, while also improving sound insulation performance.

Because the materials of the present invention are form-fitting, breathable, lightweight and retain heat even when wet, they are the best choice for an ideal winter boot. The use of thermal insulation materials according to the present invention will stimulate the world's shoe designers and manufacturers to realize the dream of technological innovation, and bring consumers new experiences and more choices in keeping feet warm and wearing fashion in winter.

Thermal insulation materials proposed according to the present invention will bring a new experience to people with certain acoustic preferences. The effects of sound insulation and sound absorption in rooms using thermal insulation materials according to the present invention will be greatly improved. At the same time, the noise is greatly reduced, the thermal insulation effect is enhanced, and people will live more comfortably.

Nowadays, the thick thermal insulation layer in the refrigerator makes it unwieldy. The use of the thermal insulation material according to the present invention can reduce the thickness of the thermal insulation layer in the refrigerator by 60%, while increasing the storage space in the refrigerator. The refrigerator, which uses new materials according to the present invention, will change its bulky appearance.

Unwanted eavesdropping is usually achieved by picking up sound that causes window glazing to vibrate. If the curtain is made of the thermal insulation material according to the present invention, not only can unwanted listening be prevented, but thermal insulation and heat retention can also be achieved.

The use of thermal insulation materials according to the present invention in winter gloves provides not only heat retention, but also provides faster finger movement and improves work efficiency.

The technical solution according to the present invention will be further described in conjunction with embodiments.

According to the present invention, the following test methods are used.

Temperature difference evaluation test (the greater the temperature difference, the better the thermal insulation performance):

Applied instruments include HP-2020 thermostatic heating table, YHT309 four-channel thermometer provided by Yuanhengtong, and TP-K03 surface grating sensor provided by Taishi TES, Taiwan.

The test method includes the following: set the temperature of the heating table at 60°C and place samples of thermal insulation material with dimensions of 5 cm in length and 3 cm in width on the heating table. During the test, maintain a constant temperature of the heating table and press an object against one end of the thermal insulation material to prevent movement until the end of the test.

One sensor is in direct contact with the surface of the heating table, and the other sensor is in contact with the surface of the thermal insulation material on the heating table. The distance between the two probes is 2 cm. Hold the probe firmly with both hands, and the YHT309 four-channel thermometer indicates that the temperature values for the two groups are stable for 10 seconds. Record the surface temperature and test time on the heating bed and the surface of the thermal insulation material, respectively. The test is carried out in one repetition every 15 minutes, a total of 4 times.

The temperature difference is the difference between the sum of the four surface temperatures of the heating table and the sum of the four surface temperatures of the thermal insulation material.

Test for determining the value in units of clo:

Testing is carried out by a third party: Jingjian Yihe Quality Control and Product Testing Center (Beijing), according to test method: GB/T11048-2008 A.

Definition of clo value: when a person who is sitting still or doing light mental work (metabolic heat release is 209.2 kJ/m ² ⋅h) feels comfortable in an environment with a room temperature of 21°C, when the relative humidity is less than 50% and the wind speed is not more than 0.1 m / s, while the thermal resistance of the clothes he wears is 1 clo.

Thermal conductivity test:

Use the method using a flat heat source (hot disk) in alternating mode, and the test conditions for determining thermal conductivity are as follows:

Instrument model: TPS3500

Test module: basic module, one-way method

Sensor Model: Kapton 7577

Thermal power: 10mW

Test time: 1s

Ambient temperature during testing: 26±0.5°C

Comparison material at the bottom: quartz

Upper Comparison Material: Styrofoam/

The composition of the products used according to the present invention is presented below. Water-dispersible resin Leasys3458: water-based anionic polyurethane dispersion (aliphatic group) with a solids content of about 50 wt. %; water-dispersible resin Impranil DLS: water-based anionic polyurethane dispersion (aliphatic group, polyester type) with a solids content of about 50 wt. %; Impranil 1537: Water-based anionic polyurethane dispersion (aliphatic group, polyester type) with a solids content of about 60 wt. %; Expancel 043 DU 80 non-expanded thermo-expandable microspheres: small spherical particles of plastic material, microspheres consist of a polymer shell and a certain substance in it (the substance can expand under certain conditions), when heated, the internal pressure of the substance increases and the thermoplastic shell becomes soft, which leads to to increase the volume of microspheres, while the specified substance remains inside the spheres; antifoam BYK 093: mixture of polysiloxane and a hydrophobic solid dispersed in polyethylene glycol; wetting agent BYK 348: polyether-modified siloxane, solids content greater than 96 wt. %; thickener LYOPRINT PTF: type of acrylic polymer dispersion; water-based pigment paste NV 6800: type of water-based dispersion with a solids content of about 40 wt. %.

Examples 1-4. Influence of the added amount of thermally expanding microspheres

Example 1

Prepare various components according to the following composition:

Water-dispersible resin Leasys3458: 100 g

Expancel 043 DU 80 non-expanded thermoexpandable microspheres: 40 g

Deionized water: 300 g

Defoamer BYK 093: 0.3 g

Wetting agent BYK 348: 1 g

Thickener LYOPRINT PTF: 1 g

Water based pigment paste NV 6800: 20 g

It should be noted that in the present application, the weight of the water-dispersible resin in the claims refers to the dry weight. The water-dispersible resin used in the embodiments is a water-based dispersion with a defined water content. Therefore, a conversion to solids content is required. The presence of water in the formulation is mainly due to the addition of deionized water, water in the water-dispersible resin, and water in the water-based pigment paste. However, with respect to the expandable microspheres, antifoam, wetting agent, and thickener, the water content is either very low, or the effect on the total amount of water in the formulation may not be taken into account due to the small amount used. The composition, after recalculation, is as follows: Leasys3458 water-dispersible resin: 50 g based on dry weight; thermal expansion microspheres Expancel 043 DU 80: 40 g; deionized water: 300 g + 50 g (from Leasys3458 water-dispersible resin) + 12 g (from NV 6800 water-based pigment paste) = 362 g; antifoam agent BYK 093: 0.3 g; wetting agent BYK 348: 1 g; thickener LYOPRINT PTF: 1 g; water-based pigment paste NV 6800: 8 g based on dry weight. The recalculation in the following examples can be done in a similar way without repetition.

When mixing using a high-speed mixer, the above components are added to the mixing vessel sequentially, while the mixing speed is 1000-1500 rpm. After adding all the components continue mixing for 0.5-1 hour. A crosslinking agent may optionally be added prior to coating, whereby the crosslinking agent may include, for example, a polycarbodiimide, a polyisocyanate, a blocked polyisocyanate, an aziridine, or an amino resin.

The above composition was applied to a base fabric with a thickness of 0.28 mm, with a coating amount (wet weight) of 65 g/m ² , and then sintered in an oven at 140° C. for 1 minute. The thickness of the coating sample is 0.52 mm. Among them, Leasys3458 is the trade name of water-dispersible resin, Expancel 043 DU 80 is the trade name of thermally expandable microspheres, BYK 093 is the trade name of antifoam, BYK 348 is the trade name of wetting agent, LYOPRINT PTF is the trade name of thickener, NV 6800 is the trade name for a water-based pigment paste. It should be noted that the specific substances mentioned above are only for the purpose of illustration and not limitation of the present invention. Among the above components, the most critical components are water-dispersible resin and non-expanded thermally expandable microspheres, while other components can be excluded according to specific application scenarios. During the heating process, non-expanded thermally expanding microspheres will expand, and their volume will increase by 2-50 times. At the same time, the water will evaporate, and finally a product with a spatial structure, with many individual elements, will be formed, consisting of a certain number (very large number) of closed spheres, pseudospheres or irregularly shaped closed cavities (formed as a result of compression during expansion microspheres). A combined product with a spatial structure with many separate elements contains a large number of closed cavities and polymer walls separating a large number of closed cavities from each other. The polymer walls contain a thermoplastic or thermoset polymer material (i.e., a thermally expandable microsphere material) on the inside of the relatively closed cavity and contain a water-dispersible resin (i.e., a water-dispersible resin material) on the outside of the relatively closed cavity. In most cases, thermally expandable microspheres are fully expanded and adjacent walls of the microspheres are in contact with each other to form a multilayer polymeric wall. The materials of the two outer layers of polymeric walls are the same (both of thermally expandable microspheres) and the materials of the two outer layers are different from the materials of the intermediate layer located between the two outer layers (of water-dispersible resin).

The operations in examples 2-4 are similar to the operations of example 1, but the values of the content of thermally expanding microspheres are adjusted. The compositions for embodiments 1-4 are presented in the following table:

Table 1 Composition (unit: gram) and performance data for Examples 1-4

Example one 2 3 four leasys3458 100 100 100 100 Expancel 043 DU 80 40 thirty twenty ten Deionized water 300 300 300 300 BYK 093 0.3 0.3 0.3 0.3 BYK 348 one one one one LYOPRINT PTF one one one one N.V.6800 twenty twenty twenty twenty Coating Amount (Wet Weight) 65±5 g/ ^m2 65±5 g/ ^m2 65±5 g/ ^m2 65±5 g/ ^m2 Sintering conditions 1 minute at 140°C 1 minute at 140°C 1 minute at 140°C 1 minute at 140°C Coating sample thickness ¹ 0.52 mm 0.42 mm 0.32mm 0.17mm temperature difference 9.3°C 10.1°C 7.6°C 4.3°C Coating strength Insufficient Insufficient Relatively insufficient Relatively insufficient Normalized temperature difference ² 17.88°C 24.05°C 23.75°C 25.29°C

¹ "Covering sample thickness" is the thickness of the dry coating attached to the base fabric, hereinafter by analogy;

² Since the temperature difference is approximately proportional to the thickness of the coating sample, the "normalized temperature difference" is calculated by normalizing the thickness of the coating sample to 1 mm. It should be noted that the effect of the base fabric (carrier) on thermal insulation characteristics (including "temperature difference", "normalized temperature difference" and hereinafter "value in units of units", "normalized value in units of klo") is not taken into account in all embodiments, presented in this application. This is due to the high thermal conductivity of the polyester fiber of the base fabric, which makes little contribution to the thermal insulation performance. For example, for a base fabric with a thickness of 0.28 mm used in Embodiments 1 to 24, the temperature difference measured under the same test conditions is less than 0.8°C, while for a base fabric with a thickness of 0.15 mm used in Embodiment 25, the temperature difference measured under the same test conditions is less than 0.2°C. This temperature difference is due to the insulating effect of the air in the fleecy thread of the base fabric. After coating the base fabric, the space between the threads was filled with thermally expanding microspheres, and the air in the base material is now removed. The influence of the thermal insulating property of the base fabric on the thermal insulating characteristics of the final product may not be taken into account.

Theoretically, if the number of thermally expandable microspheres becomes larger and the coating becomes thicker, the volume fraction of the closed cavity in the coating will be larger, while the temperature difference of the coating will be larger, and the thermal resistance will be better. However, in this case, there is a problem caused by a large number of thermally expanding microspheres, i.e. this will affect the adhesion of the dry coating. Therefore, the normalized temperature difference in Embodiment 1 (“normalized temperature difference” reflects the thermal insulation performance at the same thickness of the coating sample, so it can better reflect the thermal insulation performance compared to “temperature difference”) is not as high as in Embodiment 2. When Comparing the results of experiments in examples 2, 3 and 4, it can be concluded that with a similar amount of coating (wet weight), the higher the content of microspheres, the greater the temperature difference will be (the better the thermal insulation characteristics). Leasys 3458 water-dispersible resin exhibits conventional microsphere adhesion. If the number of thermally expandable microspheres exceeds the adhesion strength of the water-dispersible resin, the larger the number of microspheres, the worse the abrasion strength of the coating, and the stronger the abrasion of the surface (to evaluate the abrasion strength of the coating, the improvement is presented from left to right in the following order: insufficient -> relatively insufficient -> relatively sufficient -> sufficient; for garments, sufficient or relatively sufficient abrasion resistance may be allowed to meet the requirements of the application; for other applications, such as insulating materials for building walls, compliance with the application conditions may also be allowed in the case of insufficient or relatively insufficient abrasion resistance of the coating). It is only by taking into account the "normalized temperature difference" data that proper thermal insulation performance is achieved with the application rate of microspheres of 10 g, 20 g and 30 g.

Example 5-7. Effect of different water-dispersible resins on coating abrasion strength

The operations in Examples 5-7 are similar to those of Example 1, but the water-dispersible resin content has been adjusted. The compositions for embodiments 5-7 are presented in the following table:

Table 2. Composition (unit: gram) and performance characteristics for examples 5-7

Examples 5 6 7 leasys3458 100 0 0 Impranil DLS 0 thirty thirty Impranil 1537 0 70 70 Expancel 043 DU 80 ten ten twenty Deionized water 300 300 300 BYK 093 0.3 0.3 0.3 BYK 348 one one one LYOPRINT PTF one one one N.V.6800 twenty twenty twenty Coating Amount (Wet Weight) 65±5 g/ ^m2 65±5 g/ ^m2 65±5 g/ ^m2 Sintering conditions 1 minute at 140°C 1 minute at 140°C 1 minute at 140°C Coating sample thickness 0.17mm 0.22 mm 0.32mm temperature difference 4.3°C 6.9°C 8.6°C Coating strength Relatively insufficient Relatively sufficient Relatively sufficient

Compared to the use of Leasys3458 water-dispersible resin alone (Example 5), the formulation (Example 6) using a blend of two water-dispersible resins, Impranil DLS and Impranil 1537, showed significantly improved microsphere adhesion strength and enhanced coating strength. Due to the increased strength of the coating, the expanded microspheres did not decrease in size after the formation of the sample, thus, the temperature difference of the sample obtained in example 6 significantly exceeded the temperature difference of the sample obtained in example 5. At the same time, when comparing examples 6 and 7, also it can be found that under the same or similar conditions, the higher the content of microspheres, the greater the coating thickness of the sample, the greater the temperature difference, thus the better the thermal resistance (thermal insulation performance).

Examples 8-12. The influence of different water content on thermal resistance, as well as the composition and structure of thermal insulation materials

The production process of Embodiments 8-12 is similar to the production process of Embodiment 1, but the amount of water is corrected. The compositions for embodiments 8-12 are presented in the following table:

Table 3 Composition (unit: gram) and performance data for Examples 8-12

Examples eight 9 ten eleven 12 Impranil DLS thirty thirty thirty thirty thirty Impranil 1537 70 70 70 70 70 Expancel 043 DU 80 twenty twenty twenty twenty 40 Deionized water 300 200 100 0 0 BYK 093 0.3 0.3 0.3 0.3 0.3 BYK 348 one one one one one LYOPRINT PTF one 0.5 0.2 0.1 0.1 N.V.6800 twenty twenty twenty twenty twenty Coating Amount (Wet Weight) 65±5 g/ ^m2 65±5 g/ ^m2 65±5 g/ ^m2 65±5 g/ ^m2 65±5 g/ ^m2 Sintering conditions 1 minute at 140°C 1 minute at 140°C 1 minute at 140°C 1 minute at 140°C 1 minute at 140°C Coating sample thickness 0.32mm 0.37 mm 0.77 mm 0.57mm 1.22 mm temperature difference 8.6°C 9.3°C 11.5°C 10.1°C 15.1°C Coating strength Relatively sufficient Sufficient Sufficient Sufficient Sufficient Normalized temperature difference * 26.88°C 25.14°C 14.94°C 17.72°C 12.38°C

*Since the temperature difference is approximately proportional to the thickness of the coating sample, the "normalized temperature difference" is calculated by normalizing the thickness of the coating sample to 1 mm.

Compare the results for embodiments 8-12. Regarding the composition, except that the amounts of water and thickener are different, the application rates of the other components are the same, the coating amount (wet weight) is the same, and the sintering conditions are the same. The amount of water is gradually reduced from Embodiment 8 to Embodiment 12, so the amount of thickener is reduced accordingly; in Embodiments 11 and 12, there is no additional water, and the number of thermally expandable microspheres in Embodiment 12 is twice the number of thermally expandable microspheres in Embodiment 11. When comparing the results for Embodiments 8-11, it can be seen that in the case of the same amount of coating (mass when wet) the thickness of the coating sample (i.e. the thickness of the product minus the thickness of the base fabric) first increases then decreases (in Embodiments 8, 9 and 10 successively increases and then decreases to Embodiment 11). The temperature difference shows a trend similar to the trend for the thickness of the coating sample. It is easy to see that the increase in embodiments 8, 9 and 10 is consistent. If the amount of water decreases and the percentage of solids increases, the thickness of the final coating sample increases, resulting in an increase in temperature difference, and an increase in thermal insulation effect with the same amount of coating (wet weight). However, in the case of example 11, when compared with example 10, taking into account the additional reduction in water content, the thickness of the sample of the final coating decreases, and the temperature difference also decreases, which contradicts the above reasoning. To understand this result, it is necessary to consider the role of water in the above decision. The two most important components are the water-dispersible resin and the thermally expandable microspheres, with water next in importance. The function of expanding microspheres is as follows: when the microspheres are heated and expanded, a large number of closed cavities will be formed. During the expansion process of the microspheres, the water-dispersible resin will be stretched to decrease the bulk density of the thermally expandable microspheres and the water-dispersible resin and improve the thermal insulation performance. However, it is not enough to have thermally expandable microspheres. It is also necessary to bond the microspheres to form a single unit with a certain mechanical strength (for example, to form a flat layer with a certain thickness) so that they can be used in some specific application scenarios (for example, for a thermal insulation layer in clothing or for a thermal insulation layer on an internal wall of buildings). ). And at the same time, this function is performed by a water-dispersible resin. Water has two main functions: one is to dilute the water-dispersible resin to reduce the binding of the water-dispersible resin to the thermally expandable microspheres during the expansion process, so that the thermally expandable microspheres can expand more freely and fully; the other is to reduce the solids content of the water-dispersible resin to prevent the decrease in thermal resistance due to the high thermal conductivity of the water-dispersible resin. It can be assumed that no additional water is added at all (thus the mixture contains only a small amount of water from the water-dispersible resin and pigment paste), two problems can arise: the first is that the thermally expandable microspheres stick together too strongly and blocked by the water-dispersible resin during the expansion process, and cannot fully and freely expand, the expansion of the microspheres is blocked, and the stretching and dispersing ability of the water-dispersible resin is reduced, and the microspheres cannot fully expand, while the thermal insulation function of the microspheres is not fully used; the second is the high thermal conductivity of the water-dispersible resin, which leads to a decrease in thermal insulation ability: since less water is used, the amount of water-dispersible resin must be increased in the composition per unit mass, while the thermal conductivity of the water-dispersible resin is higher, and the increase in its amount will inevitably lead to an increase in thermal conductivity, i.e. decrease in thermal insulation characteristics. Considering the above factors, it is easy to understand the results for Embodiment 11. Since no additional water was added to Embodiment 11, some of the microspheres are bound by the resin that is too highly water-dispersible, so they stick together and cannot fully expand, and the content is high. water-dispersible resin reduces thermal insulation performance. Therefore, for the same amount of coating (wet weight), the thickness of the finished coating sample becomes smaller and the temperature difference becomes smaller.

According to the "normalized temperature difference" in Embodiments 8 to 12, under the same or similar other conditions, when the amount of additional water is 200 g and 300 g, the thermal insulation effect is the best. In general, it is best to add 150-350 parts by weight of water for every 100 parts by weight of water-dispersible resin (wet weight).

Next, the structure and composition of the product are examined. In FIG. 1 is an optical microscopy image of an unexpanded thermally expandable microsphere used in embodiments of the present invention. Thermally expandable microspheres used in embodiments of the present invention are Expancel 043 DU 80, with an average particle size of about 16-24 microns, the material of the walls of the microspheres is a thermoplastic or thermoset polymer material, they can expand after heating, and at the same time the diameter is increased by 2 10 times relative to the original diameter. The shape of a single thermally expandable microsphere can be seen in FIG. 2. In FIG. 1, it can be seen that the non-expanded thermally expanding microsphere is represented by regular spherical particles or pseudospherical particles. In FIG. 2, it can be seen that an individual microsphere has an almost spherical elliptical shape with a major axis (outer diameter) 24.2 µm long, a minor axis (outer diameter) 22.6 µm long, and a wall thickness of about 5 µm. It should be noted that if other thermally expandable microspheres of other materials or sizes are chosen, the respective structures and materials will change, and these constituents (specific materials and microsphere structures) should not be construed as limiting the scope of protection of the present invention.

A micrograph of the final product obtained in Example 10 is shown in FIG. 3. In FIG. 3, it can be seen that most of the expanded microspheres have a regular or pseudo-spherical shape. In some areas, the expanded microspheres may have an irregular shape due to the strong compression between the microspheres. For convenience of description, "size" in this application refers to the diameter of a regular sphere; for a pseudosphere or irregular shape, "size" in this application refers to the diameter of a sphere having the same volume as the sphere or irregular shape. Comparison of FIG. 1, fig. 3 shows that after heating and expansion, the volume of the microspheres increases several times, while the spherical wall becomes thinner and transparent.

Example 13-17. Effect of different sintering temperatures on the results

The production process of Embodiments 13-17 is similar to the production process of Embodiment 1, but the sintering temperature is corrected. The formulations for Embodiments 13-17 are shown in the table below:

Table 4. Composition (unit: g) and performance data for Embodiments 13-17

Example 13 fourteen fifteen 16 17 Impranil DLS thirty thirty thirty thirty thirty Impranil 1537 70 70 70 70 70 Expancel 043 DU 80 twenty twenty twenty twenty twenty Deionized water 200 200 200 200 200 BYK 093 0.3 0.3 0.3 0.3 0.3 BYK 348 one one one one one LYOPRINT PTF 0.5 0.5 0.5 0.5 0.5 N.V.6800 twenty twenty twenty twenty twenty Coating Amount (Wet Weight) 65±5 g/ ^m2 65±5 g/ ^m2 65±5 g/ ^m2 65±5 g/ ^m2 65±5 g/ ^m2 Sintering conditions 1 minute at 140°C 1 minute at 130°C 1 minute at 120°C 1 minute at 110°C 1 minute at 150°C Coating sample thickness 0.37mm 0.32 mm 0.24 mm 0.14 mm 0.37 mm temperature difference 9.3°C 8°C 6.8°C 4°C 9.5°C Coating strength Sufficient Sufficient Sufficient Sufficient Sufficient

Based on the results presented in the table above, it can be seen that when using the same composition and the same amount of coating (wet mass), the thickness of the coating and the thermal insulation characteristics (temperature difference) are related to the sintering temperature. The lower the temperature, the lower the thickness of the dry film of the coating and the worse the thermal insulation properties (due to insufficient expansion of thermally expanding microspheres); if the temperature is not more than 140-150°C, the coating thickness and temperature difference are the highest, and the best sintering temperature is 140-150°C. It should be noted that this optimum sintering temperature range refers to the sintering equipment and the composition and structure of the thermally expandable microspheres used. The expandable microspheres used in the embodiment according to the present invention are Expancel 043 DU 80. If other sintering equipment and/or other expandable microspheres are used, the optimum sintering temperature range may be changed.

An SEM micrograph of the final product from Example 17 is shown in FIG. 4-7. Fig. 4 is an SEM micrograph of the product obtained directly, FIG. 5 is an additional magnification SEM micrograph of the product; fig. 6 is an SEM micrograph of a cross section of the product, and FIG. 7 is an SEM micrograph of a cross section of the product with additional magnification. In FIG. 4-5, it can be seen that most of the expanded microspheres are about 100 µm in diameter. It should be noted that the ruler in the lower right corner of the figure refers to the length of the entire ruler. Let's take Fig. 4 as an example. The distance from the leftmost white line to the rightmost white line is 500 µm, so the distance between two adjacent white lines is 50 µm. The fiber seen in the upper left of FIG. 4 is a fiber in the base material, not in the thermal insulation material. Since the polyester thread used in the base fabric has high thermal conductivity, in order to achieve a better thermal insulation effect, the microspheres should be completely covered with the base fabric after expansion. The size of the expanded microspheres is influenced by many factors, such as the composition and structure of the thermally expanding microspheres, the heating temperature and the duration of the expansion process, the proportion of each component, etc. In addition, the dimensions of the expanded microspheres are also affected by many arbitrary factors, for example, insufficient heating at some positions leads to insufficient expansion of the microspheres, excessive heating at some positions leads to excessive expansion of the microspheres, and incomplete expansion of some microspheres due to structural defects (such as leakage of internal gas, etc.). Therefore, even in materials with proper foaming, there are very large or very small microspheres. For example, as can be seen in FIG. 4, most of the microspheres are distributed in the size range from 50 µm to 150 µm, but there are also some small microspheres with a size of about 20 µm, and some microspheres with sizes larger than 250 µm. In FIG. 4-6 it can be seen that the expanded microspheres are tightly packed together. Since the microspheres are bonded together by the water-dispersible resin, it can be concluded that most of the space between the microspheres is also closed. In FIG. 4 and FIG. 5, a very small number of destroyed thermally expanding microspheres can be observed (eg, in the lower left corner of Fig. 4 and in the lower right corner of Fig. 5). Ideally, each thermally expandable microsphere expands completely and does not collapse (thus ensuring that the internal space is closed). However, there are certain uncontrollable factors during the heating process, such as local overheating or some microsphere defects. However, cracking of individual microspheres does not significantly affect the thermal insulation characteristics of the final product. There are at least two reasons: 1) the proportion of microspheres destroyed is very small, judging by FIG. 4, it should be less than 1%; 2) even if individual microspheres are destroyed, due to the crowding of a large number of other microspheres around, the internal space of the destroyed microspheres closes again. Therefore, in fact, during the method for manufacturing the closed cell composite material in the embodiments of the present invention, as long as the heating temperature is not too high and the processing time is not too long, and most or most of the microspheres are not destroyed, a proper thermal insulation effect can be achieved. In addition, it should be noted that the SEM micrograph of the product according to Embodiment 17 only illustrates the method of implementation according to the present invention and cannot be construed as a limitation of the present invention. The size and shape of the microspheres in the final product can be changed as a result of changes in the material and composition of the microspheres, the heating temperature and the time of the expansion process, as well as the proportion of each component and other factors.

As shown in FIG. 4 and FIG. 5, only the surface morphology of the final product can be demonstrated in SEM micrographs. If we want to examine the internal structure of the final product, we must cut the product as shown in fig. 6 and FIG. 7. In FIG. 6 and FIG. 7, it can be seen that a large number of microspheres are collected together after expansion, occupying almost the entire space. The internal space of each microsphere is closed, so the gas inside the microspheres does not circulate. Since a large number of microspheres are gathered together, the space between the microspheres is mostly closed, so in the final product, almost all gases are in a closed space and cannot flow freely, which eliminates heat loss due to thermal conduction and air convection due to air movement. However, there is a problem in examining the shape of the product after it has been cut: the mechanical force during the cutting process will deform the cross section of the microspheres, so the shape of the microspheres in the cross section is changed compared to the shape of the microspheres in the actual product. In order to demonstrate the shape of the microspheres in the final product in the normal state, the inventors of the present invention additionally used a computed tomography (CTCT) method to obtain the internal shape of the product in Embodiment 17, as shown in FIG. 8-10. In FIG. 8, fig. 9 and FIG. 10 is a non-destructive study at various positions of the product in Embodiment 17, so they reflect the internal structure of the final product in its normal state. In FIG. 8-10, it can be seen that most of the microspheres are elliptical, and the microspheres in the positions with strong compression are irregular, and almost all spaces are filled with expanded microspheres. In FIG. 10 chose two expanded microspheres and accurately measured their sizes. The minor axis dimensions of the two microspheres were respectively 63.94 µm (upper left) and 54.53 µm (middle position). The corresponding size of the major axis should be between 100 µm and 200 µm, with most of the microspheres depicted in FIG. 10 correspond to this value. Of course, there are also some larger microspheres of 300-500 µm and some smaller microspheres of 20-30 µm. It should be noted that if the size of the unexpanded thermal expansion microspheres differs from the size of Expancel 043DU80, the diameter of the microspheres after the final expansion will be different.

Example 18 Laminated Thermal Insulation Material Produced by Laminating Process

For the experiment, a base fabric with a thickness of 0.28 mm and a density of 68.5 g/m ² was chosen. First, a base layer is applied to the base fabric, and then dried at a temperature that is below the expansion temperature of Expancel 043DU80, and then a top layer is applied to the dried base layer. The compositions of the base layer and top layer are shown below:

Proportion of each component in the base layer:

Water-dispersible resin Impranil DLS 100;

Thermally expanding microspheres Expancel 043 DU 80 40;

Deionized water 300;

Defoamer BYK 093 0.3;

Wetting agent BYK348 1.0;

Thickener LYOPRINT PTF 1.0;

Water-based pigment paste NV 6800 20.

Proportion of each component in the top layer:

Water-dispersible resin Impranil DLS 30;

Water-dispersible resin Impranil 1537 70;

Thermally expanding microspheres Expancel 043 DU 80 20;

Deionized water 200;

Defoamer BYK 093 0.3;

Wetting agent BYK348 1.0;

Thickener LYOPRINT PTF 0.5;

Water-based pigment paste NV 6800 20.

Referring to the operation mode in Example 1, under the action of shearing a high-speed mixer, various components according to the above composition are sequentially added to the mixing vessel, while all substances are supplied, and then mixed for 0.5-1 hour to obtain a base layer and an upper layer, respectively. A crosslinking agent may optionally be added prior to coating.

The base layer is applied to a base fabric with a thickness of 0.28 mm and a density of 68.5 g/m ² . The amount of applied adhesive (wet weight) is 65±5 g/m ² . It is then sintered in an oven at 100° C. for one minute. After drying (to obtain the lower insulating layer), the top layer is applied to the base of the lower insulating layer, the amount of glue applied (wet weight) is 130±5 g/m ² , and sintered in an oven at 140°C for 1 minute (with obtaining the upper insulating layer). The total thickness of the base fabric with the coating layer is 0.9 mm, with a temperature difference of 10.5°C, and the abrasion resistance of the coating is very good. The coating thickness and klo value can be increased by a dual coating design. Since the abrasion resistance of the coating mainly depends on the top layer, the requirements for the abrasion resistance of the base layer can be reduced, with the main focus on improving its thermal insulation characteristics. Therefore, the amount of thermal expansion microspheres can be increased in the base layer, or thermal expansion microspheres with different specifications can be used, and only one kind of water-dispersible resin can be used.

The production process of the mixed material in Examples 19=24 is similar to that of Example 1, but the coating equipment in Examples 19-24 is completely different from the equipment previously used and is similar to an industrial production line. The coating sample is tested to determine the klo value (the National Center for Supervision and Quality Control of Textile Products requires a sample size of 60 cm × 60 cm for the test to determine the klo value). The compositions for examples 19-24 are presented in the following table:

Table 5 Composition (unit: gram) and performance data for Examples 19-24

Example 19 twenty 21 22 23 24 Impranil DLS thirty thirty thirty thirty thirty thirty Impranil 1537 70 70 70 70 70 70 Expancel 043 DU 80 twenty twenty twenty twenty thirty thirty Deionized water 200 200 200 200 200 200 BYK 093 0.3 0.3 0.3 0.3 0.3 0.3 BYK 348 one one one one one one LYOPRINT PTF 0.5 0.5 0.5 0.5 0.5 0.5 N.V.6800 twenty twenty twenty twenty twenty twenty Coating quantity (dry weight) 6.05 g/ ^m2 16.15 g/ ^m2 16.5 g/ ^m2 23.3 g/ ^m2 25 g/ ^m2 25.7 g/ ^m2 Sintering temperature 150°C 150°C 150°C 160°C 150°C 160°C Air exchange rate 70% 70% fifty% 70% 70% 70% Sintering time 1 minute 1 minute 1 minute 1 minute 1 minute 1 minute Coating sample thickness 0.22 mm 0.37 mm 0.31 mm 0.32 mm 0.27mm 0.37 mm Base fabric thickness 0.28 mm 0.28mm 0.28mm 0.28 mm 0.28mm 0.28 mm Value in clo ¹ 0.208 0.453 0.302 0.36 0.40 0.508 Coating strength Sufficient Sufficient Sufficient Sufficient Sufficient Sufficient Normalized value in clo ² 0.95 1.22 0.97 1.13 1.48 1.37 Surface density of the base fabric (g/m ² ) 68.5 68.5 68.5 68.5 68.5 68.5 Coating density ³ (kg/m ³ ) 27.5 43.6 53.2 64.7 80.6 62.7

Note ¹ : The klo value test in Examples 19-24 was carried out by the National Textile Quality Supervision and Control Center of China. Report number for example 19: BA18001207-3; report number for example 20: BA18001207-1; report number for example 21: BA18001207-2; report number for example 22: BA18001308-3; report number for example 23: BA18001308-1; report number for example 24: BA18001308-2.

Note ² : Since the klo value is approximately proportional to the thickness of the coating sample, the "normalized klo value" is calculated by normalizing the thickness of the coating sample to 1 mm.

Note ³ : The method for calculating the coating density is as follows: subtract the mass of the base fabric from the total mass of products including the base fabric and the coating to obtain the mass of the coating; subtracting the volume of the base fabric from the total volume of the products, including the base fabric and the cover, to obtain the volume of the cover; dividing the weight of the coating by the volume of the coating to obtain the density of the coating.

Differences between coating a small sample in the laboratory and coating with equipment similar to a production line are as follows: a small sample of the coating in the laboratory can only be applied to an area of the size of an A4 sheet of paper, sintering is carried out in a dead-end furnace. A production line-like oven (also called a "pilot oven") can be blown from above and below; similar to the production line is a continuous production, the tension and the amount of coating is controlled more uniformly, while the size of the produced sample is large enough to conduct a thermal resistance test using professional instruments. The production line-like test is intended to test the performance of the solutions of the present invention under actual product manufacturing conditions and to better reflect the value of the practical application of the solutions of the present invention.

Check the characteristics of the composition in a test using a similar production line, while the abrasion resistance and experimental conditions are different; even at 150°C, the air exchange rate is different (the heating principle in similar to the production line is to use a fan that blows hot air heated by high-temperature steam or heat transfer oil onto the surface of the sample to ensure that the coating is heated, so at the same temperature, the air exchange rate is directly related with thermal energy, which in turn affects foaming of the microspheres and hence the clo value; generally, the higher the thermal energy, the better the expansion will be and the greater the clo value; however, too high thermal energy will cause excessive expansion of the microspheres, which will lead to destruction and a decrease in the value in units of klo). As long as the expansion limit set for thermal expansion microspheres is not exceeded, the larger the air volume and thickness, the better the thermal resistance will be. The highest clo values were achieved at an air exchange rate of 70% and a sintering temperature of 160°C; however, at temperatures above 160°C, the thickness of the coating sample no longer increased, and the thermal resistance decreased (indicating that excessive expansion of the microspheres occurred, which could cause destruction of some of the microspheres and thereby affect the thermal resistance).

Comparative analysis of the results in the above examples showed the following results.

When comparing example 19 and example 20, as can be seen from table 5, the compositions of the reagents, sintering conditions, etc. from example 19 and example 20 are the same, with the difference being the amount of coating (dry weight), in example 19 it is 6.05 g/m ² , and the amount of coating (dry weight) in example 20 is 16 .15 g/m ² , and ultimately leads to a difference in the thickness of the coating sample. In Example 20, the coating volume is larger (dry weight), so the coating sample is thicker and has a higher clo value. Under the same composition and sintering conditions, the higher the coating amount (dry weight), the higher the content of water-dispersible resin and the higher the water content; since both water evaporation and microsphere expansion are heat absorption processes, under the same sintering conditions, the lower the microsphere expansion capacity and the higher the density, so the foaming in Example 19 is more correct, and the density is lower, and the density in Example 20 is higher.

Example 20 and Example 21 are compared. The experimental conditions in Example 20 and Example 21 are the same except for the sintering conditions. In Example 20, sintering is performed at 150° C. for 1 minute with an air exchange rate at the top and bottom of 70%; in example 21, sintering is carried out at 150°C for 1 minute with an air exchange rate from above and below 50%; at the same time, the higher the intensity of air exchange, the more correct foaming is. Regarding the dry film thickness of the coating and the klo value of the sample, the higher thickness values, klo values, and normalized klo value of the coated sample in Example 20 indicate that it presents better sintering conditions. Under the same other conditions, the better the sintering conditions, the more correct is the expansion of the microsphere, so the coating density in example 20 is less than the coating density in example 21. It should be noted that there is a slight difference in the amount of coating (dry weight) between example 20 and example 21, because even if the composition and application conditions are guaranteed to be identical, there will be a slight difference in the amount of coating (dry weight) that will eventually be applied to the substrate, but this difference will be characterized by a negligible effect on the thermal insulation properties of the product ( for example, the difference in coating amount (dry weight) between Embodiment 20 and Embodiment 21 is only 2%. A similar situation can be observed in examples 23 and 24.

Example 20 is compared with Example 22. In Example 20, the coating amount (dry weight) is 16.15 g/m ² , the sintering temperature is 150°C, the air exchange rate at the top and bottom is 70%, the sintering time is 1 minute; in Example 22, the coating amount (dry weight) is 23.3 g/m ² , the sintering temperature is 160°C, the air exchange rate at the top and bottom is 70%, the sintering time is 1 minute; other conditions are similar. Due to the higher amount of coating (dry weight) in Example 22, it is generally assumed that Example 22 presents better thermal insulation performance and a higher clo value. However, when comparing the thickness of the coating sample and the klo value in the two examples, it can be found that the thickness of the coating sample and the klo value in Example 20 are significantly higher. The main reason for this is that the sintering temperature in Example 22 is too high, which leads to the rupture of a large number of microspheres in the final product, resulting in a decrease in the dry film thickness of the coating and a decrease in thermal insulation effect. The amount of coating (dry weight) in Example 22 is increased, while the microspheres in the middle of the coating show increased expansion resistance and insufficient expansion ratio; at the same time, the outer microspheres are broken due to the high temperature, therefore, in Example 22, a higher density is presented compared to Example 20, while the thermal insulation effect is reduced.

Example 20 is compared with Example 23. Example 23 has 50% more microspheres and 55% more coating (dry weight) than Example 20, but the thickness of the coating sample in Example 23 and the clo value are lower than in Example 20. In this case, when the amount of expanded microspheres is larger and the coating amount (dry weight) is larger, the thermal insulation effect in Example 23 is not better compared to Example 20 due to insufficient expansion of the microspheres in the product of Example 23. Since all the processes of evaporating water during sintering, heating the mixture and expanding the microspheres are accompanied by heat absorption, the strength after sintering accordingly does not increase when the amount of coating (dry weight) increases, which leads to improper expansion of the microspheres in the final product of example 23, and at the same time the dry film thickness of the coating and the value in units of klo are low.

Example 23 and Example 24 are compared. The difference between Example 23 and Example 24 is that the sintering temperature in Example 24 is 10°C higher than the sintering temperature in Example 23. A comparison of Example 20 and Example 23 shows that in Example 23 sintering is insufficient , and therefore, Example 24 shows higher coating sample thickness and clo values (including normalized clo values) after increasing the sintering temperature, indicating that sintering conditions in Example 24 are better with the same composition.

With the same composition, the density of the coating reflects the actual degree of expansion of the microspheres. The lower the density, the better the expansion of the microspheres, and thus a higher normalized clo value can be expected. When comparing examples 20 and 21, 20 and 22, 23 and 24, this pattern will be established. However, Example 19 seems to break this pattern because the amount of coating (dry weight) in Example 19 is so small that the thickness of the coating sample is too thin, and instrument testing with penetrations into micropores in the film layer causes air convection (and therefore heat loss), so the exclusion in example 19 cannot be considered as a violation of the above pattern.

In order to determine the ratio of the total volume of the closed cavity and the total volume of the polymer wall in the final product, in addition to the microsphere diameter, it is necessary to know the range of microsphere wall thicknesses. In FIG. 11-17 are microsphere wall thickness values measured by SEM, where FIG. 11 corresponds to example 19, FIG. 12-13 correspond to example 25, FIG. 14-15 correspond to example 24, and FIG. 16-17 correspond to Example 21. As can be seen in the previous FIGS. 3-10, different sizes of microspheres in the final product are very different, since the degree of expansion of different microspheres is influenced by many factors, including the thickness of the polymer in the shell of the microsphere, the amount of thermally expandable substance encapsulated inside the microspheres, etc. Due to the different degree of expansion of the microspheres, it can be assumed that the wall thicknesses of different microspheres in the final product will differ, which is confirmed by the results in Fig. 11-17. For example, in FIG. 16 and 17 are observations for the products from Example 21, but the wall thicknesses vary from over 300 nm to over 700 nm, but the observations show that the wall thicknesses of fully foamed products are generally less than those of under-foamed products. In addition, it is easy to understand that the fuller the expansion of the microspheres, the thinner their walls will be. Because the average wall thickness of the expanded microspheres in the final product cannot be accurately achieved under current conditions, FIG. 11-17 will help us determine the range of wall thickness distribution. Using as an example FIG. 13 it is clear that the polymer wall is divided into two layers separated by a black line in the middle. The walls on each side are formed by two expanded microspheres which are adjacent and in contact, with the black area in the middle being formed by a water-dispersible resin. "Polymer wall thickness" referred to in the claims means the total thickness of the polymer wall including two adjacent layers of microspheres and a layer of water-dispersible resin in between. It turns out that as a thermal insulation material, the three-layer structure of the polymer wall can be considered as a whole without any separation, since, on the one hand, the three polymer layers are actually fused together during the heating process, and, on the other hand, the thermal conductivity of the polymers, whether a polymer in microspheres, or a polymer from a water-dispersible resin, does not differ significantly from the thermal conductivity of air and significantly exceeds it, therefore, from a technical point of view, it is advisable to consider the three-layer structure of the polymer wall as a whole. In order to achieve optimum thermal insulation, the inventors of the present invention found it necessary, on the one hand, to make sure that the space inside the closed cell composite material is as closed as possible, and, on the other hand, to minimize the amount of polymer, be it polymer in a thermally expandable microsphere. or water-dispersible resin. Accordingly, the polymeric wall with the three-layer structure described above should not be considered as a limitation of the present description, and various methods can be used to achieve both of these goals (the maximum amount of enclosed space and the minimum amount of polymer), provided that they are achievable. For example, a thermally expandable microsphere is used, which is inherently sticky, so water-dispersible resin can be omitted, with only two layers of polymer formed by adjacent microspheres present in the final product. Despite this (from a technical point of view, it is not necessary to perform the separation of the internal structure of the polymer wall described above), in order to determine the ratio of the total volume of the closed cavity and the total volume of the polymer wall in the final product, it is necessary to know the range of thicknesses of the individual walls of the expanded microspheres (i.e. the thickness of the walls on both sides, separated in the middle by a black line, for example, as in Fig. 13, the black line in the middle being so thin that it actually indicates the incorporation of the water-dispersible resin, represented by the black line, into the walls of the microspheres on both sides ). The individual microsphere wall thickness values obtained in FIG. 11-17 include: 44.9 nm, 48.2 nm, 81.9 nm, 96.6 nm, 95.9 nm, 149 nm, 78.9 nm, 89 nm, 102 nm, 351 nm (border between two layers of microsphere walls in Fig. 16 is not clearly visible), 314 nm and 325 nm. As shown in FIG. 8 and 9, most of the microspheres are in contact with each other after expansion, and the top view shows many intersections. In FIG. 11-17, all microsphere wall thicknesses are chosen to be measured at a mid-position away from the above intersection.

Assuming that the thermally expandable microspheres are a regular sphere with a diameter of 100 μm (in most of the expanded microspheres observed in the examples, the diameter is about 100 μm), if the average wall thickness of an individual microsphere is 5 μm, the volume fraction of the closed cavity and the volume of the wall in the final product can be calculated as follows: the surface area of an individual sphere corresponds to S = 4πr²=4*3.14*50*50=31400, so the wall volume of an individual sphere corresponds to V _wall =S*h(thickness)=157000 µm ³ . The volume of the cavity in the microsphere corresponds to the V _cavity =πr ³ *4/3=3.14*50*50*50*4/3=523333 µm ³ . Then the ratio of the volume of the cavity and the volume of the wall corresponds to V _cavity : V _wall =523333/157000=3.33. The above ratio is 16.67, if the average wall thickness is 1 µm, is 33.3, if the average wall thickness is 0.5 µm, is 83.3, if the average wall thickness is 0.2 µm, is 166.7, if the average wall thickness is 0.1 µm, is 333.3, if the average wall thickness is 0.05 µm, is 416.7, if the average wall thickness is 0.04 µm, is 555.6, if the average wall thickness is 0.03 µm is 833.3 if the average wall thickness is 0.02 µm, is 1666.7 if the average wall thickness is 0.01 µm. It should be noted that the above calculations do not take into account the volume of space between the microspheres, so in practice the ratio of the total volume of the insulating cavity and the total volume of the polymer walls will be greater than the above estimates. In addition, based on the wall thickness measurements in the examples of the present invention, the average wall thickness of 0.01 µm is close to the microsphere expansion limit used in the experiments of the present invention, and thus the cavity volume to wall volume ratio of 1666.7, also close to the upper limit. Based on the above calculations, it is assumed that the ratio of cavity volume to wall volume in the examples according to the present invention is less than 2000, but if other microspheres with a higher expansion ratio are used, the ratio of cavity volume to wall volume may exceed 2000.

Example 25 Manufacture of Thermal Insulation Laminate by Multiple Coating Method - Production Line Test

The approach in the implementation refers to Example 18, but with a scale-up of the manufacturing method to test the effectiveness of the technical solution according to the present invention in actual large-scale production conditions. Using a base fabric with a thickness of 0.15 mm and a specific gravity of 33.3 g/m ² , a base layer was first applied to the base fabric, the temperature and sintering time were set for drying at a temperature at which unexpanded Expancel 043 DU80 microspheres do not expand, and then a top coat was applied over the dried base coat. The compositions of the base layer and top layer are shown below.

Proportion of each component in the base layer:

Water-dispersible resin Impranil DLS 100;

Thermally expanding microspheres Expancel 043 DU 80 40;

Deionized water 300;

Defoamer BYK 093 0.3;

Wetting agent BYK348 1.0;

Thickener LYOPRINT PTF 1.0;

Water-based pigment paste NV 6800 20.

Proportion of each component in the top layer:

Water-dispersible resin Impranil DLS 30;

Water-dispersible resin Impranil 1537 70;

Thermally expanding microspheres Expancel 043 DU 80 20;

Deionized water 200;

Defoamer BYK 093 0.3;

Wetting agent BYK348 1.0;

Thickener LYOPRINT PTF 0.5;

Water-based pigment paste NV 6800 20.

Referring to the operation mode in Example 1, under the action of shearing a high-speed mixer, various ingredients according to the above composition are successively added to the mixing vessel, while all substances are supplied and mixed for 0.5-1 hour. A crosslinking agent may optionally be added prior to formulation.

The base layer composition was applied to a 0.15 mm thick base fabric with 65±5 g/m ² adhesive (wet weight) and sintered in an oven at 100° C. for 1 minute. After drying, a top layer is applied on top of the base layer, with an amount of adhesive (wet weight) of 130±5 g/m ² , and sintered in an oven at 150° C. for 1 minute. The combined thickness of the base fabric and the coating samples is 0.55-0.6 mm (resulting in a coating thickness of 0.40-0.45 mm), with a clo value of 0.605 (normalized clo value 1 .34 1.51 in terms of a coating thickness of 1 mm), the abrasion resistance of the coating is sufficient and the surface of the coating is strong. The density of the thermal insulation coating for this group of experiments was 75.6 kg/m ³ . The double coating method can provide an increase in coating thickness and klo value, but the thickness is less than the total thickness when the two coatings are applied separately; while the abrasion resistance of the coating mainly depends on the top layer. Since the abrasion strength of the coating mainly depends on the top layer, the requirement for the abrasion strength of the base layer can be reduced, while focusing on improving its thermal insulation performance, so the number of thermally expandable microspheres in the base layer can be increased, and only one can be used. water-dispersible resin. The dual coating method has some effect on the expansion capacity of the microspheres in the base layer due to the increase in the bonding strength of the resin, and the thermal resistance improves as the content of the microspheres and the amount of coating increase. Note: These klo values are provided by a third party: Jingjian Yihe Quality Control and Product Testing Center (Beijing): NB201805006.

In applications, a plurality of closed cell composites may be bonded together with an adhesive, or one or more closed cell composites may be bonded together with other materials with an adhesive. For example, products made from two layers according to example 25 are bonded together "face-to-face" (i.e., the front side of one coating to the front side of the other coating) with adhesive to obtain a "sandwich" structure with two outer backing layers and an intermediate layer of closed-cell material (insulating material) (laminating by bonding the front side of a carrier to the front of another carrier is also possible). Adhesive bonding was performed using a hot melt adhesive applicator manufactured by Wuxi Nuoerte Machinery Co., Ltd., and the adhesive used was a hot-melt PU adhesive with a dry weight of 15 g/m ² . The total thickness of the sandwich structure is 1.21 mm and the clo value is 1.11. The klo value increases after the two layers are layered, indicating that the increased thickness of the two layer layer structure results in improved thermal insulation properties. Closed cell composites can also be bonded to other materials, expanding the applications of closed cell composites. Note: These klo values are provided by the Jingjian Yihe Product Testing and Control Center (Beijing): NB201805004.

Composite materials with closed cells according to the present invention can be used as sound-absorbing or noise-insulating materials. The difference between the sound absorbing material and the noise insulating material is that the sound absorbing material is aimed at the amount of reflected sound energy from the source side, the purpose being to reduce the reflected sound energy. The sound deadening material is directed to the amount of transmitted sound energy on the other side of the incident sound source, the purpose being to reduce the transmitted sound energy. As a rule, the absorption of incident sound energy by sound-absorbing materials is only a few tenths; therefore, their sound-absorbing capacity, i. sound absorption coefficient, can be expressed as a decimal fraction; however, the soundproofing materials can dampen the transmitted sound energy to an incident sound energy of 10 ^-3 -10 ^-4 or less, decibels are used to describe the level of noise reduction for the sake of convenience.

The difference between the two materials is that the sound absorbing material reflects only a very small part of the incident sound energy, which means that the sound energy can easily penetrate and pass through the material. It can be assumed that the material should be porous, loose and breathable, which is typical for a porous sound absorbing material, which is usually a fibrous, granular or foam material to form a porous structure; its structural characteristics are as follows: this material contains a large number of communicating micropores passing from the surface inward, i.e. has some degree of breathability. When sound waves are incident on the surface of a porous material, causing vibrations of air in the micropores, due to frictional resistance and viscous resistance of air, as well as heat transfer, a significant part of the acoustic energy is converted into thermal energy, thus providing a sound absorption function.

In the case of noise insulation materials, in order to reduce the transmission of sound energy by blocking the propagation of sound, they cannot be porous, loose, breathable as sound absorbing materials. Instead, they should be made of heavy and dense materials such as steel plates, lead plates, brick walls, etc. It is required that the soundproofing material be dense, without holes or slots; had a large mass. Due to the dense texture of this type of soundproofing material, it is difficult to absorb and transmit sound energy, resulting in high reflective energy, so it has insufficient sound absorption performance.

Based on the foregoing analysis, it can be seen that the closed cell composite material of the present invention combines the structural characteristics of the above sound deadening and sound absorbing material, which include porosity and sheet integrity. Therefore, the closed-cell composite material of the present invention has both sound-absorbing and sound-absorbing characteristics.

Examples 26-31. Effect of Adding Different Numbers of Microspheres on Thermal Conductivity

Table 6 Composition (unit: gram) and performance data for Examples 26-31

Example 26 27 28 29 thirty 31 Impranil DLS thirty thirty thirty thirty thirty thirty Impranil 1537 70 70 70 70 70 70 Expancel 043 DU 80 thirty twenty fifteen ten 5 0 Deionized water 100 100 100 100 100 100 Polyether-siloxane copolymer emulsions (antifoam) 0.2 0.2 0.2 0.2 0.2 0.2 Polyether modified polydimethylsiloxane (wetting and leveling agent) 0.5 0.5 0.5 0.5 0.5 0.5 Acrylic polymer (thickener) 0.2 0.2 0.2 0.2 0.2 0.2 Coating Amount (Wet Weight) 50±5 g/ ^m2 50±5 g/ ^m2 50±5 g/ ^m2 50±5 g/ ^m2 50±5 g/ ^m2 50±5 g/ ^m2 Sintering conditions 1 minute at 140°C 1 minute at 140°C 1 minute at 140°C 1 minute at 140°C 1 minute at 140°C 1 minute at 140°C Base fabric thickness (mm) 0.15 0.15 0.15 0.15 0.15 0.15 Coating sample thickness including base fabric (mm) 0.8 0.65 0.5 0.4 0.3 0.15 Thermal conductivity (W/m⋅K) 0.0158 0.016 0.0192 0.0208 0.0289 0.2093

The test method for determining thermal conductivity is a method using a flat heat source (hot disk) in alternating mode, and the test conditions for determining thermal conductivity are as follows:

Instrument model: TPS3500

Test module: basic module, one-way method

Sensor type: Kapton 7577

Thermal power: 10mW

Test time: 1s

Ambient temperature: 26±0.5°C

Comparison material at the bottom: quartz

Upper comparison material: Styrofoam.

Analysis of the results of the above tests is performed as follows.

Example 31 is a conventional polyurethane coating without thermal expansion microspheres added to the composite, the coating thickness is determined only by the coating amount, and since the wet coating amount of 50 g/m ² is a small value, the final dry coating is very thin, and the total measured thickness of the coating sample, including the base fabric, is almost equal to the thickness of the base fabric itself. Since both the base fabric and the polyurethane coating film are hard polymeric materials, the thermal conductivity is high at 0.2093 W/m⋅K.

When the intumescent microspheres are added to the composition, the intumescent microspheres expand after heating, so the coating thickness increases significantly and increases even more with an increase in the amount of microspheres added (examples 26-30); another result of adding microspheres is the formation of a large number of closed pores in the coating film, which can effectively reduce the thermal conductivity of the coating film (Examples 26-30); but when the amount of added microspheres increases to a certain extent, the microspheres squeeze each other during foaming, competing for energy absorption during sintering. Therefore, the microspheres cannot fully expand and the thermal conductivity can no longer be reduced. The lowest thermal conductivity is achieved by adding thermally expanding microspheres in the amount of 20-30 mass parts.

The above table of contents represents only exemplary embodiments of the present invention and is not intended to limit the scope of the present invention. The scope of legal protection of the present invention is determined by the attached claims.

The present application claims priority under Chinese Patent Application No. 201811051379.3 filed on September 10, 2018, and the contents of the above Chinese patent application are hereby incorporated by reference in their entirety as part of the present application.

Claims (53)

1. A method of manufacturing a composite material with closed pores, including: 1) preparing a mixture, wherein the mixture contains 30-70 parts by weight of water-dispersible resin, 10-300 parts by weight of non-expanded thermally expandable microspheres, 100-550 parts by weight of water, and stirring the mixture; 2) media preparation; 3) applying a layer of the mixture obtained in step 1) onto a support; 4) heating the layer of the mixture and the carrier for a certain time, during which the non-expanded thermally expanding microspheres expand; 5) repeating steps 3)–4) several times to obtain a closed-cell composite material containing a multilayer coating of the mixture; while non-expanded thermally expanding microspheres are hollow spherical or pseudo-spherical, with walls containing thermoplastic or thermosetting polymeric materials; while the composite material with closed pores contains many closed cavities and polymer walls that separate the closed cavities from each other; moreover, the range of sizes of the closed cavities is from 20 μm to 800 μm, and the ratio of the total volume of the closed cavities and the total volume of the polymer walls is more than 16; wherein the water-dispersible resin comprises at least one selected from the group consisting of water-dispersible polyurethane resin, water-dispersible acrylic resin, water-dispersible polyurethane-modified acrylic resin, butyl cyanide emulsion, chloroprene latex, and polyvinyl acetate latex; wherein the carrier includes at least one selected from the group consisting of woven material, non-woven material, leather and elastic film. 2. Method according to claim 1, wherein the mixture from step 1) contains 40-60 parts by weight of water-dispersible resin, 10-50 parts by weight of non-expanded thermally expandable microspheres, 100-350 parts by weight of water. 3. The method according to claim 1 or 2, wherein the mixture from step 1) contains 45-55 parts by weight of water-dispersible resin, 10-30 parts by weight of non-expanded thermally expandable microspheres, 100-250 parts by weight of water. 4. The method according to claim 1 or 2, wherein the outer diameter of the non-expanded thermally expandable microspheres is 10 µm to 40 µm and the wall thickness is 1 µm to 10 µm. 5. The method according to any one of paragraphs. 1-4, in which the water-dispersible resin contains two kinds of different water-based polyurethane dispersions, one kind being 1-25 parts by weight and the other being 49-25 parts by weight. 6. The method according to claim 5, wherein the two kinds of different water-based polyurethane dispersions are respectively a first anionic polyurethane dispersion based on an aliphatic polyester and a second anionic polyurethane dispersion based on an aliphatic polyester, the first anionic polyurethane dispersion based on an aliphatic polyester is 10-20 parts by weight, preferably 15 parts; the second anionic polyurethane dispersion based on the aliphatic polyester is 40-30 parts by weight, preferably 35 parts. 7. The method according to any one of paragraphs. 1-6, in which the mixture from step 1) additionally contains at least one of: an antifoam agent in an amount of 0-1 parts by weight, a curing agent in an amount of 0-10 parts by weight, a thickener in an amount of 0-10 parts by weight, mold inhibitor 0-5 parts by weight, wetting and leveling agent 0-2 parts by weight, tactile modifier 0-5 parts by weight, water-based pigment 0-20 parts by weight ; preferably the mixture from step 1) additionally contains at least one of: antifoam agent in the amount of 0.1-1 parts by weight, curing agent in the amount of 0.1-10 parts by weight, thickener in the amount of 0.1-10 parts by weight , mold inhibitor 0.1-5 parts by weight, wetting and leveling agent 0.1-2 parts by weight, tactile modifier 0.1-5 parts by weight, water-based pigment in amount of 0.1-20 parts by weight. 8. The method according to any one of paragraphs. 1–7, in which at stage 4) the carrier is heated to 100–180°C for 10–300 seconds; preferably the carrier is heated to 120-160°C for 60-120 seconds; preferably the carrier is heated to 130-150°C for 60-90 seconds; preferably the carrier is heated to 140-150°C for 60-80 seconds. 9. The method according to p. 7, in which the curing agent includes at least one selected from the group consisting of polycarbodiimide, polyisocyanate, blocked polyisocyanate, aziridine and amino resin; the defoamer is a silicone defoamer; the wetting and leveling agent is a silicone wetting and leveling agent; the modifier for improving tactile sensations includes at least one selected from the group consisting of high molecular weight organosilicon compounds, wax powder, wax emulsion, colloidal or precipitated silicon dioxide and a liquid for dispersing them; the mold inhibitor includes an organic or inorganic water-dispersible mold inhibitor; the thickener comprises at least one selected from the group consisting of a polyurethane associative thickener, an alkali-swellable acrylic thickener, a cellulose thickener, and an inorganic thickener. 10. The method of claim 1, wherein the ratio of the size of the expanded thermally expandable microspheres in step 4) to the size of the non-expanded thermally expandable microspheres in step 1) is between 2 and 10. 11. The method according to any one of paragraphs. 1-10, in which the closed cell composite material contains a plurality of closed cavities and polymeric walls that separate the closed cavities from each other; wherein the size range of the closed cavities is 50 µm to 300 µm, preferably the size range of the closed cavities is 60 µm to 200 µm, even more preferably the size range of the closed cavities is 80 µm to 120 µm; and the ratio of the total volume of closed cavities and the total volume of the polymer walls is more than 16; preferably, the ratio of the total volume of the closed cavities and the total volume of the polymer walls is more than 33; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 83; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 166; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 333; preferably, the ratio of the total volume of the closed cavities and the total volume of the polymer walls is more than 417; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 556; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 833. 12. The method according to any one of paragraphs. 1-10, in which the closed-cell composite material is a thermal insulation material, and the thermal insulation material contains a plurality of closed cavities and polymer walls that separate the closed cavities from each other, while if the thickness of the thermal insulation material is 1 mm, the value in units of clo thermal insulation material is greater than or equal to 0.50, or greater than or equal to 0.60, or greater than or equal to 1.0, or greater than or equal to 1.5. 13. The method according to any one of paragraphs. 1-10, in which the closed cell composite material consists of a plurality of closed cavities and polymer walls that separate the closed cavities from each other, while the size range of the closed cavities is from 20 µm to 800 µm, preferably the size range of the closed cavities is from 50 µm to 300 µm, preferably the size range of closed cavities is from 60 µm to 200 µm, even more preferably the size range of closed cavities is from 80 µm to 120 µm; wherein the density of the closed cell composite material is from 5 kg/m ³ to 300 kg/m ³ , preferably the density of the closed cell composite material is from 10 kg/m ³ to 200 kg/m ³ , preferably the density of the closed cell composite material is from 20 kg/m ³ to 150 kg/m ³ , preferably the density of the closed cell composite material is from 30 kg/m ³ to 100 kg/m ³ , preferably the density of the closed cell composite material is from 40 kg/m ³ to 90 kg/m ³ , preferably the density of the closed cell composite is 50 kg/m ³ to 80 kg/m ³ , preferably the density of the closed cell composite is 60 kg/m ³ to 80 kg/m ³ . 14. A thermally insulating or noise-insulating closed-cell composite material, where the closed-cell composite material contains a carrier and a polymer layer formed on the carrier, and the polymer layer contains a plurality of closed cavities and polymer walls that separate the closed cavities from each other; wherein the polymer walls contain a thermoplastic or thermoset polymer on the inside of the relatively closed cavities, and the polymer walls contain a water-dispersible resin on the outside of the relatively closed cavities; while the range of sizes of closed cavities is from 20 microns to 800 microns; and the ratio of the total volume of closed cavities and the total volume of the polymer walls is more than 16; and the thickness of the polymer walls is from 0.01 µm to 5 µm; wherein the water-dispersible resin comprises at least one selected from the group consisting of water-dispersible polyurethane resin, water-dispersible acrylic resin, water-dispersible polyurethane-modified acrylic resin, butyl cyanide emulsion, chloroprene latex, and polyvinyl acetate latex; wherein the carrier includes at least one selected from the group consisting of woven material, non-woven material, leather and elastic film. 15. The closed cell composite material of claim 14, wherein the closed cavity size range is 50 µm to 300 µm, preferably the closed cavity size range is 60 µm to 200 µm, even more preferably the closed cavity size range is 80 µm to 120 µm; and the ratio of the total volume of closed cavities and the total volume of the polymer walls is more than 33; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 83; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 166; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 333; preferably, the ratio of the total volume of the closed cavities and the total volume of the polymer walls is more than 417; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 556; preferably, the ratio of the total volume of the closed cavities to the total volume of the polymer walls is greater than 833. 16. The closed cell composite material of claim 14 or 15, wherein the closed cell composite material consists of a plurality of closed cavities and polymeric walls that separate the closed cavities from each other. 17. Composite material with closed pores according to any one of paragraphs. 14-16, in which the thickness of the polymer walls is from 0.02 microns to 2 microns; preferably the thickness of the polymer walls is from 0.03 μm to 1.0 μm; preferably the thickness of the polymer walls is from 0.04 µm to 0.8 µm; preferably the thickness of the polymer walls is from 0.05 µm to 0.6 µm; preferably, the thickness of the polymer walls is between 0.1 µm and 0.5 µm. 18. Composite material with closed pores according to any one of paragraphs. 14-16, in which the shape of the closed cavities includes spherical, pseudospherical, and irregular shapes. 19. Composite material with closed pores according to any one of paragraphs. 14-16, in which closed cavities are formed as a result of an increase in the diameter of non-expanded thermally expanding microspheres by 2–10 times. 20. Composite material with closed pores according to any one of paragraphs. 14-16, where the closed cell composite material is a thermal insulation material, wherein if the thickness of the thermal insulation material is 0.2 to 3.0 mm, the clo value of the thermal insulation material is from 0.1 to 3.0. 21. Composite material with closed pores according to any one of paragraphs. 14-16, in which the polymer walls have a three-layer structure, while the three-layer structure contains two outer layers and an intermediate layer located between the two outer layers, while the materials of the two outer layers are the same, and the materials of the two outer layers are different from the material of the intermediate layer located between the two outer layers. 22. A thermally insulating or noise-insulating closed-cell composite material, where the closed-cell composite material contains a carrier and a polymer layer formed on the carrier, and the polymer layer contains a plurality of closed cavities and polymer walls that separate the closed cavities from each other; at the same time, the polymer walls have a three-layer structure, while the three-layer structure contains two outer layers and an intermediate layer located between the two outer layers, while the materials of the two outer layers are the same, and the materials of the two outer layers are different from the material of the intermediate layer located between the two outer layers; wherein the material of the two outer layers is a thermally expandable microsphere polymer and the material of the intermediate layer located between the two outer layers is a polymer obtained from a water-dispersible resin; wherein the water-dispersible resin comprises at least one selected from the group consisting of water-dispersible polyurethane resin, water-dispersible acrylic resin, water-dispersible polyurethane-modified acrylic resin, butyl cyanide emulsion, chloroprene latex, and polyvinyl acetate latex; wherein the carrier includes at least one selected from the group consisting of woven material, non-woven material, leather and elastic film; while the range of sizes of closed cavities is from 20 microns to 800 microns; while the density of the composite material with closed pores is from 5 kg/m ³ to 100 kg/m ³ . 23. The closed cell composite material of claim 22, wherein the size range of the closed cavities is 50 µm to 300 µm, preferably the size range of the closed cavities is 60 µm to 200 µm, even more preferably the size range of the closed cavities is 80 µm to 120 µm; and the density of the closed cell composite material is from 10 kg/m ³ to 100 kg/m ³ , preferably the density of the closed cell composite material is from 20 kg/m ³ to 100 kg/m ³ , preferably the density of the closed cell composite material is from 30 kg/m ³ to 100 kg/m ³ , preferably the density of the closed cell composite is 40 kg/m ³ to 90 kg/m ³ , preferably the density of the closed cell composite is 50 kg/m ³ to 80 kg /m ³ , preferably the density of the closed cell composite material is from 60 kg/m ³ to 80 kg/m ³ . 24. The closed cell composite material of claim 22 or 23, wherein the closed cell composite material consists of a plurality of closed cavities and polymeric walls that separate the closed cavities from one another. 25. Composite material with closed pores according to claim 22 or 23, in which the thickness of the polymer walls is from 0.01 microns to 5 microns; preferably the thickness of the polymer walls is from 0.02 μm to 2 μm; preferably the thickness of the polymer walls is from 0.03 μm to 1.0 μm; preferably the thickness of the polymer walls is from 0.04 µm to 0.8 µm; preferably the thickness of the polymer walls is from 0.05 µm to 0.6 µm; preferably, the thickness of the polymeric walls is between 0.1 µm and 0.5 µm. 26. Composite material with closed pores according to any one of paragraphs. 14–25, where the thermal conductivity of the closed cell composite material is less than 0.030 W/m⋅K; preferably, the thermal conductivity of the closed cell composite material is less than 0.025 W/m⋅K; preferably, the thermal conductivity of the closed cell composite material is less than 0.020 W/m⋅K; preferably, the thermal conductivity of the closed cell composite material is less than 0.016 W/m⋅K.

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