A waterproof and breathable composite membrane with thermal insulation function and a preparation method thereof

Abstract

The application discloses a waterproof and breathable composite film with a heat insulation function and a preparation method thereof, and relates to the technical field of high polymer materials. The waterproof and breathable composite film with the heat insulation function comprises, from inside to outside, a heat preservation layer, a transition layer and a waterproof layer; the waterproof layer is a polyolefin heat insulation and breathable film; the transition layer is a spun-bonded non-woven fabric; and the heat preservation layer is an aerogel glass fiber needle felt. The aerogel glass fiber needle felt comprises composite fiber filaments, and the raw material of the composite fiber filaments comprises 50-70 wt% of glass fibers, 30-50 wt% of polyester fibers and 0-20 wt% of viscose fibers. The application prepares a composite film with waterproof and breathable functions and a heat insulation function.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to a waterproof and breathable composite film with heat insulation function and a preparation method thereof. BACKGROUND

[0002] The waterproof building material film is a kind of high polymer waterproof material, which is used for wrapping or covering on the surface of the building, so as to isolate the surface of the building from water, thereby playing a waterproof and sealing role. The original waterproof building material film only has a waterproof function. Due to the tightness of the characteristics, the water vapor in the building structure cannot be dispersed, resulting in the problem of mold growth. Later, the waterproof and breathable film was developed, which has both waterproof and breathable functions. By rapidly discharging the water vapor in the building structure, the growth of mold is avoided.

[0003] With the emphasis on building energy saving, it is found that the waterproof and breathable film does not have heat insulation function. In the high temperature environment in summer, the radiant heat and ultraviolet rays can all reach the indoor through the waterproof and breathable film, resulting in the rise of indoor temperature. In the low temperature environment in winter, the waterproof and breathable film cannot block the heat in the room from diffusing to the external environment. In this case, the temperature in the room needs to be maintained for a long time by relying on the operation of air conditioner, which increases the energy consumption.

[0004] Therefore, a composite film with both waterproof and breathable functions and heat insulation function is needed, which can isolate heat transfer and ultraviolet radiation in high temperature environment and ensure that heat will not diffuse to the environment in low temperature environment. SUMMARY

[0005] In order to prepare a composite film with both waterproof and breathable functions and heat insulation function, the present application provides a waterproof and breathable composite film with heat insulation function and a preparation method thereof.

[0006] The waterproof and breathable composite film with heat insulation function and the preparation method thereof provided by the present application adopt the following technical scheme:

[0007] In a first aspect, the present application discloses a waterproof and breathable composite film with heat insulation function, which comprises a heat preservation layer, a transition layer and a waterproof layer arranged in sequence from inside to outside. The waterproof layer is a polyolefin heat insulation and breathable film. The transition layer is a spun-bonded non-woven fabric. The heat preservation layer is an aerogel glass fiber needle felt. The aerogel glass fiber needle felt comprises composite fiber filaments. The raw materials of the composite fiber filaments comprise 50-70wt% of glass fiber, 30-50wt% of polyester fiber and 0-20wt% of viscose fiber.

[0008] The aerogel glass fiber needled felt is prepared by the following steps: glass fiber needled felt is prepared from composite fiber filaments; silica aerogel is prepared, and a composite material is obtained by using glass fiber needled felt and silica aerogel; the surface of the composite material is modified by trimethylchlorosilane / n-hexane solution, washed and dried to obtain aerogel glass fiber needled felt.

[0009] Optionally, the composite fiber filament comprises 50-60 wt% glass fiber, 30-40 wt% polyester fiber, and 10-20 wt% viscose fiber.

[0010] Optionally, the composite fiber filament comprises 50 wt% glass fiber, 40 wt% polyester fiber, and 10 wt% viscose fiber.

[0011] By adopting the above technical solutions, the polyolefin heat-insulating and breathable membrane plays a role in waterproofing and heat insulation, and maintains sufficient hydrostatic pressure in the composite membrane; the transition layer enables better adhesion between the waterproof layer and the heat insulation layer, enhances the overall tensile strength and mechanical properties of the composite membrane, and reduces heat conduction from the waterproof layer to the heat insulation layer while maintaining waterproofness and breathability; the heat insulation layer has good heat insulation effect, as well as hydrophobic properties and good mechanical properties.

[0012] In aerogel glass fiber needle-punched felt, silica aerogel and glass fiber needle-punched felt are composited, solving the molding problem and addressing the brittleness of silica aerogel while retaining its advantages of low thermal conductivity and hydrophobicity. Polyester and viscose fibers are added to the composite fiber filaments, ensuring the tensile strength and bending resistance of the aerogel glass fiber needle-punched felt, while also providing a certain degree of air permeability and moisture wicking. Therefore, the aerogel glass fiber needle-punched felt, acting as an inner barrier, can play a role in thermal insulation.

[0013] Optionally, the aerogel glass fiber needled felt is prepared through the following specific steps:

[0014] (1). Preparation of glass fiber needled felt:

[0015] The composite fiber filaments are opened and mixed, mechanically laid, pre-needled, main needled, heat-set, wound and cut to obtain glass fiber mat. The needled glass fiber mat is heated to separate phases, sent to a strong acid bath for leaching, washed with water, treated with a neutralization solution, and dried to obtain glass fiber needled mat.

[0016] (2). Synthesis of sol:

[0017] Using Na + The water in the ion exchange resin membrane is diluted with water glass to obtain a mixed solution, and 0.3-0.6 mol / L ammonia water is added to carry out a condensation reaction. The mixture is stirred for 10-20 min to obtain a silica-containing sol.

[0018] (3) Preparation of aerogel glass fiber needle felt:

[0019] The silica-containing sol was poured into a mold and left to wait for it to gel and solidify into silica aerogel. The glass fiber needle felt was immersed in ethanol and taken out. The glass fiber needle felt soaked with ethanol was heated to 40-45℃ and placed in the solidified silica aerogel for aging for 6-6.5h. The glass fiber needle felt was taken out and the aging and taking-out process was repeated to obtain a composite material.

[0020] A trimethylchlorosilane / n-hexane solution with a molar ratio of 1:2 was added to the composite material to modify the surface of the composite material. The reaction was carried out at 40-45℃ for 24h. The composite material was washed and finally placed in an oven at 120-125℃ for drying for 8-10h to obtain an aerogel glass fiber needle felt.

[0021] Optionally, in step (3), the mass ratio of the composite material to the glass fiber needle felt is 1.3-2:1.

[0022] By using the above technical solution, in the preparation of the aerogel glass fiber needle felt, the silica aerogel can be wrapped around the glass fiber needle felt by using the sol-gel method to realize the combination of the silica aerogel and the fiber. The high porosity and particle of the silica aerogel prevent the contact between the fibers, lengthen the heat transfer path, and reduce the gas convection effect between the material voids, thereby realizing the heat insulation effect.

[0023] In the process of preparing the aerogel glass fiber needle felt, water glass is selected as the silicon source, which has a lower cost. The sodium ions in the water glass can be removed by diluting the water flowing through the Na+ exchange resin membrane, which can improve the low thermal conductivity and high specific surface area of the silica aerogel, and reduce the risk of cracking of the aerogel. There are a large number of unaggregated hydrogen bonds after gelation, so trimethylchlorosilane and n-hexane are selected for hydrophobic modification. The n-hexane can exchange with the water in the pores of the aerogel, and the trimethylchlorosilane can modify the inner surface of the pores to replace the surface hydrogen bonds, thereby realizing the hydrophobicity.

[0024] Optionally, the glass fiber is a modified glass fiber modified by a mercaptosilane coupling agent and calcium carbonate. The modified glass fiber is prepared by the following method:

[0025] The glass fiber is pretreated with a sodium hydroxide solution, ultrasonically treated, and taken out. The glass fiber is washed to neutral to obtain washed glass fiber.

[0026] The 3-mercapto propyl triethoxysilane is dissolved in ethanol to prepare B liquid, the cleaned glass fiber is added into the B liquid and mixed thoroughly, ultrasonic oscillation is performed for 10-15 min, the temperature is 20-25℃, the glass fiber is taken out after standing for 22-24 h, and the glass fiber is rinsed with acetone and dried at 90-100℃ to obtain the preliminary treated fiber;

[0027] The preliminary treated fiber is immersed in a calcium chloride aqueous solution, a dispersant EDTA-2Na is added after sufficient stirring, and sodium carbonate is added, stirring is performed at 40-50℃ for 15-20 min, the fiber is taken out, washed, and dried to obtain the modified glass fiber.

[0028] By adopting the above technical scheme, the fiber after alkali treatment has more reactive active sites, which is beneficial to the adhesion of the mercapto silane coupling agent and calcium carbonate; the mercapto silane coupling agent and calcium carbonate are combined for modification, the mercapto silane coupling agent produces a chemical bonding effect between the glass fiber and the silica aerogel through the introduction of mercapto, the reinforcing effect on the aerogel is improved, and the influence on the thermal conductivity is smaller; the calcium carbonate is deposited on the surface of the glass fiber, the hydrophobicity is enhanced, and the surface roughness of the glass fiber is improved, which is beneficial to improving the tensile strength of the needle punched felt; the porosity of the needle punched felt is improved through combined modification, thereby the air permeability and moisture permeability are improved, the surface of the needle punched felt is roughened due to the presence of calcium carbonate, which is further beneficial to the bonding force between the aerogel glass fiber needle punched felt and the spun-bonded non-woven fabric, and the mechanical properties of the waterproof and air permeable membrane are improved.

[0029] Optionally, the viscose fiber is a cross-linked modified viscose fiber, and the cross-linked modified viscose fiber is prepared by the following method:

[0030] The viscose fiber is soaked in a 20-30g / L sodium sulfite solution, treated at 75-78℃ for 1-1.5h, and then washed to obtain the pretreated viscose fiber;

[0031] A treatment liquid is prepared by using sodium hypophosphite and BTCA cross-linking agent, the mass ratio of BTCA to sodium hypophosphite is 8: (3-5), and the pretreated viscose fiber is treated by three immersions and three wrappings in the treatment liquid.

[0032] Then, the viscose fiber is dried at a high temperature of 150-180℃ for 3-5 min, and the cross-linked fiber is washed and dried to obtain the cross-linked modified viscose fiber.

[0033] By adopting the above technical scheme, the viscose fiber is cross-linked and reinforced by the chemical cross-linking agent BTCA, the physical strength of the viscose fiber is improved, the free movement between the molecules is reduced, the viscose fiber, the glass fiber, and the silica aerogel are connected into a stable three-dimensional network system, and the mechanical properties of the composite membrane are improved.

[0034] Optionally, the needle density in the needle punching process is 100-500 needles / cm 2 , the needle punching depth is 8-15mm, the needle punching frequency is 800-1500 times / min, and the heat setting temperature is 200-300℃.

[0035] Optionally, the polyolefin heat-insulating and breathable film comprises the following raw materials by weight:

[0036] Polypropylene 20-32 parts;

[0037] POE plastic 4-9 parts;

[0038] Low-density polyethylene 6-12 parts;

[0039] Calcium carbonate 45-52 parts;

[0040] Nano-silicon dioxide 2-5 parts;

[0041] Silane coupling agent KH-550 1-3 parts;

[0042] Rutile titanium dioxide 3-7 parts.

[0043] By adopting the above technical scheme, polypropylene and calcium carbonate are selected as the main raw materials, and POE plastic and low-density polyethylene are added at the same time, so that the polyolefin heat-insulating and breathable film prepared has excellent waterproof and breathable properties and mechanical properties, and the processing fluidity and stability meet the film preparation requirements. Rutile titanium dioxide and nano-silicon dioxide are added in the raw materials of the polyolefin heat-insulating and breathable film to synergistically play a heat-insulating effect, and at the same time, ultraviolet rays can be isolated; the addition of the silane coupling agent improves the dispersibility and compatibility of the filler in the polypropylene system.

[0044] Optionally, the calcium carbonate is calcium carbonate subjected to surface coating treatment, and the specific treatment steps are as follows:

[0045] The calcium carbonate and lauric acid are placed in a high-speed mixer, and high-speed mixing and coating treatment are carried out at a temperature of 90-120℃, and the treatment time is 25-30min, wherein the weight of the lauric acid is 0.8-2.2% of the calcium carbonate.

[0046] By adopting the above technical scheme, lauric acid is used as a surface treatment agent to improve the dispersibility of calcium carbonate in the polypropylene system by surface coating treatment of calcium carbonate, so that the uniformity and breathability of the polyolefin heat-insulating and breathable film are improved.

[0047] Optionally, the polyolefin heat-insulating and breathable film has a grammage of 20-200g / cm 2 , and a thickness of 10-150μm.

[0048] Optionally, the polyolefin heat-insulating and breathable film is prepared by the following specific steps.

[0049] After mixing various raw materials and granulating, the polyolefin heat-insulating and breathable film is obtained through melt extrusion casting, uniaxial stretching, heat setting, cooling, corona, and winding, wherein the melt extrusion temperature is 170-230℃, the heat setting temperature is 80-95℃, and the stretching ratio is 1.8-4.5.

[0050] By controlling the film preparation process and parameters, the polyolefin heat-insulating and breathable film with good processing performance, uniform thickness, good waterproof and breathable properties, and good heat insulation effect is obtained.

[0051] Optionally, the spun-bonded non-woven fabric is selected from one of PP spun-bonded non-woven fabric, PET spun-bonded non-woven fabric, PP / PET double-component non-woven fabric, and PE / PP double-component non-woven fabric, and the grammage of the spun-bonded non-woven fabric is 15-30g / cm 2 , and the thickness is 0.1-0.3mm.

[0052] By using the above technical solution, the spun-bonded non-woven fabric serves as an intermediate transition layer connecting the polyolefin heat-insulating and breathable film and the aerogel glass fiber needle felt, thereby enhancing the tensile strength and mechanical properties of the entire composite film.

[0053] In a second aspect, the application discloses a preparation method of a waterproof and breathable composite film with heat insulation function, which comprises the following steps:

[0054] The aerogel glass fiber needle felt, the spun-bonded non-woven fabric, and the polyolefin heat-insulating and breathable film are prepared respectively, and then they are sequentially compounded by using hot melt adhesive, the adhesive is heated and melted, and then roll coating, pressing, and cooling and setting are performed to obtain the composite film, wherein the temperature of the heating component of the compounding equipment is 90-150℃, and the adhesive amount is 2-15g / m 2 .

[0055] By using the above technical solution, the hot melt adhesive is used for compounding to realize the combination and connection between the layers, thereby preparing the composite film with waterproof and breathable functions and heat insulation function.

[0056] In summary, the application has the following beneficial effects:

[0057] 1. The polyolefin heat-insulating and breathable film plays a waterproof and heat insulation role, so that the composite film maintains sufficient hydrostatic pressure; the filter layer makes the waterproof layer and the heat insulation layer better adhere, thereby enhancing the tensile strength and mechanical properties of the entire composite film, reducing heat conduction from the waterproof layer to the heat insulation layer while maintaining waterproof and breathable properties, and the heat insulation layer has good heat insulation effect, good hydrophobic property, and good mechanical properties.

[0058] In the aerogel glass fiber needle felt, the silica aerogel and the glass fiber needle felt are compounded, the forming problem and the brittleness of the silica aerogel are solved, the low thermal conductivity and the hydrophobicity are retained, the polyester fiber and the viscose fiber are added in the composite fiber, the tensile strength and the bending resistance of the aerogel glass fiber needle felt are ensured, and the aerogel glass fiber needle felt has certain air permeability and moisture permeability. Therefore, the aerogel glass fiber needle felt can play a role of heat insulation and heat preservation as a lining barrier.

[0059] 2. The fiber after alkali treatment has more reactive sites, which is beneficial to the adhesion of the mercapto silane coupling agent and the calcium carbonate; the mercapto silane coupling agent and the calcium carbonate are combined to modify, the mercapto silane coupling agent produces a chemical bonding effect between the glass fiber and the silica aerogel through the introduction of the mercapto group, the reinforcing effect on the aerogel is improved, and the influence on the thermal conductivity is smaller; the calcium carbonate is deposited on the surface of the glass fiber, so that the hydrophobicity is enhanced, and the surface roughness of the glass fiber is improved, which is beneficial to improving the tensile strength of the needle felt; and the presence of the calcium carbonate makes the surface of the needle felt rough, which is further beneficial to the bonding force between the aerogel glass fiber needle felt and the spun-bonded non-woven fabric, and the mechanical properties of the waterproof and breathable membrane are improved. BRIEF DESCRIPTION OF DRAWINGS

[0060] Figure 1 It is a schematic diagram of each layer structure of the composite membrane of the application.

[0061] Explanation of reference signs:

[0062] 1, waterproof layer; 2, transition layer; 3, thermal insulation layer. DETAILED DESCRIPTION

[0063] The application will be further described in detail in combination with Examples 1-11 and Comparative Examples 1-5.

[0064] The polypropylene is selected from Guangdong Chuanheng New Material Technology Co., Ltd., and the model is CH-PP5-0012 polypropylene;

[0065] The POE plastic is selected from Haozheng New Material Technology (Dongguan) Co., Ltd., and the model is American Exxon Mobil 3980 POE plastic;

[0066] The low-density polyethylene is selected from Guangzhou Hongcheng Plasticizing Co., Ltd., and the model is LE3003 low-density polyethylene;

[0067] The calcium carbonate is selected from Shijiazhuang Yitian Mineral Products Co., Ltd., and the model is heavy calcium carbonate;

[0068] The nano-silicon dioxide is selected from Foshan Shunde Jinchun Silicon Material Co., Ltd., and the model is nano-silicon dioxide;

[0069] Silane coupling agent KH-550 is selected from silane coupling agent KH-550 of Dongguan Zhenming Chemical Co., Ltd.;

[0070] Rutile titanium dioxide is selected from rutile titanium dioxide 2233 of Foshan Jiuruoxing New Material Co., Ltd., with the brand of German Konos;

[0071] Glass fibers are purchased from Taian Haili New Material Co., Ltd., with a length of 3 mm;

[0072] Polyester fibers are purchased from Taian Senyang Composite Material Co., Ltd., with a length of 4-6 mm;

[0073] Viscose fibers are purchased from Shandong Fuhui Textile Technology Co., Ltd., with a length of 8-10 mm. Embodiment

[0074] Embodiment 1

[0075] The embodiment discloses a waterproof and breathable composite film with heat insulation function, which comprises, from inside to outside, a heat preservation layer, a transition layer and a waterproof layer, the heat preservation layer is aerogel glass fiber needle felt, the transition layer is spun-bonded non-woven fabric, and the waterproof layer is polyolefin heat insulation and breathable film. Figure 1

[0076] The aerogel glass fiber needle felt comprises composite fiber filaments, and raw materials of the composite fiber filaments comprise 50 wt% of glass fibers, 40 wt% of polyester fibers and 10 wt% of viscose fibers.

[0077] The aerogel glass fiber needle felt is prepared by the following method:

[0078] (1) Preparation of glass fiber needle felt:

[0079] After the composite fiber filaments are subjected to opening and mixing, mechanical laying, pre-needling, main needling, heat setting and winding and slitting, the glass fiber felt is obtained, the glass fiber felt after needling is heated and separated, is sent into a strong acid tank for leaching, is washed with water until the pH of the water is 7.5, and is dried to obtain the glass fiber needle felt;

[0080] The needling density in the needling process is 100 strokes / cm 2 , the needling depth is 8 mm, the needling frequency is 800 times / min, and the heat setting temperature is 200°C;

[0081] (2) Synthesis of sol:

[0082] The mixed solution is obtained by diluting the water glass with water flowing through the Na+ exchange resin membrane, the volume ratio of water to water glass is 5:1, 0.3 mol / L of ammonia water is added until the pH of the solution is 10.5, the condensation reaction is carried out, and the silicon-containing sol is obtained after stirring for 10 min; ​

[0083] (3) Preparation of aerogel glass fiber needle felt:

[0084] The silica-containing sol was poured into a mold and left to stand for 30 min, waiting for it to gel and solidify into silica aerogel. The glass fiber needle felt was immersed in a 95% ethanol solution for 20 min, then taken out and heated to 40°C. After being placed in the solidified silica aerogel for 6 h, it was taken out and the above aging and taking-out process was repeated until the weight of the composite material was 4 / 3 of the weight of the glass fiber needle felt, i.e. the weight increase was 1 / 3 of the original glass fiber needle felt. The composite material was obtained;

[0085] A trimethylchlorosilane / n-hexane solution with a molar ratio of 1:2 was added to the above composite material for surface modification, and the volume ratio of the composite material to the trimethylchlorosilane / n-hexane solution was 1:0.6. The reaction was carried out at 40°C for 24 h. The remaining modifier and other products were washed away. Finally, the modified composite material was placed in an oven at 120°C for 8 h to dry, and the aerogel glass fiber needle felt was obtained.

[0086] The obtained aerogel glass fiber needle felt had a grammage of 70 g / cm 2 , a thickness of 4 mm, and a porosity of 80%.

[0087] The spun-bonded non-woven fabric was made of PP spun-bonded non-woven fabric with a grammage of 20 g / cm 2 and a thickness of 0.1 mm.

[0088] The polyolefin heat-insulating and breathable film was prepared by the following method (all the following amounts are by weight):

[0089] After high-speed mixing of 20 parts of polypropylene, 4 parts of POE plastic, 6 parts of low-density polyethylene, 45 parts of calcium carbonate, 2 parts of nano-silicon dioxide, 1 part of silane coupling agent KH-550, and 3 parts of rutile titanium dioxide, granulation was performed. The polyolefin heat-insulating and breathable film was obtained after melt extrusion casting, uniaxial stretching, heat setting, cooling, corona discharge, and winding. The melt extrusion temperature was 210°C, the heat setting temperature was 80°C, and the stretching ratio was 1.8.

[0090] The obtained polyolefin heat-insulating and breathable film had a grammage of 30 g / cm 2 and a thickness of 20.5 μm.

[0091] The preparation method of the waterproof and breathable composite film with heat-insulating function included the following steps:

[0092] The preparation of the aerogel glass fiber needle felt, the spun-bonded non-woven fabric, and the polyolefin heat-insulating and breathable film was carried out respectively.

[0093] The aerogel glass fiber needle felt, the spun-bonded non-woven fabric and the polyolefin heat-insulating and breathable film are compounded in sequence by using hot melt adhesive, the adhesive is heated and melted, and then is roll-coated, pressed and cooled to obtain a composite film, the temperature of the heating part of the compounding equipment is 110℃, and the adhesive amount is 2.5g / m 2 .

[0094] After detection, the waterproof and breathable composite film obtained has a grammage of 125g / cm 2 .

[0095] Example 2

[0096] The embodiment discloses a waterproof and breathable composite film with heat insulation function, which comprises, from inside to outside, a heat preservation layer, a transition layer and a waterproof layer, the heat preservation layer is an aerogel glass fiber needle felt, the transition layer is a spun-bonded non-woven fabric, and the waterproof layer is a polyolefin heat-insulating and breathable film.

[0097] The aerogel glass fiber needle felt comprises composite fiber filaments, and the raw material of the composite fiber filaments comprises 50wt% of glass fiber, 30wt% of polyester fiber and 20% of adhesive fiber.

[0098] The aerogel glass fiber needle felt is prepared by the following method:

[0099] (1) Preparation of glass fiber needle felt:

[0100] The composite fiber filaments are subjected to opening and mixing, mechanical laying, pre-needling, main needling, heat setting and winding and cutting to obtain a glass fiber felt, the needled glass fiber felt is heated and separated, is leached in a strong acid tank, is washed with water, is treated by a sodium hydroxide solution until the pH is 7, and is dried to obtain the glass fiber needle felt;

[0101] The needling density in the needling process is 300 strokes / cm 2 , the needling depth is 10mm, the needling frequency is 1100 times / min, and the heat setting temperature is 250℃;

[0102] (2) Synthesis of sol:

[0103] The water glass is diluted by water flowing through a Na+ exchange resin membrane to obtain a mixed solution, the volume ratio of water to water glass is 4:1, 0.6mol / L of ammonia water is added until the pH of the solution is 10.5, a condensation reaction is performed, and stirring is performed for 20min to obtain a silicon-containing sol;

[0104] (3) Preparation of aerogel glass fiber needle felt:

[0105] The silica-containing sol is poured into a mold and left to stand for 40 min, waiting for it to gel and solidify into a silica aerogel. The glass fiber needle felt is immersed in a 95% ethanol solution for 25 min, then taken out. The glass fiber needle felt soaked with ethanol is heated to 45℃, and then placed in the solidified silica hydrogel for aging for 6.5 h. The above aging and taking-out process is repeated until the weight of the composite material is 2 times that of the glass fiber needle felt, i.e. the weight is increased by 1 times the original glass fiber needle felt, to obtain a composite material;

[0106] A trimethylchlorosilane / n-hexane solution with a molar ratio of 1:2 is added to the above-mentioned composite material for surface modification of the composite material, wherein the volume ratio of the composite material and the trimethylchlorosilane / n-hexane solution is 1:0.5, and the reaction is carried out at 45℃ for 24 h. The remaining modifier and other products are washed away, and finally the modified composite material is placed in an oven at 125℃ for drying for 10 h to obtain an aerogel glass fiber needle felt.

[0107] The obtained aerogel glass fiber needle felt has a grammage of 100 g / cm 2 , a thickness of 6 mm, and a porosity of 75%.

[0108] The spun-bonded non-woven fabric is selected from a PP / PET bi-component spun-bonded non-woven fabric, which has a grammage of 30 g / cm 2 and a thickness of 0.2 mm.

[0109] The polyolefin heat-insulating and breathable film is prepared by the following method:

[0110] 32 parts of polypropylene, 9 parts of POE plastic, 12 parts of low-density polyethylene, 52 parts of calcium carbonate, 5 parts of nano-silicon dioxide, 3 parts of silane coupling agent and 7 parts of rutile titanium dioxide are high-speed mixed and then granulated. The polyolefin heat-insulating and breathable film is obtained after melt extrusion casting, uniaxial stretching, heat setting, cooling, corona and winding, wherein the melt extrusion temperature is 230℃, the heat setting temperature is 95℃, and the stretching ratio is 4.5.

[0111] The obtained polyolefin heat-insulating and breathable film has a grammage of 60 g / cm 2 and a thickness of 80 μm.

[0112] The preparation method of the waterproof and breathable composite film with heat-insulating function comprises the following steps:

[0113] The preparation of the aerogel glass fiber needle felt, the spun-bonded non-woven fabric and the polyolefin heat-insulating and breathable film is carried out respectively;

[0114] The aerogel glass fiber needle felt, the spun-bonded non-woven fabric and the polyolefin heat-insulating and breathable film are compounded in the order by using hot melt adhesive. The glue is heated and melted, and then roll-coated, pressed and cooled to obtain a composite film. The temperature of the heating part of the compounding equipment is 150℃, and the glue amount is 7 g / m.2 .

[0115] After detection, the weight of the waterproof and breathable composite film obtained is 200 g / cm 2 .

[0116] Example 3

[0117] The embodiment discloses a waterproof and breathable composite film with heat insulation function, which comprises, from inside to outside, a heat preservation layer, a transition layer and a waterproof layer, the heat preservation layer is aerogel glass fiber needle felt, the transition layer is spun-bonded non-woven fabric, and the waterproof layer is polyolefin heat insulation and breathable film.

[0118] The aerogel glass fiber needle felt comprises composite fiber filaments, and raw materials of the composite fiber filaments comprise 60 wt% of glass fibers, 30 wt% of polyester fibers and 10% of viscose fibers.

[0119] The aerogel glass fiber needle felt is prepared by the following method:

[0120] (1) Preparation of glass fiber needle felt:

[0121] After the composite fiber filaments are subjected to opening and mixing, mechanical laying, pre-needling, main needling, heat setting and winding and slitting, the glass fiber felt is obtained, the glass fiber felt after needling is heated and separated, is leached in a strong acid tank, is washed with water, is treated by a sodium hydroxide solution until the pH is 7, and is dried to obtain the glass fiber needle felt;

[0122] The needling density in the needling process is 500 times / cm 2 , the needling depth is 15 mm, the needling frequency is 1500 times / min, and the heat setting temperature is 300 DEG C;

[0123] (2) Synthesis of sol:

[0124] The water glass is diluted with water flowing through a Na+ exchange resin membrane to obtain a mixed solution, wherein the volume ratio of water to water glass is 5:1, and 0.4 mol / L of ammonia water is added to the solution until the pH is 10 for condensation reaction, and stirring is performed for 10 min to obtain a silicon-containing sol;

[0125] (3) Preparation of aerogel glass fiber needle felt:

[0126] The silicon-containing sol is poured into a mold and left to stand for 35 min, and the silica aerogel is gelled and solidified; the glass fiber needle felt is immersed in a 95% ethanol solution for 23 min, then taken out, and the glass fiber needle felt immersed in ethanol is heated to 42 DEG C and placed in the solidified silica aerogel for aging for 6 h, then taken out, and the above-mentioned aging and taking-out process is repeated until the weight of the composite material is 5 / 3 of the weight of the glass fiber needle felt, that is, the weight increase is 2 / 3 of the original glass fiber needle felt, to obtain the composite material.

[0127] The composite material is surface modified by adding a trimethylchlorosilane / n-hexane solution with a molar ratio of 1:2 to the composite material, wherein the volume ratio of the composite material and the trimethylchlorosilane / n-hexane solution is 1:0.8, and the reaction is carried out at 42°C for 24 hours. The remaining modifier and other products are washed away, and finally the modified composite material is placed in an oven at 122°C for drying for 9 hours to obtain an aerogel glass fiber needle felt.

[0128] The obtained aerogel glass fiber needle felt has a grammage of 130 g / cm 2 , a thickness of 8 mm, and a porosity of 70%.

[0129] The spun-bonded non-woven fabric is selected from a PE / PP bi-component spun-bonded non-woven fabric, which has a grammage of 23 g / cm 2 and a thickness of 0.3 mm.

[0130] The polyolefin heat-insulating and breathable film is prepared by the following method:

[0131] After high-speed mixing of 28 parts of polypropylene, 7 parts of POE plastic, 9 parts of low-density polyethylene, 49 parts of calcium carbonate, 3 parts of nano-silicon dioxide, 2 parts of a silane coupling agent, and 5 parts of rutile titanium dioxide, granulation is performed, and then melt extrusion casting, uniaxial stretching, heat setting, cooling, corona, and winding are performed to obtain the polyolefin heat-insulating and breathable film, wherein the melt extrusion temperature is 190°C, the heat setting temperature is 90°C, and the stretching ratio is 3.4.

[0132] The obtained polyolefin heat-insulating and breathable film has a grammage of 130 g / cm 2 and a thickness of 115 μm.

[0133] The preparation method of the waterproof and breathable composite film with a heat-insulating function includes the following steps:

[0134] The preparation of the aerogel glass fiber needle felt, the spun-bonded non-woven fabric, and the polyolefin heat-insulating and breathable film is performed respectively;

[0135] The aerogel glass fiber needle felt, the spun-bonded non-woven fabric, and the polyolefin heat-insulating and breathable film are sequentially compounded by using hot melt glue. After the glue is heated and melted, roll coating, pressing, and cooling and setting are performed to obtain the composite film. The temperature of the heating component of the compounding equipment is 130°C, and the glue amount is 8.5 g / m 2 .

[0136] After detection, the obtained waterproof and breathable composite film has a grammage of 280 g / cm 2 .

[0137] Example 4

[0138] The difference between this embodiment and embodiment 1 is that the polyolefin heat-insulating and air-permeable film in the waterproof and air-permeable composite film is different.

[0139] The polyolefin heat-insulating and air-permeable film in this embodiment is prepared by the following method:

[0140] After high-speed mixing and granulation of 20 parts of polypropylene, 4 parts of POE plastic, 6 parts of low-density polyethylene, 45 parts of surface-coated calcium carbonate, 2 parts of nano-silicon dioxide, 1 part of silane coupling agent and 3 parts of rutile titanium dioxide, polyolefin heat-insulating and air-permeable film is obtained after melt extrusion casting, uniaxial stretching, heat setting, cooling, corona and winding, wherein the melt extrusion temperature is 210℃, the heat setting temperature is 80℃, and the stretching ratio is 1.8.

[0141] The surface-coated calcium carbonate is prepared by the following steps:

[0142] The calcium carbonate and lauric acid are placed in a high-speed mixer and coated at a temperature of 90℃ for 25min, wherein the weight of lauric acid is 0.8% of the weight of calcium carbonate.

[0143] Embodiment 5

[0144] The difference between this embodiment and embodiment 1 is that the polyolefin heat-insulating and air-permeable film in the waterproof and air-permeable composite film is different.

[0145] The polyolefin heat-insulating and air-permeable film in this embodiment is prepared by the following method:

[0146] After high-speed mixing and granulation of 20 parts of polypropylene, 4 parts of POE plastic, 6 parts of low-density polyethylene, 45 parts of surface-coated calcium carbonate, 2 parts of nano-silicon dioxide, 1 part of silane coupling agent and 3 parts of rutile titanium dioxide, polyolefin heat-insulating and air-permeable film is obtained after melt extrusion casting, uniaxial stretching, heat setting, cooling, corona and winding, wherein the melt extrusion temperature is 210℃, the heat setting temperature is 80℃, and the stretching ratio is 1.8.

[0147] The surface-coated calcium carbonate is prepared by the following steps:

[0148] The calcium carbonate and lauric acid are placed in a high-speed mixer and coated at a temperature of 120℃ for 30min, wherein the weight of lauric acid is 2.2% of the weight of calcium carbonate.

[0149] Embodiment 6

[0150] The difference between this embodiment and embodiment 1 is that the polyolefin heat-insulating and air-permeable film in the waterproof and air-permeable composite film is different.

[0151] The aerogel glass fiber needle felt in the embodiment comprises composite fiber filaments, and the composite fiber filaments comprise 50 wt% of modified glass fibers, 40 wt% of polyester fibers and 10 wt% of viscose fibers.

[0152] The modified glass fibers are modified glass fibers modified by a mercapto silane coupling agent and calcium carbonate in combination, and are prepared by the following method:

[0153] The glass fibers are pretreated by using a sodium hydroxide solution with a mass concentration of 5%, the mass ratio of the glass fibers to the sodium hydroxide solution is 1:150, and the glass fibers are ultrasonically treated for 8 min; the glass fibers are washed to be neutral by using deionized water, and washed glass fibers are obtained;

[0154] The 3-mercaptopropyl triethoxysilane is dissolved in 95% ethanol at a mass fraction of 1% to prepare B liquid; the washed glass fibers are added into the B liquid and mixed thoroughly, the mass ratio of the glass fibers to the 3-mercaptopropyl triethoxysilane is maintained at 1:0.1, ultrasonic oscillation is performed for 10 min at a temperature of 20°C, the glass fibers are taken out after being left to stand for 22 h, and the glass fibers are rinsed by using acetone and dried at 90°C to obtain preliminary treated fibers;

[0155] The preliminary treated fibers are immersed in a calcium chloride aqueous solution, a dispersant EDTA-2Na is added after being stirred thoroughly, and sodium carbonate is added; the fibers are taken out after being stirred for 15 min at 40°C, and the fibers are washed to be free of obvious white particles by using deionized water and dried to obtain modified glass fibers; the concentration of the calcium chloride and the sodium carbonate is 0.5 mol / L, and the amount of the dispersant EDTA-2Na is 4 g / L.

[0156] Embodiment 7

[0157] The difference between the embodiment and the embodiment 1 is that the aerogel glass fiber needle felt in the waterproof and breathable composite film is different.

[0158] The aerogel glass fiber needle felt in the embodiment comprises composite fiber filaments, and the composite fiber filaments comprise 50 wt% of modified glass fibers, 40 wt% of polyester fibers and 10 wt% of viscose fibers.

[0159] The modified glass fibers are modified glass fibers modified by a mercapto silane coupling agent and calcium carbonate in combination, and are prepared by the following method:

[0160] The glass fibers are pretreated by using a sodium hydroxide solution with a mass concentration of 5%, the mass ratio of the glass fibers to the sodium hydroxide solution is 1:120, and the glass fibers are ultrasonically treated for 10 min; the glass fibers are washed to be neutral by using deionized water, and washed glass fibers are obtained;

[0161] The 3-mercaptopropyl triethoxysilane was dissolved in 95% ethanol to form B liquid at a mass fraction of 1%. The cleaned glass fibers were added to the B liquid and mixed thoroughly, and the mass ratio of the glass fibers to the 3-mercaptopropyl triethoxysilane was maintained at 1:0.15. Ultrasonic oscillation was performed for 15 min at a temperature of 25°C. The glass fibers were taken out after standing for 24 h and rinsed with acetone, and were then dried at 100°C to obtain the preliminary treated fibers.

[0162] The preliminary treated fibers were immersed in a calcium chloride aqueous solution, and a dispersant EDTA-2Na was added after thorough stirring. Then, sodium carbonate was added, and stirring was performed at 50°C for 20 min. The fibers were taken out, washed with deionized water until no obvious white particles were present, and dried to obtain the modified glass fibers. The concentrations of the calcium chloride and the sodium carbonate were 0.5 mol / L, and the amount of the dispersant EDTA-2Na was 3 g / L.

[0163] Example 8

[0164] The difference between this example and Example 6 is that the aerogel glass fiber needle felt in the waterproof and breathable composite membrane is different.

[0165] The aerogel glass fiber needle felt of this example comprises composite fiber filaments, and the composite fiber filaments comprise 50 wt% of modified glass fibers, 40 wt% of polyester fibers, and 10 wt% of cross-linked modified viscose fibers. The modified glass fibers are selected from modified glass fibers that are modified by a mercapto silane coupling agent and calcium carbonate, and the preparation method is the same as that of Example 6. The cross-linked modified viscose fibers are prepared by the following steps:

[0166] The viscose fibers were immersed in a 25 g / L sodium sulfite solution and treated at 75°C for 1.5 h. After thorough water washing, the pre-treated viscose fibers were obtained.

[0167] A treatment liquid was prepared using sodium hypophosphite and a BTCA cross-linking agent, and the mass ratio of the BTCA to the sodium hypophosphite was 8:3. The concentration of the sodium hypophosphite in the treatment liquid was 5 wt%. The pre-treated viscose fibers were subjected to three immersions and three wrappings in the treatment liquid, and the wrappings were performed at a wrappings rate of 120%.

[0168] Then, the viscose fibers were dried at 45°C until the weight was constant, and were then cross-linked at a high temperature of 150°C for 5 min. The cross-linked fibers were rinsed with warm water, and were then dried at 45°C to obtain the cross-linked modified viscose fibers.

[0169] Example 9

[0170] The difference between this example and Example 6 is that the aerogel glass fiber needle felt in the waterproof and breathable composite membrane is different.

[0171] The aerogel glass fiber needle felt of the embodiment comprises composite fiber filaments, and the composite fiber filaments comprise 50 wt% of modified glass fibers, 40 wt% of polyester fibers and 10 wt% of cross-linked modified viscose fibers. The modified glass fibers are modified glass fibers modified by a mercapto silane coupling agent and calcium carbonate, and the preparation method is the same as that in Embodiment 6. The cross-linked modified viscose fibers are prepared by the following steps:

[0172] The viscose fibers are soaked in a 25 g / L sodium sulfite solution, treated at 78°C for 1 h, and after sufficient water washing, pretreated viscose fibers are obtained.

[0173] A treatment solution is prepared by using sodium hypophosphite and BTCA cross-linking agent, wherein the mass ratio of BTCA to sodium hypophosphite is 8:5, and the concentration of sodium hypophosphite in the treatment solution is 5 wt%. The pretreated viscose fibers are treated by three-dip-three-nip in the treatment solution, and the nip percentage is 120%.

[0174] Then the viscose fibers are dried at 50°C to constant weight, and cross-linked at high temperature at 180°C for 3 min. The cross-linked fibers are washed with warm water, and dried at 45°C to obtain cross-linked modified viscose fibers.

[0175] Embodiment 10

[0176] The difference between the embodiment and Embodiment 8 is that the aerogel glass fiber needle felt in the waterproof and breathable composite film is different.

[0177] The aerogel glass fiber needle felt of the embodiment comprises composite fiber filaments, and the composite fiber filaments comprise 40 wt% of modified glass fibers, 40 wt% of polyester fibers and 20 wt% of cross-linked modified viscose fibers. The modified glass fibers are modified glass fibers modified by a mercapto silane coupling agent and calcium carbonate, and the preparation method is the same as that in Embodiment 6.

[0178] Embodiment 11

[0179] The difference between the embodiment and Embodiment 8 is that the aerogel glass fiber needle felt in the waterproof and breathable composite film is different.

[0180] The aerogel glass fiber needle felt of the embodiment comprises composite fiber filaments, and the composite fiber filaments comprise 50 wt% of modified glass fibers, 40 wt% of polyester fibers and 10 wt% of cross-linked modified viscose fibers. The modified glass fibers are modified glass fibers modified by a mercapto silane coupling agent and calcium carbonate, and the preparation method is the same as that in Embodiment 6. The preparation method of the cross-linked modified viscose fibers is the same as that in Embodiment 8.

[0181] The aerogel glass fiber needle felt is prepared by the following method:

[0182] (1) Preparation of glass fiber needle felt:

[0183] The composite fiber filaments are opened and mixed, mechanically laid into a web, pre-needled, main needled, heat-set, wound and slit to obtain glass fiber mat. The needled glass fiber mat is heated to separate the phases, sent to a strong acid bath for leaching, washed with water and then treated with sodium hydroxide solution until the pH is 7.5. After drying, glass fiber needled mat is obtained.

[0184] The needle density in the needle-punching process is 100 needles / cm². 2 The needle puncture depth is 8mm, the needle puncture frequency is 800 times / min, and the heat setting temperature is 200℃.

[0185] (2). Synthesis of sol:

[0186] The water glass was diluted with deionized water to obtain a mixed solution with a water to water glass volume ratio of 5:1. 0.5 mol / L hydrogen peroxide was added to adjust the pH of the solution to 10.5, and a condensation reaction was carried out. The mixture was stirred for 10 min to obtain a silica-containing sol.

[0187] (3). Preparation of aerogel glass fiber needled felt:

[0188] Pour the silica-containing sol into a mold and let it stand for 30 minutes to allow it to gel and solidify into silica aerogel. Immerse the glass fiber needled felt in 95% ethanol for 20 minutes and then remove it. Heat it to 40°C and place it in the solidified silica hydrogel for 6 hours of aging. Remove it and repeat the above aging and removal process until the weight of the composite material is 4 / 3 of the original glass fiber needled felt, that is, the weight is increased to 1 / 3 of the original glass fiber needled felt, and the composite material is obtained.

[0189] The above composite material was washed with deionized water, replaced with an equal volume of ethanol, and modified with an ethanol solution containing 20% ​​trimethylchlorosilane. The mixture was reacted at 40°C for 24 hours. The remaining modifier and other products were washed away. Finally, the gel was dried in an oven at 120°C for 8 hours to obtain aerogel glass fiber needled felt. Comparative Example

[0190] Comparative Example 1

[0191] The difference between this comparative example and Example 1 is that the aerogel glass fiber needled felt in the composite membrane is replaced with glass fiber needled felt that does not contain silica aerogel.

[0192] In preparing the glass fiber needled mat of this comparative example, the steps are the same as step (1) in the preparation of aerogel glass fiber needled mat in Example 1.

[0193] The composite steps for spunbond nonwoven fabric, polyolefin heat-insulating and breathable membrane, and the whole are the same as in Example 1.

[0194] Comparative Example 2

[0195] The difference between this comparative example and Example 8 is that the aerogel glass fiber needle-punched felt in the waterproof and breathable composite film is different.

[0196] The aerogel glass fiber needle-punched felt in this example includes composite fiber filaments, which include 50wt% modified glass fiber, 40wt% polyester fiber, and 10wt% cross-linked modified viscose fiber.

[0197] The modified glass fiber is modified glass fiber modified by mercapto silane coupling agent, which is prepared by the following method:

[0198] The glass fiber is pretreated with a 5% sodium hydroxide solution, the mass ratio of glass fiber to sodium hydroxide solution is 1:150, ultrasonic treatment for 8 min, and washed with deionized water until neutral, to obtain the washed glass fiber;

[0199] 3-mercaptopropyl triethoxysilane is dissolved in 95% ethanol at a mass fraction of 1% to prepare B liquid, the washed glass fiber is added to B liquid and mixed thoroughly, the mass ratio of glass fiber to 3-mercaptopropyl triethoxysilane is maintained at 1:0.1, ultrasonic oscillation for 10 min at a temperature of 20°C, and the glass fiber is taken out after standing for 22 h and rinsed with acetone, and dried at 90°C to obtain modified glass fiber.

[0200] Comparative Example 3

[0201] The difference between this comparative example and Example 8 is that the aerogel glass fiber needle-punched felt in the waterproof and breathable composite film is different.

[0202] The aerogel glass fiber needle-punched felt in this example includes composite fiber filaments, which include 50wt% modified glass fiber, 40wt% polyester fiber, and 10wt% cross-linked modified viscose fiber.

[0203] The modified glass fiber is modified glass fiber modified by calcium carbonate, which is prepared by the following method:

[0204] The glass fiber is pretreated with a 5% sodium hydroxide solution, the mass ratio of glass fiber to sodium hydroxide solution is 1:150, ultrasonic treatment for 8 min, and washed with deionized water until neutral, to obtain the washed glass fiber;

[0205] The pretreated fiber is immersed in a calcium chloride aqueous solution, after being fully stirred, a dispersing agent EDTA-2Na is added, then sodium carbonate is added, and the fiber is stirred at 40℃ for 15 min. The fiber is taken out and washed with deionized water until no obvious white particles are present, and is dried to obtain the modified glass fiber, wherein the concentration of calcium chloride and sodium carbonate is 0.5 mol / L, and the amount of the dispersing agent EDTA-2Na is 4 g / L.

[0206] Comparative Example 4

[0207] The difference between the present comparative example and Example 8 is that the aerogel glass fiber needle felt in the waterproof and breathable composite membrane is different.

[0208] The aerogel glass fiber needle felt in the present example comprises composite fiber filaments, and the composite fiber filaments comprise 60 wt% of the modified glass fiber and 40 wt% of the polyester fiber, wherein the modified glass fiber is prepared as in Example 8.

[0209] Comparative Example 5

[0210] The difference between the present comparative example and Example 8 is that the aerogel glass fiber needle felt in the waterproof and breathable composite membrane is different.

[0211] The aerogel glass fiber needle felt in the present example comprises composite fiber filaments, and the composite fiber filaments comprise 60 wt% of the cross-linked modified viscose fiber and 40 wt% of the polyester fiber, wherein the cross-linked modified viscose fiber is prepared as in Example 8. Performance Test

[0212] The waterproof and breathable composite membranes prepared in Examples 1-11 and Comparative Examples 1-5 are subjected to performance tests, and the test results are recorded.

[0213] Air permeability: tested according to the standard GB / T 5453-1997 "Determination of air permeability of textile fabrics";

[0214] Moisture permeability: tested according to the standard GB / T 12704.1-2009 "Moisture resistance test methods for fabrics Part 1: hygroscopic method";

[0215] Hydrostatic pressure: tested according to the standard GB / T 4744-2013 "Textiles - Determination and evaluation of waterproof performance - Hydrostatic pressure method";

[0216] Tear resistance: tested according to the standard GB / T 3917.3-2009 "Textiles - Determination of tear resistance of fabrics - Part 3: determination of tear strength of trapezoidal specimens";

[0217] Thermal conductivity: tested according to the standard ASTM D 5470.

[0218] Table 1

[0219] Table 1 Example Air permeability (mm / s) WVTR (g / m 2 24h) hydrostatic pressure (mm H2O) Example 1 2100 2382 3210 Example 2 1765 1620 5630 Example 3 1275 1190 6325 Example 4 2188 2416 3580 Example 5 2194 2413 3565 Example 6 2213 2434 3368 Example 7 2207 2429 3364 Example 8 2368 2579 3502 Example 9 2371 2583 3498 Example 10 2225 2442 3135 Example 11 2085 2358 3170 Comparative Example 1 2130 2434 3195 Comparative Example 2 2193 2390 3237 Comparative Example 3 2004 2359 3286 Comparative Example 4 1926 1857 3562 Comparative Example 5 2060 2262 2350

[0220] Table 2

[0221] Example Tear strength cross-machine / machine (N) thermal conductivity (W m -1 ·K -1 )]]> Example 1 441 / 462 0.023 Example 2 520 / 506 0.018 Example 3 660 / 672 0.015 Example 4 432 / 418 0.021 Example 5 436 / 424 0.023 Example 6 495 / 508 0.019 Example 7 502 / 483 0.018 Example 8 536 / 518 0.015 Example 9 532 / 520 0.015 Example 10 465 / 449 0.024 Example 11 408 / 416 0.076 Comparative Example 1 425 / 407 0.367 Comparative Example 2 468 / 459 0.023 Comparative Example 3 472 / 478 0.022 Comparative Example 4 394 / 402 0.025 Comparative Example 5 378 / 356 0.108

[0222] According to Table 1 and Table 2, in the preparation of the thermal insulation layer, the composite film prepared in the application uses silica aerogel and glass fiber needle felt for compounding, which can maximize the thermal insulation effect. Compared with the three-layer composite film without adding silica aerogel in Comparative Example 1, the thermal conductivity of Example 1 is significantly reduced, indicating that silica aerogel and glass fiber needle felt play a certain synergistic effect on thermal insulation effect.

[0223] In the composite film of the application, the polyolefin thermal insulation breathable film as the outer layer mainly provides waterproof effect, and at the same time adds thermal insulation filler to play the role of thermal insulation and ultraviolet shielding; the spun-bonded non-woven fabric as the transition layer is conducive to maintaining waterproof and breathable properties and improving the overall mechanical properties of the composite film; the thermal insulation layer mainly plays a thermal insulation role, and the selected glass fiber is a hydrophobic fiber with excellent waterproof performance.

[0224] According to Examples 1-3, as the grammage increases, the composite film is thicker and more compact, which is not conducive to the transmission of internal water vapor to the air, resulting in a decreasing trend of air permeability and moisture permeability, but as the structure of the composite film becomes compact, the tear resistance, tensile strength and waterproof performance show an increasing trend.

[0225] Compared with Example 1, the composite film of Examples 4-5 makes changes in the polyolefin thermal insulation breathable film, and the calcium carbonate in the raw material of the polyolefin thermal insulation breathable film is modified by coating. By improving the compatibility and dispersibility of the polyolefin system, the polyolefin thermal insulation breathable film becomes more uniform, thereby improving the air permeability and moisture permeability.

[0226] Compared with Example 1, the composite film of Examples 6-7 makes changes in the aerogel glass fiber needle felt, and the modified glass fiber is selected by combining modification with mercapto silane coupling agent and calcium carbonate, which improves the chemical bonding between the needle felt and the silica aerogel, the needle felt and the spun-bonded non-woven fabric, and significantly improves the overall mechanical properties and tear strength of the composite film. The thermal insulation effect of the thermal insulation layer is further improved; at the same time, due to the increased porosity of the modified glass fiber after the combined modification, it is beneficial to the passage of water molecules, resulting in a certain degree of improvement in air permeability and moisture absorption, and at the same time, due to the improvement of the structure and the improvement of the hydrophobicity.

[0227] Compared with Examples 6-7, in Comparative Example 2 and Comparative Example 3, only one of the mercapto silane coupling agent and calcium carbonate is applied for the modification of the glass fiber, and it can be seen from the combination data that there is a synergistic effect of the combined modification of the glass fiber by the mercapto silane coupling agent and calcium carbonate in improving the mechanical properties. And through different aspects, the mercapto silane coupling agent promotes the chemical bonding of the needle felt inside the thermal insulation layer and the silica aerogel, and the calcium carbonate is beneficial to promote the combination of the aerogel glass fiber needle felt and the transition layer and the waterproof layer outside.

[0228] In Examples 8-9, the aerogel glass fiber needle felt selects the combination of modified glass fiber, cross-linked modified viscose fiber and polyester fiber, and compared with Example 6, the mechanical properties and tear strength of the composite film are further improved, because the cross-linked modified viscose fiber can connect with the glass fiber and the silica aerogel into a more stable three-dimensional network system after chemical cross-linking, thereby improving the mechanical properties.

[0229] Although Example 10 also selects the combination of modified glass fiber, cross-linked modified viscose fiber and polyester fiber, the mixing ratio of the fibers is changed, which affects the performance of the composite film and reduces the mechanical strength.

[0230] In Comparative Example 4 and Comparative Example 5, no specific combination of glass fiber, viscose fiber and polyester fiber is selected to form composite fiber yarn, and according to the data, when the three fibers are not selected together, even if the glass fiber / viscose fiber is modified, the tear strength and thermal conductivity after the combination with the silica aerogel will still decrease.

[0231] Compared with Example 1, Example 11 selects a different method for the preparation of the silica aerogel, and the difference between the steps is that the use of deionized water after ion exchange and the selection of the subsequent hydrophobic modification treatment agent are different. It is illustrated that the silica aerogel prepared by the sol-gel method selected in the present application has a higher degree of removal of sodium ions in the water glass by water washing, and the aerogel does not crack, and the hydrophobicity and heat insulation effect are better.

[0232] The specific embodiment is only an explanation of the present application, and is not a limitation of the present application. Those skilled in the art can make modifications to the specific embodiment without creative contribution after reading the present specification, but as long as the modifications are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A waterproof and breathable composite membrane with thermal insulation function, characterized in that: The thermal insulation layer, the transition layer and the waterproof layer are sequentially arranged from inside to outside, the waterproof layer is a polyolefin heat-insulating and breathable film, the transition layer is a spun-bonded non-woven fabric, and the thermal insulation layer is an aerogel glass fiber needle-punched felt, the aerogel glass fiber needle-punched felt comprises composite fiber filaments, and raw materials of the composite fiber filaments comprise 50-70 wt% of glass fibers, 30-50 wt% of polyester fibers and 0-20 wt% of viscose fibers; The aerogel glass fiber needle-punched felt is prepared by the following steps: preparing a glass fiber needle-punched felt from the composite fiber filaments; preparing silica aerogel; obtaining a composite material by using the glass fiber needle-punched felt and the silica aerogel; and performing surface modification on the composite material by using a trimethylchlorosilane / n-hexane solution, and then washing and drying to obtain the aerogel glass fiber needle-punched felt; The glass fibers are modified glass fibers that are modified by a mercapto silane coupling agent and calcium carbonate, and the modified glass fibers are prepared by the following method: The glass fibers are pretreated by using a sodium hydroxide solution, ultrasonic treatment, and then taken out, washed to neutral, and obtained as washed glass fibers; 3-mercaptopropyltriethoxysilane is dissolved in ethanol to prepare B liquid, the washed glass fibers are added into the B liquid, mixed, ultrasonic oscillation is performed for 10-15 min at a temperature of 20-25 DEG C, the glass fibers are taken out after standing for 22-24 h, rinsed with acetone, and dried at 90-100 DEG C to obtain preliminary treated fibers; The preliminary treated fibers are immersed in a calcium chloride aqueous solution, fully stirred, then a dispersing agent EDTA-2Na is added, followed by the addition of sodium carbonate, stirring is performed at 40-50 DEG C for 15-20 min, the fibers are taken out, washed, and dried to obtain the modified glass fibers.

2. The waterproof and breathable composite membrane with thermal insulation function according to claim 1, characterized in that: The aerogel glass fiber needle-punched felt is prepared by the following specific steps: (1) Preparation of the glass fiber needle-punched felt: The composite fiber filaments are subjected to opening and mixing, mechanical laying, pre-needling, main needling, heat setting, winding and slitting to obtain a glass fiber felt, the needled glass fiber felt is heated and separated, sent into a strong acid tank for leaching, washed with water, treated by a neutralizing solution, dried, and obtained as the glass fiber needle-punched felt; (2) Synthesis of sol: Water flowing through a Na+ ion exchange resin membrane is used to dilute water glass to obtain a mixed solution, and 0.3-0.6 mol / L of ammonia water is added for condensation reaction, and stirring is performed for 10-20 min to obtain a silicon-containing sol; (3) Preparation of the aerogel glass fiber needle-punched felt: The silicon-containing sol is poured into a mold and left to stand, and the sol is gelled and solidified into silica aerogel, the glass fiber needle-punched felt is immersed in ethanol, taken out, the glass fiber needle-punched felt immersed in ethanol is heated to 40-45 DEG C, placed in the solidified silica aerogel for aging for 6-6.5 h, taken out, and the process of aging and taking out is repeated to obtain a composite material; A trimethylchlorosilane / n-hexane solution with a molar ratio of 1:2 is added to the composite material to perform surface modification on the composite material, and the reaction is performed at 40-45 DEG C for 24 h, and then the composite material is washed, finally placed in an oven at 120-125 DEG C for drying for 8-10 h to obtain the aerogel glass fiber needle-punched felt.

3. The waterproof and breathable composite membrane with thermal insulation function according to claim 2, characterized in that: The mass ratio of the composite material to the glass fiber needle-punched felt in the step (3) is 1.3-2:

1.

4. The waterproof and breathable composite membrane with thermal insulation function according to claim 1, characterized in that: The viscose fiber is cross-linked modified viscose fiber prepared by the following method: The viscose fiber is soaked in a 20-30 g / L sodium sulfite solution and treated at 75-78 ℃ for 1-1.5 h, and then washed to obtain pretreated viscose fiber. The pretreated viscose fiber is treated by three-dip-three-nip in a treatment solution prepared from sodium hypophosphite and BTCA cross-linking agent, wherein the mass ratio of BTCA to sodium hypophosphite is 8:(3-5). Then the viscose fiber is dried and cross-linked at high temperature of 150-180 ℃ for 3-5 min, and then washed and dried to obtain cross-linked modified viscose fiber.

5. The waterproof and breathable composite membrane with thermal insulation function according to claim 1, characterized in that: The polyolefin heat-insulating and breathable film comprises the following raw materials by weight: Polypropylene 20-32 parts; POE plastic 4-9 parts; Low-density polyethylene 6-12 parts; Calcium carbonate 45-52 parts; Nano-silicon dioxide 2-5 parts; Silane coupling agent KH-550 1-3 parts; Rutile titanium dioxide 3-7 parts.

6. The waterproof and breathable composite membrane with thermal insulation function according to claim 5, characterized in that: The calcium carbonate is surface-coated calcium carbonate, and the specific treatment steps are as follows: The calcium carbonate and lauric acid are placed in a high-speed mixer and mixed and coated at a temperature of 90-120 ℃ for 25-30 min, and the weight of lauric acid is 0.8-2.2% of the weight of calcium carbonate.

7. The waterproof and breathable composite membrane with thermal insulation function according to claim 5, characterized in that: The polyolefin heat-insulating and breathable film is prepared by the following specific steps: The raw materials are mixed and granulated, and then melt-extruded, drawn, heat-set, cooled, corona-treated, and wound to obtain the polyolefin heat-insulating and breathable film, wherein the melt-extrusion temperature is 170-230 ℃, the heat-setting temperature is 80-95 ℃, and the draw ratio is 1.8-4.

5.

8. The waterproof and breathable composite membrane with thermal insulation function according to claim 1, characterized in that: The spun-bonded non-woven fabric is selected from one of PP spun-bonded non-woven fabric, PET spun-bonded non-woven fabric, PP / PET bicomponent non-woven fabric, and PE / PP bicomponent non-woven fabric.

9. A method of manufacturing a waterproof and breathable composite membrane having a thermal barrier function according to any one of claims 1 to 8, characterized in that, The following steps are included: The aerogel glass fiber needle-punched felt, the spun-bonded non-woven fabric, and the polyolefin heat-insulating and breathable film are prepared in sequence, and then the aerogel glass fiber needle-punched felt, the spun-bonded non-woven fabric, and the polyolefin heat-insulating and breathable film are compounded by using hot melt adhesive, and then the adhesive is heated and melted, and then roll-coated, pressed, and cooled and shaped to obtain a composite film.

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