CN112011854A - Waterproof and breathable composite fiber material and manufacturing method thereof - Google Patents
Waterproof and breathable composite fiber material and manufacturing method thereof Download PDFInfo
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- CN112011854A CN112011854A CN202010921803.6A CN202010921803A CN112011854A CN 112011854 A CN112011854 A CN 112011854A CN 202010921803 A CN202010921803 A CN 202010921803A CN 112011854 A CN112011854 A CN 112011854A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Nonwoven Fabrics (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a waterproof and breathable composite fiber material and a manufacturing method thereof, wherein the composite fiber is prepared from the following raw materials in parts by weight: 45-50 parts of modified polyurethane, 8-15 parts of clove oil extract, 6-10 parts of wintergreen oil extract, 32-36 parts of polylactic acid fiber, 28-32 parts of polyvinyl butyral nanofiber, 3-5 parts of nano silicon dioxide, 1-3 parts of hydrophobic agent, 0.6-0.8 part of simethicone and 2-4 parts of nano zinc oxide; the composite fiber is prepared by adopting modified polyurethane consisting of the flatting agent, polyurethane and the breathable waterproof auxiliary agent, polylactic acid fiber and polyvinyl butyral nanofiber as base materials and adding clove oil extract, wintergreen oil extract, nano silicon dioxide, nano zinc oxide, dimethyl silicone oil and a hydrophobic agent.
Description
Technical Field
The invention belongs to the technical field of composite fiber materials, and particularly relates to a waterproof and breathable composite fiber material and a manufacturing method thereof.
Background
In recent years, the market for clothing has become increasingly large due to the constant pursuit of health. With the development and progress of science and technology, people have higher and higher requirements on clothes, and novel clothes with high science and technology content and comprehensive functions are inevitable in development. People begin to have a plurality of requirements on clothes, such as requirements of waterproof injection, ventilation and the like, and the clothes are required to have good movement comfort function when being worn, each part of a human body can stretch freely, have good extensibility and elasticity, and have good protection effect on the human body; the fabric is required to have good moisture permeability and quick drying property, and the generated sweat can be quickly led out from the surface layer of the skin and quickly evaporated under the conditions of vigorous exercise and large amount of sweating of a human body, so that the dryness of the skin is kept.
The composite fiber is a main material for designing clothes by people due to high specific strength, good high-temperature performance, dimensional stability, chemical stability, fatigue resistance, creep resistance, impact resistance, fracture toughness resistance and functional performance.
However, the performance of the existing composite fiber material is not perfect, for example, when the design clothes only focus on the waterproof function, when people wear the clothes, the air permeability in the clothes is poor, and the clothes are uncomfortable to wear, meanwhile, when the air permeability is focused, the clothes are stuck to the skin after being soaked with water, the experience feeling is poor, the waterproof and air permeable performance of the existing clothes fabric is poor, and the requirements of people cannot be met, therefore, the waterproof and air permeable composite fiber material and the manufacturing method thereof are provided.
Disclosure of Invention
The present invention aims to provide a waterproof and breathable composite fiber material and a manufacturing method thereof, so as to solve the problems in the background art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the waterproof and breathable composite fiber material is prepared from the following raw materials in parts by weight:
45-50 parts of modified polyurethane, 8-15 parts of clove oil extract, 6-10 parts of wintergreen oil extract, 32-36 parts of polylactic acid fiber, 28-32 parts of polyvinyl butyral nanofiber, 3-5 parts of nano silicon dioxide, 1-3 parts of hydrophobic agent, 0.6-0.8 part of simethicone and 2-4 parts of nano zinc oxide.
Preferably: the clove oil extract is methyl benzoate, the wintergreen oil extract is methyl salicylate, and the diameter of the polyvinyl butyral nanofiber is 300-450 nm.
Preferably: the modified polyurethane consists of a flatting agent, polyurethane and a breathable waterproof auxiliary agent, wherein the ratio of the flatting agent to the polyurethane to the breathable waterproof auxiliary agent is 0.5-1:8: 1-1.5.
The invention also provides a manufacturing method of the waterproof and breathable composite fiber material, which comprises the following steps:
step one, washing modified polyurethane, polylactic acid fiber and polyvinyl butyral nano fiber with sterile water, mixing uniformly, preserving heat and softening in sterile water at 85-90 ℃ for 18-20h, and taking out the mixed fiber;
step two, pouring the mixed fiber into a mixing tank, adding the clove oil extract, the wintergreen oil extract and the nano-silica, mixing and stirring for 35-40min at the rotation speed of 250-;
step three, adding the secondary mixture into a homogenizer, and intermittently irradiating by adopting ultraviolet rays, wherein the irradiation intensity is 2300-;
step four, feeding the fiber into a spinning machine for wet spinning, taking out the spun fiber, and washing the spun fiber by deionized water until the spun fiber is neutral to obtain nascent fiber;
and fifthly, placing the nascent fiber in a vacuum rotary evaporator at the temperature of 70-80 ℃ and the rotating speed of 40-45r/min, and drying to a moisture-free state to obtain the waterproof and breathable composite fiber material.
Preferably: in the first step, after the mixed fiber is softened under heat preservation, the mixed fiber is taken out and dried for standby application under warm air at 70-75 ℃.
Preferably: in the third step, the pressure of the homogenizer is 20-30Mpa, the temperature is 65-70 ℃, and the time is 35-40 min.
Preferably: in the fourth step, the spinning condition is that the temperature is 28 plus or minus 3 ℃; the humidity is 35 +/-5%, the spinning voltage is 16-19kV, the receiving distance is 15-20cm, and the spinning speed is 0.8-1.2 mL/h.
Preferably: the bath liquid of the coagulating bath in wet spinning consists of 30-45g/L sulfuric acid, 80-100g/L sodium sulfate, 65-85g/L zinc sulfate and 10-12g/L S653 assistant solution, and the coagulating bath liquid has temperature of 45-50 deg.c and stretching bath temperature of 55-60 deg.c.
The invention has the technical effects and advantages that: compared with the prior art, the waterproof and breathable composite fiber material and the manufacturing method thereof provided by the invention have the following advantages:
the composite fiber is prepared by adopting modified polyurethane consisting of the flatting agent, polyurethane and the breathable waterproof auxiliary agent, polylactic acid fiber and polyvinyl butyral nanofiber as base materials and adding clove oil extract, wintergreen oil extract, nano silicon dioxide, nano zinc oxide, dimethyl silicone oil and a hydrophobic agent.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to data in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. The specific embodiments described herein are merely illustrative of the invention and do not delimit the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
The invention provides a waterproof and breathable composite fiber material, which is prepared from the following raw materials in parts by weight:
45 parts of modified polyurethane, 8 parts of clove oil extract, 6 parts of wintergreen oil extract, 32 parts of polylactic acid fiber, 28 parts of polyvinyl butyral nanofiber, 3 parts of nano silicon dioxide, 1 part of hydrophobic agent, 0.6 part of simethicone and 2 parts of nano zinc oxide.
In this embodiment, specifically: the clove oil extract is methyl benzoate, the wintergreen oil extract is methyl salicylate, and the diameter of the polyvinyl butyral nanofiber is 300 nm.
In this embodiment, specifically: the modified polyurethane consists of a flatting agent, polyurethane and a breathable waterproof auxiliary agent, wherein the ratio of the flatting agent to the polyurethane to the breathable waterproof auxiliary agent is 0.5:8: 1.
The invention also provides a manufacturing method of the waterproof and breathable composite fiber material, which comprises the following steps:
step one, washing modified polyurethane, polylactic acid fiber and polyvinyl butyral nano fiber with sterile water, mixing uniformly, preserving heat in sterile water at 85 ℃ for softening for 18h, and taking out the mixed fiber;
pouring the mixed fibers into a mixing tank, adding the clove oil extract, the wintergreen oil extract and the nano-silicon dioxide, mixing and stirring at the rotating speed of 250r/min for 35min, then adding the hydrophobic agent, the simethicone and the nano-zinc oxide, stirring at the rotating speed of 450r/min for 60min, and obtaining a secondary mixture;
step three, adding the secondary mixture into a homogenizer, and intermittently irradiating by adopting ultraviolet rays, wherein the irradiation intensity is 2300 mu W/cm2, and stopping for 15min every 10 min;
step four, feeding the fiber into a spinning machine for wet spinning, taking out the spun fiber, and washing the spun fiber by deionized water until the spun fiber is neutral to obtain nascent fiber;
and fifthly, placing the nascent fiber in a vacuum rotary evaporator at 70 ℃ and at the rotating speed of 40r/min, and drying to a moisture-free state to obtain the waterproof and breathable composite fiber material.
In this embodiment, specifically: in the first step, after the mixed fiber is softened under heat preservation, the mixed fiber is taken out and dried for later use under warm air at 70 ℃.
In this embodiment, specifically: in the third step, the pressure of the homogenizer is 20Mpa, the temperature is 65 ℃, and the time is 35 min.
In this embodiment, specifically: in the fourth step, the spinning condition is that the temperature is 25 ℃; the humidity is 30%, the spinning voltage is 16kV, the receiving distance is 15cm, and the spinning speed is 0.8 mL/h.
In this embodiment, specifically: the bath liquid of the coagulating bath in wet spinning consists of 30g/L sulfuric acid, 80g/L sodium sulfate, 65g/L zinc sulfate and 10g/L S653 assistant solution, the temperature of the coagulating bath liquid is 45 ℃, and the temperature of the stretching bath is 55 ℃.
Example two
The invention provides a waterproof and breathable composite fiber material, which is prepared from the following raw materials in parts by weight:
48 parts of modified polyurethane, 12 parts of clove oil extract, 8 parts of wintergreen oil extract, 34 parts of polylactic acid fiber, 30 parts of polyvinyl butyral nanofiber, 4 parts of nano silicon dioxide, 2 parts of hydrophobic agent, 0.7 part of simethicone and 3 parts of nano zinc oxide.
In this embodiment, specifically: the clove oil extract is methyl benzoate, the wintergreen oil extract is methyl salicylate, and the diameter of the polyvinyl butyral nanofiber is 380 nm.
In this embodiment, specifically: the modified polyurethane consists of a flatting agent, polyurethane and a breathable waterproof auxiliary agent, wherein the ratio of the flatting agent to the polyurethane to the breathable waterproof auxiliary agent is 1:8:1.
The invention also provides a manufacturing method of the waterproof and breathable composite fiber material, which comprises the following steps:
step one, washing modified polyurethane, polylactic acid fiber and polyvinyl butyral nano fiber with sterile water, mixing uniformly, preserving heat in sterile water at 88 ℃ for softening for 19 hours, and taking out the mixed fiber;
pouring the mixed fibers into a mixing tank, adding the clove oil extract, the wintergreen oil extract and the nano-silicon dioxide, mixing and stirring at the rotation speed of 270r/min for 38min, then adding the hydrophobic agent, the simethicone and the nano-zinc oxide, stirring at the rotation speed of 480r/min for 69min, and obtaining a secondary mixture;
step three, adding the secondary mixture into a homogenizer, and intermittently irradiating by adopting ultraviolet rays, wherein the irradiation intensity is 2350 mu W/cm2, and stopping for 15min every 10 min;
step four, feeding the fiber into a spinning machine for wet spinning, taking out the spun fiber, and washing the spun fiber by deionized water until the spun fiber is neutral to obtain nascent fiber;
and step five, placing the nascent fiber in a vacuum rotary evaporator at the temperature of 75 ℃ and the rotating speed of 42r/min, and drying to a moisture-free state to obtain the waterproof and breathable composite fiber material.
In this embodiment, specifically: in the first step, after the mixture is softened under heat preservation, the mixed fiber is taken out and dried for later use under the warm air of 73 ℃.
In this embodiment, specifically: in the third step, the pressure of the homogenizer is 25MPa, the temperature is 68 ℃, and the time is 39 min.
In this embodiment, specifically: in the fourth step, the spinning condition is that the temperature is 28 ℃; the humidity was 35%, the spinning voltage was 18kV, the take-up distance was 18cm, and the spinning speed was 1 mL/h.
In this embodiment, specifically: the bath liquid of the coagulating bath in wet spinning consists of 30-45g/L sulfuric acid, 90g/L sodium sulfate, 75g/L zinc sulfate and 11g/L S653 assistant solution, and the temperature of the coagulating bath liquid is 48 ℃ and the stretching bath temperature is 58 ℃.
EXAMPLE III
The invention provides a waterproof and breathable composite fiber material, which is prepared from the following raw materials in parts by weight:
50 parts of modified polyurethane, 15 parts of clove oil extract, 10 parts of wintergreen oil extract, 36 parts of polylactic acid fiber, 32 parts of polyvinyl butyral nanofiber, 5 parts of nano silicon dioxide, 3 parts of hydrophobic agent, 0.8 part of simethicone and 4 parts of nano zinc oxide.
In this embodiment, specifically: the clove oil extract is methyl benzoate, the wintergreen oil extract is methyl salicylate, and the diameter of the polyvinyl butyral nanofiber is 450 nm.
In this embodiment, specifically: the modified polyurethane consists of a flatting agent, polyurethane and a breathable waterproof auxiliary agent, wherein the ratio of the flatting agent to the polyurethane to the breathable waterproof auxiliary agent is 1:8: 1.5.
The invention also provides a manufacturing method of the waterproof and breathable composite fiber material, which comprises the following steps:
step one, washing modified polyurethane, polylactic acid fiber and polyvinyl butyral nano fiber with sterile water, mixing uniformly, preserving heat in sterile water at 90 ℃ for softening for 20 hours, and taking out the mixed fiber;
pouring the mixed fibers into a mixing tank, adding the clove oil extract, the wintergreen oil extract and the nano-silicon dioxide, mixing and stirring for 40min at the rotating speed of 300r/min, then adding the hydrophobic agent, the simethicone and the nano-zinc oxide, stirring for 75min at the rotating speed of 500r/min, and obtaining a secondary mixture;
step three, adding the secondary mixture into a homogenizer, and intermittently irradiating by adopting ultraviolet rays, wherein the irradiation intensity is 2400 mu W/cm2Stopping for 15min every 10min of irradiation;
step four, feeding the fiber into a spinning machine for wet spinning, taking out the spun fiber, and washing the spun fiber by deionized water until the spun fiber is neutral to obtain nascent fiber;
and step five, placing the nascent fiber in a vacuum rotary evaporator at the temperature of 80 ℃ and the rotating speed of 45r/min, and drying to a moisture-free state to obtain the waterproof and breathable composite fiber material.
In this embodiment, specifically: in the first step, after the mixed fiber is softened under heat preservation, the mixed fiber is taken out and dried for later use under 75 ℃ of warm air.
In this embodiment, specifically: in the third step, the pressure of the homogenizer is 30Mpa, the temperature is 70 ℃, and the time is 40 min.
In this embodiment, specifically: in the fourth step, the spinning condition is that the temperature is 31 ℃; the humidity was 40%, the spinning voltage was 19kV, the take-up distance was 20cm, and the spinning speed was 1.2 mL/h.
In this embodiment, specifically: the bath liquid of the coagulating bath in wet spinning consists of 45g/L sulfuric acid, 100g/L sodium sulfate, 85g/L zinc sulfate and 12g/L S653 assistant solution, the temperature of the coagulating bath liquid is 50 ℃, and the temperature of the stretching bath is 60 ℃.
Examples of the experiments
The invention also provides test data for the composite fiber material of the invention, as shown in the following table:
TABLE 1 Water and air permeability of composite fiber
| Air permeability (L/nn)2·s） | Water permeability (g.cm/cm)2·h·mmHg） | |
| Example one | 2.93 | 9.7X10-2 |
| Example two | 2.98 | 9.9X10-2 |
| EXAMPLE III | 2.95 | 9.8X10-2 |
As can be seen from the data in the table above, the air permeability and water permeability of the composite fiber prepared by the method of the invention are far greater than those of the composite fiber in the prior art.
The working principle is as follows: the composite fiber is prepared by adopting modified polyurethane consisting of the flatting agent, polyurethane and the breathable waterproof auxiliary agent, polylactic acid fiber and polyvinyl butyral nanofiber as base materials and adding clove oil extract, wintergreen oil extract, nano silicon dioxide, nano zinc oxide, dimethyl silicone oil and a hydrophobic agent.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (8)
1. A waterproof breathable composite fiber material is characterized in that: the composite fiber is prepared from the following raw materials in parts by weight:
45-50 parts of modified polyurethane, 8-15 parts of clove oil extract, 6-10 parts of wintergreen oil extract, 32-36 parts of polylactic acid fiber, 28-32 parts of polyvinyl butyral nanofiber, 3-5 parts of nano silicon dioxide, 1-3 parts of hydrophobic agent, 0.6-0.8 part of simethicone and 2-4 parts of nano zinc oxide.
2. The waterproof breathable composite fiber material of claim 1, wherein: the clove oil extract is methyl benzoate, the wintergreen oil extract is methyl salicylate, and the diameter of the polyvinyl butyral nanofiber is 300-450 nm.
3. The waterproof breathable composite fiber material of claim 1, wherein: the modified polyurethane consists of a flatting agent, polyurethane and a breathable waterproof auxiliary agent, wherein the ratio of the flatting agent to the polyurethane to the breathable waterproof auxiliary agent is 0.5-1:8: 1-1.5.
4. A manufacturing method of a waterproof and breathable composite fiber material is characterized by comprising the following steps:
step one, washing modified polyurethane, polylactic acid fiber and polyvinyl butyral nano fiber with sterile water, mixing uniformly, preserving heat and softening in sterile water at 85-90 ℃ for 18-20h, and taking out the mixed fiber;
step two, pouring the mixed fiber into a mixing tank, adding the clove oil extract, the wintergreen oil extract and the nano-silica, mixing and stirring for 35-40min at the rotation speed of 250-;
step three, adding the secondary mixture into a homogenizer, and intermittently irradiating by adopting ultraviolet rays, wherein the irradiation intensity is 2300-;
step four, feeding the fiber into a spinning machine for wet spinning, taking out the spun fiber, and washing the spun fiber by deionized water until the spun fiber is neutral to obtain nascent fiber;
and fifthly, placing the nascent fiber in a vacuum rotary evaporator at the temperature of 70-80 ℃ and the rotating speed of 40-45r/min, and drying to a moisture-free state to obtain the waterproof and breathable composite fiber material.
5. The method for manufacturing a waterproof breathable composite fiber material according to claim 1, wherein the waterproof breathable composite fiber material comprises the following steps: in the first step, after the mixed fiber is softened under heat preservation, the mixed fiber is taken out and dried for standby application under warm air at 70-75 ℃.
6. The method for manufacturing a waterproof breathable composite fiber material according to claim 1, wherein the waterproof breathable composite fiber material comprises the following steps: in the third step, the pressure of the homogenizer is 20-30Mpa, the temperature is 65-70 ℃, and the time is 35-40 min.
7. The method for manufacturing a waterproof breathable composite fiber material according to claim 1, wherein the waterproof breathable composite fiber material comprises the following steps: in the fourth step, the spinning condition is that the temperature is 28 plus or minus 3 ℃; the humidity is 35 +/-5%, the spinning voltage is 16-19kV, the receiving distance is 15-20cm, and the spinning speed is 0.8-1.2 mL/h.
8. The method for manufacturing a waterproof breathable composite fiber material according to claim 7, wherein the waterproof breathable composite fiber material comprises the following steps: the bath liquid of the coagulating bath in wet spinning consists of 30-45g/L sulfuric acid, 80-100g/L sodium sulfate, 65-85g/L zinc sulfate and 10-12g/L S653 assistant solution, and the coagulating bath liquid has temperature of 45-50 deg.c and stretching bath temperature of 55-60 deg.c.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010921803.6A CN112011854A (en) | 2020-09-04 | 2020-09-04 | Waterproof and breathable composite fiber material and manufacturing method thereof |
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| CN202010921803.6A CN112011854A (en) | 2020-09-04 | 2020-09-04 | Waterproof and breathable composite fiber material and manufacturing method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912969A (en) * | 2021-11-18 | 2022-01-11 | 青岛仟亿新材料科技有限公司 | Breathable waterproof textile material and preparation method thereof |
| CN115142152A (en) * | 2022-07-04 | 2022-10-04 | 苏州国康医疗科技有限公司 | Graphene modified polyurethane environment-friendly fiber fabric and production process thereof |
-
2020
- 2020-09-04 CN CN202010921803.6A patent/CN112011854A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912969A (en) * | 2021-11-18 | 2022-01-11 | 青岛仟亿新材料科技有限公司 | Breathable waterproof textile material and preparation method thereof |
| CN115142152A (en) * | 2022-07-04 | 2022-10-04 | 苏州国康医疗科技有限公司 | Graphene modified polyurethane environment-friendly fiber fabric and production process thereof |
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