阅读说明：本技术 辐射制冷涂层及其应用、辐射制冷涂料、纺织品 (Radiation refrigeration coating and application thereof, radiation refrigeration coating and textile ) 是由 陈孝行 万容兵 杨宇龙 王明辉 其他发明人请求不公开姓名 于 2020-05-26 设计创作，主要内容包括：本发明涉及一种辐射制冷涂层及其应用、辐射制冷涂料、纺织品,其中辐射制冷涂层包括层叠设置的第一功能层和第二功能层,第一功能层对太阳光中的可见光和/或红外光的反射率≥85％,第二功能层对紫外光的反射率≥87％；第一功能层包括第一水性聚氨酯树脂和分布于第一水性聚氨酯树脂中的热反射颜填料；第二功能层包括第二水性聚氨酯树脂和分布于第二水性聚氨酯树脂中的紫外反射颜填料；第一水性聚氨酯树脂和第二水性聚氨酯树脂的分子结构中的软链段占比各自独立地为50％～90％；第一水性聚氨酯树脂和第二水性聚氨酯树脂的断裂伸长率各自独立地为400％～1500％。该辐射制冷涂层可以赋予户外纺织品良好的降温效果和优异的紫外线防护效果。(The invention relates to a radiation refrigeration coating and application thereof, a radiation refrigeration coating and a textile, wherein the radiation refrigeration coating comprises a first functional layer and a second functional layer which are arranged in a laminated manner, the reflectivity of the first functional layer to visible light and/or infrared light in sunlight is more than or equal to 85%, and the reflectivity of the second functional layer to ultraviolet light is more than or equal to 87%; the first functional layer comprises a first aqueous polyurethane resin and heat reflection pigment and filler distributed in the first aqueous polyurethane resin; the second functional layer comprises second aqueous polyurethane resin and ultraviolet reflecting pigment and filler distributed in the second aqueous polyurethane resin; the soft segment proportion in the molecular structure of the first aqueous polyurethane resin and the second aqueous polyurethane resin is respectively and independently 50-90%; the elongation at break of the first aqueous polyurethane resin and the elongation at break of the second aqueous polyurethane resin are each independently 400 to 1500%. The radiation refrigeration coating can endow outdoor textiles with good cooling effect and excellent ultraviolet protection effect.)

1. The radiation refrigeration coating is characterized by comprising a first functional layer and a second functional layer which are arranged in a stacked mode, wherein the reflectivity of the first functional layer to visible light and/or infrared light in sunlight is larger than or equal to 85%, and the reflectivity of the second functional layer to ultraviolet light is larger than or equal to 70%;

wherein the first functional layer comprises a first aqueous polyurethane resin and a heat-reflecting pigment filler distributed in the first aqueous polyurethane resin; the second functional layer comprises a second aqueous polyurethane resin and ultraviolet reflecting pigment and filler distributed in the second aqueous polyurethane resin;

the soft segment proportion in the molecular structure of the first aqueous polyurethane resin and the soft segment proportion in the molecular structure of the second aqueous polyurethane resin are respectively and independently 50-90%; the first aqueous polyurethane resin and the second aqueous polyurethane resin have respective elongation at break of 400% to 1500% independently.

2. The radiation refrigeration coating of claim 1 wherein in the first functional layer, the weight ratio of the heat reflective pigment to the first aqueous polyurethane resin is from 1:1 to 2: 1; and/or

In the second functional layer, the weight ratio of the ultraviolet reflection pigment filler to the second waterborne polyurethane resin is 1: 1-3: 1.

3. The radiation refrigeration coating of claim 1 wherein the heat reflective pigment filler is selected from inorganic particles having a refractive index > 2, the heat reflective pigment filler being at least one of titanium dioxide, zinc oxide, zirconium oxide, cerium oxide, zinc sulfide, zinc selenide, and glass beads; and/or

The ultraviolet reflection pigment filler comprises a mesoporous material and a nano material, wherein the mesoporous material is MCM-41 and/or SBA-15, the nano material is selected from inorganic particles with the refractive index of 1.4-2, and the nano material is at least one of magnesium oxide, aluminum oxide, calcium oxide, barium sulfate, calcium carbonate and ceramic beads.

4. The radiation refrigeration coating of claim 3 wherein the heat reflective color filler has a particle size of 200nm to 900 nm; the particle size of the nano material is 100 nm-200 nm; the aperture of the mesoporous material is 2 nm-50 nm.

5. The radiation refrigeration coating of claim 3, wherein the weight ratio of the mesoporous material in the ultraviolet reflecting pigment filler is 50-90%.

6. A radiation-cooling coating according to claim 1, wherein said first aqueous polyurethane resin and said second aqueous polyurethane resin are each independently selected from at least one of polyether polyurethane resin, polyester polyurethane resin, polycarbonate polyurethane, acrylic-modified polyurethane, and organosiloxane-modified polyurethane.

7. The radiation cooling coating of any one of claims 1 to 6, wherein the first functional layer has a thickness of 20 μm to 120 μm and the second functional layer has a thickness of 10 μm to 30 μm.

8. The radiation refrigeration coating according to claim 7, wherein the coating for preparing the first functional layer comprises the following raw material components in percentage by mass: 20-50% of the first waterborne polyurethane resin, 30-50% of the heat reflection pigment and filler, 1-10% of a first cross-linking agent, 0.1-0.5% of a first pH regulator, 1-10% of a first film forming auxiliary agent, 0.1-1% of a first defoaming agent, 0.1-1% of a first base material wetting agent, 1-5% of a first dispersing agent, 0.1-2% of a first leveling agent, 0.1-2% of a first thickening agent and 10-30% of water; and/or

The coating for preparing the second functional layer comprises the following raw material components in percentage by mass: 20-50% of second aqueous polyurethane resin, 35-60% of ultraviolet reflection pigment and filler, 1-8% of second cross-linking agent, 0.1-0.5% of second pH regulator, 1-10% of second film forming assistant, 0.1-1% of second defoaming agent, 0.1-1% of second base material wetting agent, 1-5% of second dispersing agent, 0.1-2% of second leveling agent, 0.1-2% of second thickening agent and 10-30% of water.

9. The radiation-cooled coating of claim 8, wherein the first crosslinker and/or the second crosslinker are aliphatic blocked isocyanate crosslinkers.

10. A radiation refrigeration coating is characterized by comprising a component A and a component B,

said a component being used to form a first functional layer as described in claims 1-9;

the B component is used to form the second functional layer described in claims 1-9.

11. Use of a radiation-refrigerating coating as claimed in any of claims 1 to 9 for the preparation of an article having radiation refrigeration.

12. A textile article, comprising a textile substrate and a radiation refrigeration coating according to any of claims 1 to 9, wherein the radiation refrigeration layer is disposed on the textile substrate, and a first functional layer of the radiation refrigeration coating is in contact with the textile substrate.

Technical Field

The invention relates to the technical field of textiles, in particular to a radiation refrigeration coating and application thereof, a radiation refrigeration coating and a textile.

Background

Under the continuous irradiation of sunlight, a large amount of heat can be accumulated on the fabric, so that the temperature of the surface and the inner side of the fabric is increased, particularly in hot summer and high-temperature areas, meanwhile, with the aggravation of the global warming trend, the highest historical temperature is frequently reported all over the world, and the energy consumption of an air conditioner is greatly increased; ozone layer depletion, leading to an increase in patients with skin diseases worldwide. These environmental problems bring inconvenience to people in production and life. The market urgently requires that the related coating for the fabric is generated, the coating is coated on the surface of the fabric, the heat transfer on the surface of the fabric is inhibited, the temperature inside a fabric covering is reduced, the effects of energy conservation and heat insulation are achieved, and the fabric is endowed with certain special functions of ultraviolet resistance, water resistance, ventilation and moisture permeability, flame retardance, stain resistance, shading and reflection and the like, so that the problems are solved or the harm caused by the phenomena is weakened.

At present, the main research direction of textile coatings is the development of functional coatings, such as flame retardance, temperature-adjusting phase change, air permeability and moisture permeability, four-prevention coatings, self-cleaning, water resistance, oil resistance, antibiosis, organosilicon softness, color luminescence and the like. The research and production of heat-insulating and cooling coating paint at home and abroad mainly focuses on the fields of building industry, industrial equipment, aviation and the like. But the research and the report aiming at the heat insulation and cooling coating for outdoor textiles such as tents and the like are less. The textile heat insulation coating on the market mainly comprises a silver colloid coating, a foaming coating and an ultraviolet protection coating, wherein the thermal emissivity of the silver colloid coating is about 50-60%, and although the silver colloid coating has a certain heat insulation function, the overall heat absorption is serious, the temperature reduction function is not provided, and the energy-saving effect is limited; the foaming coating has a certain heat insulation effect, but the thickness of the coating is thicker, the stripping strength of the coating is only (2-5) N/25mm, and the coating is easy to strip and fall off; the ultraviolet protective coating mainly realizes ultraviolet absorption and obstruction by adding an ultraviolet absorbent, but the ultraviolet absorption and obstruction can cause the heat absorption of the coating, and the heat insulation effect and the long-term weather-resistant aging effect are influenced.

Disclosure of Invention

Therefore, a radiation refrigeration coating with good cooling effect and ultraviolet protection effect for outdoor textiles and application thereof, a radiation refrigeration coating and textiles are needed to be provided.

The invention provides a radiation refrigeration coating, which comprises a first functional layer and a second functional layer which are arranged in a stacked mode, wherein the reflectivity of the first functional layer to visible light and/or infrared light in sunlight is larger than or equal to 85%, and the reflectivity of the second functional layer to ultraviolet light is larger than or equal to 70%;

wherein the first functional layer comprises a first aqueous polyurethane resin and a heat-reflecting pigment filler distributed in the first aqueous polyurethane resin; the second functional layer comprises a second aqueous polyurethane resin and ultraviolet reflecting pigment and filler distributed in the second aqueous polyurethane resin;

the soft segment proportion in the molecular structure of the first aqueous polyurethane resin and the soft segment proportion in the molecular structure of the second aqueous polyurethane resin are respectively and independently 50-90%; the first aqueous polyurethane resin and the second aqueous polyurethane resin have respective elongation at break of 400% to 1500% independently.

In some embodiments, in the first functional layer, the weight ratio of the heat-reflecting pigment and filler to the first aqueous polyurethane resin is 1: 1-2: 1.

In some embodiments, in the second functional layer, the weight ratio of the ultraviolet reflecting pigment and filler to the second aqueous polyurethane resin is 1:1 to 3: 1.

In some of these embodiments, the heat reflective pigment and filler is selected from inorganic particles with a refractive index > 2, and the heat reflective pigment and filler is at least one of titanium dioxide, zinc oxide, zirconium oxide, cerium oxide, zinc sulfide, zinc selenide, and glass beads.

In some embodiments, the ultraviolet reflecting pigment filler comprises a mesoporous material and a nanomaterial, the nanomaterial is selected from inorganic particles with refractive index of 1.4-2, the nanomaterial is at least one of magnesium oxide, aluminum oxide, calcium oxide, barium sulfate, calcium carbonate and ceramic beads, and the mesoporous material is MCM-41 and/or SBA-15.

In some embodiments, the weight ratio of the mesoporous material in the ultraviolet reflecting pigment filler is 50% to 90%.

In some of these embodiments, the heat reflective color filler has a particle size of 200nm to 900 nm; the particle size of the nano material is 100 nm-200 nm; the aperture of the mesoporous material is 2 nm-50 nm.

In some of these embodiments, the first and second aqueous polyurethane resins are each independently selected from at least one of a polyether polyurethane resin, a polyester polyurethane resin, a polycarbopolyurethane, an acrylic-modified polyurethane, and an organosiloxane-modified polyurethane.

In some of these embodiments, the first functional layer has a thickness of 20 μm to 120 μm and the second functional layer has a thickness of 10 μm to 30 μm.

In some embodiments, the coating for preparing the first functional layer comprises the following raw material components in percentage by mass: 20-50% of the first waterborne polyurethane resin, 30-50% of the heat reflection pigment and filler, 1-10% of the first cross-linking agent, 0.1-0.5% of the first pH regulator, 1-10% of the first film forming auxiliary agent, 0.1-1% of the first defoaming agent, 0.1-1% of the first base material wetting agent, 1-5% of the first dispersing agent, 0.1-2% of the first leveling agent, 0.1-2% of the first thickening agent and 10-30% of water.

In some embodiments, the coating for preparing the second functional layer comprises the following raw material components in percentage by mass: 20-50% of second aqueous polyurethane resin, 35-60% of ultraviolet reflection pigment and filler, 1-8% of second cross-linking agent, 0.1-0.5% of second pH regulator, 1-10% of second film forming assistant, 0.1-1% of second defoaming agent, 0.1-1% of second base material wetting agent, 1-5% of second dispersing agent, 0.1-2% of second leveling agent, 0.1-2% of second thickening agent and 10-30% of water.

In some of these embodiments, the first crosslinker and/or the second crosslinker are aliphatic blocked isocyanate crosslinkers.

According to still another aspect of the present invention, there is provided a radiation-curable coating material comprising an a component for forming the above-mentioned first functional layer and a B component; the B component is used to form the second functional layer described above.

According to another aspect of the invention there is provided the use of a radiation refrigeration coating as described above in the manufacture of an article having radiation refrigeration.

According to a further aspect of the present invention there is provided a textile product comprising a textile substrate and a radiation refrigerating coating as described above, the radiation refrigerating layer being provided on the textile substrate and the first functional layer of the radiation refrigerating coating being in contact with the textile substrate.

Compared with the prior art, the invention has the beneficial effects that:

the radiation refrigeration coating of the invention takes the water-based polyurethane resin with the soft segment accounting for 50-90 percent and the breaking elongation of 400-1500 percent as the matrix resin of the first functional layer and the second functional layer, can overcome the defects of hot adhesion, cold brittleness, poor hand feeling and the like existing in the traditional coating taking acrylic resin and the like as the matrix, and the first functional layer and the second functional layer are respectively endowed with the function of respectively reflecting visible light/infrared light and ultraviolet light by respectively dispersing the heat reflection pigment and the ultraviolet reflection pigment and the filler in the water-based polyurethane resin matrix, the first functional layer is utilized to reflect the visible light and/or the infrared light in sunlight, the absorption of solar heat is reduced to the minimum by the high reflection capacity of solar radiation energy, meanwhile, the heat is emitted out through an atmospheric window in the infrared radiation mode, the obvious cooling effect is achieved, and the second functional layer is utilized to reflect the ultraviolet light, the ultraviolet protection coating has an excellent ultraviolet protection effect, and the second functional layer further improves the emissivity of the coating at an atmospheric window waveband.

When the radiation refrigeration coating is used for outdoor textiles, the outdoor textiles can be endowed with good cooling effect and excellent ultraviolet protection effect, and the coating has high peeling strength, good weather resistance and good flexibility, so that the coating has good bonding force with textile substrates, and the obtained textiles have good flexibility and long-term weather resistance.

Detailed Description

In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

An embodiment of the invention provides a water-based radiation refrigeration coating, which comprises a first functional layer and a second functional layer which are arranged in a stacked mode, wherein the reflectivity of the first functional layer to visible light and/or infrared light in sunlight is larger than or equal to 85%, and the reflectivity of the second functional layer to ultraviolet light is larger than or equal to 70%.

The first functional layer comprises a first aqueous polyurethane resin and heat reflection pigment and filler distributed in the first aqueous polyurethane resin; the second functional layer comprises second aqueous polyurethane resin and ultraviolet reflecting pigment and filler distributed in the second aqueous polyurethane resin; the soft segment proportion in the molecular structure of the first aqueous polyurethane resin and the second aqueous polyurethane resin is respectively and independently 50-90%; the elongation at break of the first aqueous polyurethane resin and the elongation at break of the second aqueous polyurethane resin are each independently 400 to 1500%.

The polyurethane resin is a high polymer material formed by blocking a rigid hard chain segment and a flexible soft chain segment, wherein the hard chain segment consists of isocyanate and a micromolecular chain extender, the soft chain segment is oligomeric polyol, the glass transition temperature of the hard chain segment is higher than the normal temperature, the glass transition temperature of the soft chain segment is lower than the normal temperature, and the polyurethane resin has microphase separation due to incompatibility of the soft chain segment and the hard chain segment, so that the polyurethane resin with adjustable soft and hard segments can be obtained through structural design. In the present invention, the glass transition temperature of the soft segment and the glass transition temperature of the hard segment mean the glass transition temperatures of homopolymers of monomers constituting the soft segment or the hard segment. The invention adopts the waterborne polyurethane resin, and has the advantages of low toxicity, environmental protection and the like. The soft segment proportion in the first waterborne polyurethane resin and the soft segment proportion in the second waterborne polyurethane resin are respectively and independently 50-90%, and the first waterborne polyurethane resin and the second waterborne polyurethane resin can keep elasticity at the use temperature of-30-80 ℃, are not easy to yellow under the irradiation of sunlight, and have the advantages of good flexibility and strong adhesive force; the elongation at break of the fabric is 400-1500 percent, so that the requirement of the fabric on flexibility can be met; if the elongation at break of the matrix resin is less than 400%, the resulting coating does not meet the flexibility requirements of the textile.

The inventor tests the performance of the waterborne polyurethane resin of the invention, and the result is shown in the following table:

detecting items	Test standard	Test conditions	Performance of
				Normal temperature folding endurance	ISO32100	23℃	More than 20 ten thousand times
Low temperature folding endurance at minus 10 DEG C	ISO32100	-10℃	More than 18 ten thousand times
				Hydrolysis resistance	ISO1419	95% humidity at 70 deg.C	Greater than 1344 hours
Elongation at break	DIN53504	/	400％～1500％
				(adhesion) coating peeling Strength	FZT 01010-2012	/	>15N/25mm

The invention takes the waterborne polyurethane resin as the matrix resin of the first functional layer and/or the second functional layer, can overcome the defects of hot sticking, cold brittleness, poor hand feeling and the like of the traditional coating taking acrylic resin and the like as the matrix, and has the advantages of low volatilization and low toxicity of the waterborne coating. The radiation refrigeration coating takes the waterborne polyurethane resin as a base material, the first functional layer and the second functional layer are respectively endowed with the effect of respectively reflecting visible light/infrared light and ultraviolet light by respectively dispersing the heat reflection pigment filler and the ultraviolet reflection pigment filler in the base material, the first functional layer is utilized to reflect the visible light and/or the infrared light in sunlight, the absorption of solar heat is reduced to the minimum by the high reflection capacity of solar radiation energy, meanwhile, the heat is emitted in the mode of radiation of an atmospheric window waveband, the radiation refrigeration coating has a remarkable cooling effect, the second functional layer is utilized to reflect the ultraviolet light, the radiation refrigeration coating has an excellent ultraviolet protection effect, and the emissivity of the coating in the atmospheric window waveband can be further improved. The coating is used for outdoor textiles, so that the outdoor textiles can be endowed with a good cooling effect and an excellent ultraviolet protection effect, and the coating is high in peel strength, good in weather resistance and good in flexibility, so that the binding force with the textile substrate is good, the obtained textiles are good in flexibility and resistant to weather for a long time.

In some embodiments, the aqueous polyurethane resin has an elongation at break of 700% to 1100%.

In some embodiments, in the first functional layer, the weight ratio of the heat-reflecting pigment filler to the first aqueous polyurethane resin is 1:1 to 2: 1.

In some embodiments, the heat reflective pigment and filler is selected from inorganic particles with refractive index > 2, and the heat reflective pigment and filler is at least one of titanium dioxide, zinc oxide, zirconium oxide, cerium oxide, zinc sulfide, zinc selenide and glass beads.

The titanium dioxide has the characteristics of high covering power and low oil absorption, so that the base resin can fully wrap the filler when the coating is formed into a film, and the coating is not easy to crack after the film is formed; barium sulfate, zinc oxide, zirconium oxide, cerium oxide, zinc sulfide, zinc selenide and glass beads have the characteristic of high refractive index.

Furthermore, the particle size of the heat reflection pigment and filler is 200 nm-900 nm.

The refractive index of the first aqueous polyurethane resin is 1.4-1.5, the refractive index of the heat reflection pigment and filler is more than 2, and the larger the difference between the refractive indexes of the aqueous polyurethane resin and the heat reflection pigment and filler is, the higher the reflectivity of the first functional layer to visible light and near infrared light is. The particle size of the heat reflection pigment and filler is 200-900 nm, which is half of the wavelength range of visible and near-infrared bands, and the reflectivity of the first functional layer to visible light/infrared light can be fully ensured to be more than or equal to 85%.

In some embodiments, the weight ratio of the ultraviolet reflecting pigment filler to the second aqueous polyurethane resin in the second functional layer is 1:1 to 3: 1.

In some embodiments, the ultraviolet reflecting pigment filler comprises a mixture of mesoporous materials and nano materials, the nano materials are selected from inorganic particles with the refractive index of 1.4-2, the nano materials are at least one of magnesium oxide, aluminum oxide, calcium oxide, barium sulfate, calcium carbonate and ceramic beads, and the mesoporous materials are MCM-41 and/or SBA-15.

Further, the weight ratio of the mesoporous material in the ultraviolet reflecting pigment filler is 50% to 90%, and more preferably, the weight ratio of the mesoporous material in the ultraviolet reflecting pigment filler is 60% to 80%.

Further, the particle size of the nanomaterial is 100nm to 200nm, and more preferably, the particle size of the nanomaterial is 140nm to 160 nm.

Further, the mesoporous material has an ordered nano-channel structure, and the pore diameter of the mesoporous material is 2nm to 50nm, and more preferably, the pore diameter of the mesoporous material is 8nm to 15 nm.

Through the matching of the second waterborne polyurethane resin and the ultraviolet reflection pigment and filler, the reflectivity of the second functional layer to ultraviolet light is more than or equal to 70 percent, and the reflectivity heat to visible light/infrared light is 40 to 50 percent.

In some embodiments, the first and second aqueous polyurethane resins are each independently selected from at least one of a polyether polyurethane resin, a polyester polyurethane resin, a polycarbopolyurethane, an acrylic-modified polyurethane, and an organosiloxane-modified polyurethane.

In some embodiments, the first functional layer has a thickness of 20 μm to 120 μm and the second functional layer has a thickness of 10 μm to 30 μm.

In some embodiments, the coating for preparing the first functional layer comprises the following raw material components in percentage by weight: 20-50% of first waterborne polyurethane resin, 30-50% of heat reflection pigment and filler, 1-10% of first cross-linking agent, 0.1-0.5% of first pH regulator, 1-10% of first film forming auxiliary agent, 0.1-1% of first defoaming agent, 0.1-1% of first base material wetting agent, 1-5% of first dispersing agent, 0.1-2% of first leveling agent, 0.1-2% of first thickening agent and 10-30% of water.

In some embodiments, the coating for preparing the second functional layer comprises the following raw material components in percentage by weight: 20-50% of second aqueous polyurethane resin, 30-50% of ultraviolet reflection pigment and filler, 1-8% of second cross-linking agent, 0.1-0.5% of second pH regulator, 1-10% of second film forming auxiliary agent, 0.1-1% of second defoaming agent, 0.1-1% of second base material wetting agent, 1-5% of second dispersing agent, 0.1-2% of second leveling agent, 0.1-2% of second thickening agent and 10-30% of water.

It is understood that the film forming aid, the defoaming agent, the pH adjuster, the wetting agent, the dispersant, the leveling agent, the thickener, and other aids used in the raw materials of the first functional layer and the second functional layer, respectively, may be common aids for aqueous coating materials.

Further, the crosslinking agent is selected from at least one of aziridine crosslinking agent, aliphatic blocked isocyanate crosslinking agent, aqueous isocyanate crosslinking agent, polyamine crosslinking agent, polyol crosslinking agent, and metal organic compound. Preferably, the crosslinker is an aliphatic blocked isocyanate crosslinker.

When the first functional layer and/or the second functional layer are/is prepared, the water-based polyester resin and the cross-linking agent can form a three-dimensional network structure, so that the water resistance, the solvent resistance, the flexibility and other properties of the coating can be improved.

Furthermore, the molecular structure of the aliphatic blocked isocyanate crosslinking agent does not contain benzene rings, so that the waterborne polyurethane resin and the base material do not have yellowing at high temperature. Meanwhile, the blocking group in the molecular structure of the aliphatic blocked isocyanate crosslinking agent reacts with an isocyanate group to generate a urethane bond, the urethane bond is cracked under the heating condition (generally over 100 ℃) to generate isocyanate, and the isocyanate reacts with hydroxyl, carboxyl and amino of the textile to generate crosslinking, so that the bonding force of the polyurethane resin coating and the textile substrate can be further increased. If the cross-linking agent is a non-blocked isocyanate cross-linking agent (such as water-based isocyanate or aziridine) which needs to be added into the coating and stirred before the functional layer raw material is used, the non-blocked isocyanate cross-linking agent can react at normal temperature to influence the adhesive force of the coating and the textile fibers; and the operable time of the non-blocked isocyanate crosslinking agent is short, so that the coating is very inconvenient in the construction of fabric coatings.

In another embodiment of the present invention, a radiation refrigeration coating is provided for forming the radiation refrigeration coating, and the radiation refrigeration coating includes an a component and a B component, wherein the a component is used for forming the first functional layer, and the B component is used for forming the second functional layer.

In some embodiments, the A component comprises a first aqueous polyurethane resin and a heat reflection pigment, the B component comprises a second aqueous polyurethane resin and an ultraviolet reflection pigment, and the soft segment proportion in the molecular structure of the first aqueous polyurethane resin and the soft segment proportion in the molecular structure of the second aqueous polyurethane resin are respectively and independently 50-90%; the elongation at break of the first aqueous polyurethane resin and the elongation at break of the second aqueous polyurethane resin are each independently 400 to 1500%.

In some embodiments, the a component comprises the following raw material components in percentage by weight: 20-50% of first waterborne polyurethane resin, 30-50% of heat reflection pigment and filler, 1-10% of first cross-linking agent, 0.1-0.5% of first pH regulator, 1-10% of first film forming auxiliary agent, 0.1-1% of first defoaming agent, 0.1-1% of first base material wetting agent, 1-5% of first dispersing agent, 0.1-2% of first leveling agent, 0.1-2% of first thickening agent and 10-30% of water.

Thus, after the raw material components of the component A are uniformly mixed, the first functional layer is formed on the textile by coating processes such as dip coating, spray coating, spin coating and the like.

Specifically, the heat reflection pigment and filler, a first film forming auxiliary agent, a first defoaming agent, a first wetting agent, a first dispersing agent and a first leveling agent are dispersed in water at a low speed and ground to a proper fineness to obtain a first dispersion system; uniformly mixing the first dispersion system with a first aqueous polyurethane dispersion, a first thickening agent, a first cross-linking agent and a first pH regulator to obtain a first functional layer coating; and coating the first functional layer coating on the textile substrate, and drying to form the first functional layer. The first functional layer has the function of reflecting visible light and infrared light in sunlight, and the reflectivity is not lower than 85%.

Further, the component A comprises the following raw material components in percentage by weight:

25-45% of first aqueous polyurethane resin dispersoid, 30-50% of heat reflection pigment and filler, 3-7% of first cross-linking agent, 0.2-0.4% of first pH regulator, 3-8% of first film forming assistant, 0.2-0.8% of first defoaming agent, 0.2-0.8% of first base material wetting agent, 1-3% of first dispersing agent, 0.5-1% of first leveling agent, 0.3-1.6% of first thickening agent and 15-25% of water.

In some embodiments, the B component comprises the following raw material components in percentage by weight: 20-50% of second aqueous polyurethane resin, 35-60% of ultraviolet reflection pigment and filler, 1-8% of second cross-linking agent, 0.1-0.5% of second pH regulator, 1-10% of second film forming auxiliary agent, 0.1-1% of second defoaming agent, 0.1-1% of second base material wetting agent, 1-5% of second dispersing agent, 0.1-2% of second leveling agent, 0.1-2% of second thickening agent and 10-30% of water.

After the raw material components of the component B are uniformly mixed, the second functional layer is formed on the textile by coating processes such as dip coating, spray coating, spin coating and the like.

Specifically, dispersing ultraviolet reflection pigment and filler, a second film forming auxiliary agent, a second defoaming agent, a second wetting agent, a second dispersing agent and a second leveling agent in water at a low speed, and grinding to a proper fineness to obtain a second dispersion system; uniformly mixing the second dispersion system with a second aqueous polyester dispersion, a second thickening agent, a second crosslinking agent and a second pH regulator to obtain a second functional layer coating; and coating the second functional layer coating on the first functional layer, and drying to form the second functional layer. The second functional layer has the function of reflecting ultraviolet light, and the reflectivity is not lower than 70%.

Further, the component B comprises the following raw material components in percentage by weight: 25-35% of second aqueous polyurethane resin, 35-45% of ultraviolet reflection pigment and filler, 1.5-6% of second cross-linking agent, 0.1-0.4% of second pH regulator, 2-7% of second film forming assistant, 0.3-0.8% of second defoaming agent, 0.2-0.8% of second base material wetting agent, 1.5-4% of second dispersing agent, 0.5-1.5% of second leveling agent, 0.3-1.5% of second thickening agent and 15-25% of water.

The invention also provides a preparation method of the radiation refrigeration coating, which is used for preparing the radiation refrigeration coating and comprises the following steps: forming a first functional layer and a second functional layer which are arranged in a stacked manner;

the reflectivity of the first functional layer to visible light and/or infrared light in sunlight is larger than or equal to 85%, and the reflectivity of the second functional layer to ultraviolet light is larger than or equal to 70%;

the first functional layer comprises a first aqueous polyurethane resin and heat reflection pigment and filler distributed in the first aqueous polyurethane resin; the second functional layer comprises second aqueous polyurethane resin and ultraviolet reflecting pigment and filler distributed in the second aqueous polyurethane resin; the soft segment proportion in the molecular structure of the first aqueous polyurethane resin and the second aqueous polyurethane resin is respectively and independently 50-90%; the elongation at break of the first aqueous polyurethane resin and the elongation at break of the second aqueous polyurethane resin are each independently 400 to 1500%.

In another embodiment, the present invention provides a use of the radiation-curable coating described above in the preparation of an article having radiation-curable properties.

Specifically, the radiation-cooled coating described above can be disposed on a surface of a substrate, and the first functional layer of the radiation-cooled coating can be in contact with the textile substrate. Therefore, visible light, infrared light and ultraviolet light in sunlight can be reflected, heat in the base material is emitted in an atmospheric window waveband radiation mode, the temperature of the base material is effectively reduced, and meanwhile, a human body is protected from being damaged by excessive ultraviolet light.

In another embodiment of the present invention, there is also provided a textile product comprising a textile substrate and the radiation refrigeration coating described above, wherein the radiation refrigeration layer is disposed on the textile substrate, and the first functional layer of the radiation refrigeration coating is in contact with the textile substrate.

The following are specific examples

The solid content of the aqueous polyurethane dispersion used in the specific embodiment of the invention is 50%; the acrylic acid dispersion has a solid content of 50%; the solid content of the silicone dispersion was 50%; the average particle size of the titanium dioxide is 600 nm; the average particle size of the coarse whiting powder is 600 nm; the average grain diameter of the aluminum silver powder is 600 nm; the average grain diameter of the zinc oxide is 600 nm; the average pore diameter of SBA-15 is 15 nm; the average pore diameter of the MCM-41 is 15 nm; the average grain diameter of the nano zinc oxide is 120 nm; the average grain diameter of the nano calcium carbonate is 140 nm; the average grain diameter of the nano ceramic ball is 200 nm.

Firstly, preparing a first functional layer coating:

1) the respective raw material components (in parts by weight) of the first functional layer coating materials of examples 1 to 6 and comparative examples 1 to 3 were prepared as shown in table 1.

TABLE 1

2) Preparing a first functional layer coating:

respectively and uniformly dispersing the titanium dioxide, or the coarse whiting powder, or the aluminum silver powder, or the zinc oxide, the film forming assistant, the defoaming agent, the wetting agent, the dispersing agent and the leveling agent in water at a low speed, and grinding the mixture to a proper fineness by using a ball milling surface to respectively obtain first dispersion systems of the examples and the comparative examples.

The dispersions, thickeners, crosslinking agents, and pH adjusters of the examples and comparative examples were added to the first dispersion system, respectively, and uniformly dispersed to obtain the first functional layer paints of examples 1 to 6 and comparative examples 1 to 3, respectively.

Secondly, preparing a second functional layer coating:

1) the respective raw material components (in parts by weight) of the second functional layer paints of examples 7 to 11 and comparative examples 4 to 6 were prepared as shown in Table 2.

TABLE 2

2) Preparing a second functional layer coating:

the mesoporous material and/or the nano material, the film forming assistant, the defoaming agent, the wetting agent, the dispersing agent and the leveling agent in each example and comparative example are uniformly dispersed in water at a low speed, and are ground to appropriate fineness by using a ball milling surface, so that second dispersion systems in each example and comparative example are obtained.

The dispersions, the thickening agent, the crosslinking agent and the pH adjusting agent of the examples and the comparative examples are respectively added into the second dispersion system, and are uniformly dispersed, so that the second functional layer coatings of the examples 7 to 11 and the comparative examples 4 to 6 are respectively obtained.

The soft segment ratios in the molecular structures of the dispersions used in examples 1 to 11 and comparative examples 1 to 6 are shown in Table 3; the dispersions used in examples 1 to 11 and comparative examples 1 to 6 described above were tested for elongation at break with reference to the method of DIN53504 rubber elastomer test, the results of which are shown in Table 3.

TABLE 3

	Soft segment ratio	Elongation at break
			Example 1	87％	1220％
Example 2	57％	530％
			Example 3	77％	840％
Example 4	85％	1170％
			Example 5	90％	1500％
Example 6	50％	400％
			Example 7	81％	830％
Example 8	65％	670％
			Example 9	76％	790％
Example 10	84％	1050％
			Example 11	84％	1080％
Comparative example 1	75％	770％
			Comparative example 2	52％	450％
Comparative example 3	52％	440％
			Comparative example 4	64％	650％
Comparative example 5	76％	780％
			Comparative example 6	65％	670％

Thirdly, preparing the textile

1) The first functional layer coating prepared in each of the above examples and comparative examples is respectively coated on a fiber base fabric, and after drying, a first functional layer with a certain thickness is formed on the surface of the fiber base fabric.

2) Coating the second functional layer coating prepared in each of the above examples and comparative examples on the fiber base cloth or the first functional layer of the above step 1), and drying to form a second functional layer with a certain thickness.

The thicknesses of the corresponding layers of the textiles A-W and the combination mode of the functional layers are shown in the following table 4; the coating raw materials and components of comparative example 7 in table 4 are the raw materials and components of examples 2 and 8, and the preparation method comprises the steps of uniformly dispersing the titanium dioxide, the mesoporous materials and the nano materials, the film forming auxiliary agent, the defoaming agent, the wetting agent, the dispersing agent and the leveling agent in examples 5 and 8 in water at a low speed, and grinding the mixture to a proper fineness by using a ball milling surface to obtain a first dispersion system of comparative example 7.

Then, the dispersions of examples 5 and 8, a thickener, a crosslinking agent, and a pH adjuster were added to the first dispersion system, and uniformly dispersed to obtain the first functional layer coating of comparative example 7.

The prepared functional layers and the radiation refrigeration coating are tested for relevant performance, and the results are shown in the following table 4.

The test items and test methods are as follows:

1. heat reflectance: the reflectance of the textile was measured with a platinum elmer spectrophotometer lambda950 at an angle of incidence of 5 ° and the average reflectance of the entire spectrum (wavelength range 0.38 μm to 2.5 μm) was calculated as the value of the thermal reflectance of the textile. The incident angle is an angle with respect to a line perpendicular to the film surface.

2. Ultraviolet reflectance: the reflectance of the textile was measured with a platinum elmer spectrophotometer lambda950 at an angle of incidence of 5 ° and the average reflectance over the entire ultraviolet spectrum (wavelength range 0.3 μm to 0.38 μm) was calculated as the value of the ultraviolet reflectance of the textile. The incident angle is an angle with respect to a line perpendicular to the film surface.

3. Coating stripping strength: reference FZT 01010-.

4. Folding endurance times: test with reference to ISO 32100.

TABLE 4

As can be seen from Table 4, the thermal reflectivity of the first functional layer in the embodiment of the invention is not less than 85%, the visible light and the infrared light in sunlight can be well reflected, the bonding force with the textile substrate is good, the peel strength is more than 15N/25mm, and the flexibility is good, as can be seen from A to J, when the thickness of the first functional layer is not more than 120 μm, the folding endurance time is not less than 10 ten thousand times, and when the thickness is more than 120 μm, the thermal reflectivity is not obviously improved, but the flexibility of the coating can be reduced; k, M-P show that the ultraviolet reflectivity of the second functional layer is more than or equal to 70%, and the textile comprising the first functional layer and the second functional layer has good heat reflection and ultraviolet reflection effects, and can well play roles in cooling and preventing ultraviolet rays.

However, from W, it is known that a coating material prepared by mixing a coating material having a first functional layer reflecting infrared or visible light with a coating material having a second functional layer reflecting ultraviolet light has an ultraviolet reflectance of only 7% and does not function as an ultraviolet ray protection, and a heat reflectance of only 72%.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.