CN113306243A - Polyurethane composite cloth with anti-radiation heat and preparation method thereof - Google Patents
Polyurethane composite cloth with anti-radiation heat and preparation method thereof Download PDFInfo
- Publication number
- CN113306243A CN113306243A CN202110598613.XA CN202110598613A CN113306243A CN 113306243 A CN113306243 A CN 113306243A CN 202110598613 A CN202110598613 A CN 202110598613A CN 113306243 A CN113306243 A CN 113306243A
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- Prior art keywords
- parts
- layer
- cloth
- radiation
- antibacterial
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004744 fabric Substances 0.000 title claims abstract description 164
- 230000003471 anti-radiation Effects 0.000 title claims abstract description 94
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- 239000003431 cross linking reagent Substances 0.000 claims abstract description 20
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- WJLVQTJZDCGNJN-UHFFFAOYSA-N Chlorhexidine hydrochloride Chemical compound Cl.Cl.C=1C=C(Cl)C=CC=1NC(N)=NC(N)=NCCCCCCN=C(N)N=C(N)NC1=CC=C(Cl)C=C1 WJLVQTJZDCGNJN-UHFFFAOYSA-N 0.000 claims description 12
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
The invention provides a polyurethane composite cloth with radiant heat resistance and a preparation method thereof, wherein the polyurethane composite cloth comprises a radiant heat resistance antibacterial layer, a thermoplastic polyurethane layer, a base cloth layer and a waterproof layer which are sequentially arranged; the anti-radiation antibacterial layer is obtained through the curing reaction of anti-radiation antibacterial slurry and a curing agent, wherein the anti-radiation antibacterial slurry comprises the following components in parts by weight: 5-12 parts of nano silver, 10-20 parts of ionol, 2-10 parts of aluminum powder, 30-50 parts of unsaturated polyester resin and 0.1-5 parts of cross-linking agent. According to the invention, the anti-radiation antibacterial layer is arranged on the surface of the material, so that the polyurethane composite cloth has excellent antibacterial property, radiation resistance and thermal conductivity; meanwhile, the multi-layer structure consisting of the anti-radiation antibacterial layer, the thermoplastic polyurethane layer, the base cloth layer and the waterproof layer endows the polyurethane composite cloth with high water washing resistance, durability, waterproof and air permeability, and can be used for a long time without performance attenuation.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a polyurethane composite cloth with radiant heat resistance and a preparation method thereof.
Background
Along with the rapid development of the textile industry, the types and the performances of the textile fabrics are more diversified, and the textile fabrics not only need to meet the requirements of hand feeling and attractiveness, but also need to have a certain protection effect, so that cross infection is prevented, and health is maintained. As people pay more attention to the public health problem, the development and production of protective functional fabrics become an important research topic in the textile industry.
Whether the performance index of protection surface fabric lies in shielding harmful substance, effective antibacterial antibiotic, and let the people use and feel good specifically includes: firstly, the ability of resisting physical failure, because the textile fabric may be subjected to different forces in application, the textile fabric needs to have certain mechanical strength, and can resist breakage and stretch; secondly, the barrier property requires that the textile fabric has the anti-permeability property for substances which are harmful or potentially harmful to human bodies, such as water, oil, blood, alcohol, bacteria and the like, so as to play a barrier role; thirdly, the comfort, textile fabric is usually applied to clothing, household articles, medical supplies, all need to contact with human body, therefore need possess softness, gas permeability and thermal diffusivity etc.. At present, the research direction of protective fabrics is mainly based on the solution of the performance problem.
CN102991065A discloses a waterproof and antistatic composite cloth, comprising: the base cloth layer is connected with the antistatic layer through an adhesive layer; the antistatic layer is formed by interweaving carbon fiber multifilament and silver fiber multifilament, and the bottom of the base cloth layer is coated with the Fefu Longtu coating. The composite cloth has better performance in the aspects of waterproofness and antistatic performance, and has certain antibacterial and deodorizing effects; however, the composite cloth is not high in air permeability and moisture permeability, and generates heat when contacting with a human body for a long time, so that sweat cannot be removed, and stuffy feeling is generated.
CN103753876A discloses a double-layer adsorption protective fabric, which comprises an adsorption fabric layer on the surface layer and a protective fabric layer on the inner layer; the absorption fabric layer is formed by blending and weaving activated carbon fibers and ramie fibers, and the protection fabric layer is formed by blending and weaving apocynum venetum fibers and far infrared ceramic fibers. The fabric adopts a double-layer structure design, can adsorb harmful substances in the air, and has the effects of resisting bacteria, deodorizing and preventing radiation; however, the anti-penetration performance of the fabric is poor, and the external pollutants are difficult to completely obstruct.
CN111424420A discloses medical protective clothing and textile fabric with active spectrum lasting antibacterial and antiviral effects and a preparation method thereof, wherein the preparation method comprises the following steps: preparing nano silver sol, an inorganic antibacterial agent and an organic antibacterial agent into sol mixed solution; soaking the non-woven material in the sol mixed solution for a period of time; drying, flattening and rolling to obtain the antibacterial and antiviral textile fabric. The textile obtained by the method has antibacterial property, but the washing resistance is poor, and the antibacterial property is seriously reduced along with the prolonging of the use time or after the washing, so that the textile cannot be used for a long time.
Therefore, the existing protective fabric has single functionality and cannot simultaneously meet the performance requirements of multiple aspects such as obstruction, ventilation, moisture permeability, antibiosis, durability and the like. Therefore, it is an important research in the field to develop a protective fabric having antibacterial, waterproof, air-permeable, and durable properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polyurethane composite cloth with radiant heat resistance and a preparation method thereof, wherein the polyurethane composite cloth is provided with an anti-radiation antibacterial layer on the surface, so that the polyurethane composite cloth has excellent antibacterial property, radiation resistance and heat conductivity; meanwhile, the multi-layer structure consisting of the anti-radiation antibacterial layer, the thermoplastic polyurethane layer, the base cloth layer and the waterproof layer endows the polyurethane composite cloth with high water washing resistance, durability, waterproof and moisture permeability, and can be used for a long time without performance attenuation.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a polyurethane composite cloth with radiant heat resistance, which comprises a radiant heat resistant antibacterial layer, a thermoplastic polyurethane layer, a base cloth layer and a waterproof layer, which are sequentially arranged;
the anti-radiation antibacterial layer is obtained through the curing reaction of anti-radiation antibacterial slurry and a curing agent, wherein the anti-radiation antibacterial slurry comprises the following components in parts by weight: 5-12 parts of nano silver, 10-20 parts of ionol, 2-10 parts of aluminum powder, 30-50 parts of unsaturated polyester resin and 0.1-5 parts of cross-linking agent.
According to the polyurethane composite cloth provided by the invention, the thermoplastic polyurethane layer and the waterproof layer are respectively arranged on the two sides of the base cloth layer, so that the problems of permeation and barrier property caused by large porosity of the base cloth (woven fabric) are solved; the anti-radiation antibacterial layer is arranged on the thermoplastic polyurethane layer, and the multi-layer structure has excellent waterproof and barrier properties and has outstanding performances in the aspects of antibacterial property, radiation resistance, air permeability and heat conductivity; meanwhile, the composite fabric has a multi-layer structure, so that the performance of the composite fabric is more stable, the protection function cannot be attenuated along with the prolonging of the service time or the repeated washing, and the composite fabric can be repeatedly recycled.
The anti-radiation antibacterial layer is formed by solidifying anti-radiation antibacterial slurry and a curing agent, the anti-radiation antibacterial slurry contains nano silver, is a good inorganic antibacterial agent and cannot generate drug resistance; the ionol has the functions of coating and modifying the nano silver to avoid the nano silver and the aluminum powder from agglomerating on one hand, and on the other hand, the ionol forms a flexible and compact crosslinking system based on the reaction of hydroxyl and double bonds in a molecular structure with a crosslinking agent, unsaturated polyester resin and a curing agent to fix the nano silver and the aluminum powder in a polymer network structure, thereby exerting the effects of bacteriostasis, radiation resistance, heat conduction and air permeability to the maximum extent.
In the anti-radiation bacteriostatic slurry of the present invention, the nano-silver is 5 to 12 parts, for example, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 10.5 parts, 11 parts or 11.5 parts, and specific values between the above values are limited to space and for brevity, and the present invention does not exhaust the specific values included in the range.
The ionol is 10-20 parts, such as 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts or 19 parts, and the specific values therebetween are not intended to be exhaustive for the sake of brevity and clarity.
The aluminum powder is 2 to 10 parts, for example, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts or 9.5 parts, and specific values therebetween are limited to space and for brevity, and the invention is not exhaustive.
The unsaturated polyester resin is 30 to 50 parts, such as 31 parts, 33 parts, 35 parts, 37 parts, 39 parts, 40 parts, 41 parts, 43 parts, 45 parts, 47 parts or 49 parts, and specific values therebetween, which are not limited by space and for the sake of brevity, the present invention is not exhaustive of the specific values included in the range.
The crosslinking agent is 0.1-5 parts, such as 0.2 part, 0.5 part, 0.8 part, 1 part, 1.5 part, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts, and specific values therebetween are not intended to be exhaustive for the sake of brevity and clarity.
Preferably, the thickness of the anti-radiation antibacterial layer is 10-200 μm, such as 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 120 μm, 140 μm, 150 μm, 170 μm or 190 μm, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the thickness of the thermoplastic polyurethane layer is 0.05-2 mm, for example, 0.08mm, 0.1mm, 0.3mm, 0.5mm, 0.7mm, 0.9mm, 1mm, 1.1mm, 1.3mm, 1.5mm, 1.7mm or 1.9mm, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values included in the range.
Preferably, the material of the base cloth layer is nylon cloth,
preferably, the nylon cloth is any one of 840D nylon cloth, 420D nylon cloth or 210D nylon cloth,
preferably, the material of the waterproof layer is a TPU middle permeable membrane.
Preferably, the thickness of the waterproof layer is 0.01 to 0.5mm, such as 0.03mm, 0.05mm, 0.08mm, 0.1mm, 0.12mm, 0.15mm, 0.18mm, 0.2mm, 0.25mm, 0.3mm, 0.35mm, 0.4mm, 0.45mm or 0.48mm, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the base fabric layer and the thermoplastic polyurethane layer are bonded by an adhesive.
Preferably, the base cloth layer and the waterproof layer are bonded through an adhesive.
Preferably, the adhesive is a polyurethane hot melt adhesive.
Preferably, the curing agent is an isocyanate curing agent.
Preferably, the molar ratio of the NCO groups of the isocyanate curing agent to the hydroxyl groups of the unsaturated polyester resin is (1.05-1.3): 1, and may be, for example, 1.06:1, 1.08:1, 1.1:1, 1.12:1, 1.15:1, 1.18:1, 1.2:1, 1.22:1, 1.25:1, or 1.28: 1.
Preferably, the mass ratio of the nano silver to the ionol is 1 (1.5-3), such as 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8 or 1: 2.9.
As a preferred technical scheme of the invention, the mass ratio of the nano silver to the ionol is 1 (1.5-3), and the ionol effectively modifies and coats the nano silver, so that the decrease of antibacterial performance caused by the agglomeration of the nano silver is avoided. If the using amount of the ionol is too low, on one hand, the modification effect of the nano-silver is weakened, and the antibacterial performance is reduced, and on the other hand, the crosslinking density of the anti-radiation antibacterial layer and the flexibility of the molecular chain segment are influenced, so that the toughness is reduced; if the amount of ionol is too large, the water-washability and mechanical strength of the radiation-resistant antibacterial layer are affected.
Preferably, the unsaturated polyester resin has a number average molecular weight of 2500 to 6000g/mol, such as 2600g/mol, 2800g/mol, 3000g/mol, 3200g/mol, 3500g/mol, 3800g/mol, 4000g/mol, 4200g/mol, 4500g/mol, 4800g/mol, 5000g/mol, 5200g/mol, 5500g/mol or 5800g/mol, and the specific values therebetween are limited to space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the hydroxyl value of the unsaturated polyester resin is 20-120 mg KOH/g, for example, 25mg KOH/g, 30mg KOH/g, 40mg KOH/g, 50mg KOH/g, 60mg KOH/g, 70mg KOH/g, 80mg KOH/g, 90mg KOH/g, 100mg KOH/g, 110mg KOH/g, or 115mg KOH/g, and the specific points therebetween are limited by space and for brevity, and the invention is not exhaustive.
Preferably, the crosslinking agent is an organic peroxide.
Preferably, the organic peroxide is selected from any one of cyclohexanone peroxide, benzoyl peroxide, dicumyl peroxide or tert-butyl peroxybenzoate or a combination of at least two of the above.
Preferably, the radiation-resistant bacteriostatic slurry further comprises 0.01-3 parts by weight of an organic bacteriostatic agent, for example, the organic bacteriostatic agent may be 0.03 part, 0.05 part, 0.08 part, 0.1 part, 0.3 part, 0.5 part, 0.8 part, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.3 parts, 2.5 parts or 2.8 parts, and specific point values between the above point values are limited by space and for the sake of brevity, and the specific point values included in the range are not exhaustive.
Preferably, the organic bacteriostatic agent comprises any one or combination of at least two of chlorhexidine hydrochloride, chlorhexidine acetate, chlorhexidine gluconate or quaternary ammonium salt bacteriostatic agents.
Preferably, the anti-radiation bacteriostatic slurry further comprises 0.01-2 parts by weight of wetting dispersant, for example, the wetting dispersant may be 0.03 part, 0.05 part, 0.08 part, 0.1 part, 0.3 part, 0.5 part, 0.8 part, 1 part, 1.2 parts, 1.5 parts or 1.8 parts, and specific points between the above points are limited by space and for brevity, and the invention is not exhaustive of the specific points included in the range.
Preferably, the anti-radiation bacteriostatic slurry further comprises 2-30 parts by weight of solvent, for example, the solvent may be 3 parts, 5 parts, 7 parts, 9 parts, 10 parts, 11 parts, 13 parts, 15 parts, 18 parts, 20 parts, 21 parts, 23 parts, 25 parts or 28 parts, and specific points between the above points are limited by space and for conciseness, and the invention is not exhaustive enumeration of the specific points included in the range.
Preferably, the solvent comprises any one or a combination of at least two of an alcohol solvent, an ester solvent, an alkane solvent or an aromatic hydrocarbon solvent; the type and amount of solvent can be adjusted according to the viscosity requirement of the spray coating.
Preferably, the anti-radiation bacteriostatic slurry is prepared by a method comprising the following steps of: uniformly mixing nano silver, ionol and an optional solvent, adding aluminum powder and an optional wetting dispersant, and performing ultrasonic dispersion to obtain a material A; and mixing and mechanically dispersing the material A, the unsaturated polyester resin, the cross-linking agent, the optional organic bacteriostatic agent and the optional solvent to obtain the anti-radiation bacteriostatic slurry.
Preferably, the power of the ultrasonic dispersion is 0.5 to 3kW, for example, 0.6kW, 0.8kW, 1kW, 1.2kW, 1.5kW, 1.8kW, 2kW, 2.2kW, 2.5kW or 2.8kW, and specific values therebetween are not exhaustive, and for simplicity, the specific values included in the range are not exhaustive.
Preferably, the ultrasonic dispersion has a frequency of 15 to 25kHz, for example, 16kHz, 17kHz, 18kHz, 19kHz, 20kHz, 21kHz, 22kHz, 23kHz or 24kHz, and specific values therebetween, which are not exhaustive for the invention and are included in the range for brevity.
Preferably, the time of the ultrasonic dispersion is 10-60 min, for example, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min or 55min, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive.
In a second aspect, the present invention provides a method for preparing the polyurethane composite cloth according to the first aspect, the method comprising the following steps:
(1) coating adhesives on two surfaces of the base cloth, and compounding the base cloth with the thermoplastic polyurethane film and the waterproof film to obtain the pretreated cloth;
(2) activating the thermoplastic polyurethane membrane surface of the pre-treated cloth obtained in the step (1) to obtain activated cloth;
(3) uniformly mixing the anti-radiation antibacterial slurry and the curing agent to obtain a coating agent; and (3) coating the coating agent on the activated surface of the activated treatment cloth obtained in the step (2), and curing to obtain the polyurethane composite cloth.
Preferably, the compounding method in step (1) is hot press compounding.
Preferably, the temperature of the thermal press-compounding is 35 to 60 ℃, for example, 36 ℃, 38 ℃, 40 ℃, 41 ℃, 43 ℃, 45 ℃, 48 ℃, 50 ℃, 51 ℃, 53 ℃, 55 ℃ or 58 ℃, and the specific values therebetween are limited by the space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the pressure of the hot-pressing compounding is 1-6 kg/cm2For example, it may be 1.5kg/cm2、2kg/cm2、2.5kg/cm2、3kg/cm2、3.5kg/cm2、4kg/cm2、4.5kg/cm2、5kg/cm2、5.5kg/cm2Or 5.8kg/cm2And the specific values between the foregoing, are not intended to be exhaustive or to limit the invention to the precise values encompassed within the scope, for reasons of brevity and clarity.
Preferably, the activating reagent in the step (2) is chromic acid solution.
Preferably, the method of the activation treatment in step (2) is: and spraying chromic acid solution on the thermoplastic polyurethane membrane surface of the pretreated cloth, and then washing with water to finish the activation treatment.
As a preferable technical scheme of the invention, after the surface of the thermoplastic polyurethane film is activated by chromic acid solution, hydroxyl functional groups are formed, so that the surface of the thermoplastic polyurethane film is crosslinked with a coating agent consisting of the radiation-resistant antibacterial sizing agent and the curing agent to form a stable coating, and the polyurethane composite cloth has excellent durability and washing resistance.
Preferably, the retention time of the chromic acid solution on the thermoplastic polyurethane membrane surface is 0.2-2 min, for example, 0.3min, 0.5min, 0.7min, 0.9min, 1min, 1.1min, 1.3min, 1.5min, 1.7min or 1.9min, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive. If the residence time is too short, sufficient activated groups cannot be formed on the surface of the thermoplastic polyurethane film; if the retention time is too long, the thermoplastic polyurethane film can be corroded, and the mechanical property and the appearance of the polyurethane composite cloth are influenced.
Preferably, the curing temperature in the step (3) is 25 to 60 ℃, for example, 28 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃, 42 ℃, 45 ℃, 48 ℃, 50 ℃, 52 ℃, 55 ℃ or 58 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the curing time in step (3) is 1 to 6 hours, for example, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours or 5.5 hours, and specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not limited to the specific values included in the range.
Compared with the prior art, the invention has the following beneficial effects:
the polyurethane composite cloth provided by the invention comprises an anti-radiation antibacterial layer, a thermoplastic polyurethane layer, a base cloth layer and a polyurethane layerThe waterproof layer, the introduction of the functional anti-radiation antibacterial layer and the mutual matching of the multilayer structure enable the polyurethane composite cloth to have excellent antibacterial property, anti-radiation property, thermal conductivity, air permeability and waterproofness, the air permeability is more than 1340, and the hydrostatic pressure is more than or equal to 510cm H2And O, the antibacterial rate of the detergent on staphylococcus aureus is more than or equal to 99%, the detergent has good mechanical property, good strength and toughness and good stability, the antibacterial rate after washing for 100 times is still more than or equal to 99%, the detergent has good durability, can meet the requirement of long-time repeated use, and has wide market prospect.
Drawings
Fig. 1 is a schematic structural diagram of a polyurethane composite fabric provided in example 1;
wherein, the coating comprises 1-an anti-radiation antibacterial layer, 2-a thermoplastic polyurethane layer, 3-a base fabric layer and 4-a waterproof layer.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In the following examples of the present invention, the thermoplastic polyurethane film used was a commercially available polyether TPU film having a thickness of 0.15 mm; the waterproof membrane is a commercially available TPU (thermoplastic polyurethane) middle permeable membrane, and the thickness of the waterproof membrane is 0.1 mm; the base cloth is 840D nylon cloth;
the unsaturated polyester resin was a commercially available product having a number average molecular weight of 3350g/mol (as determined by gel chromatography GPC) and a hydroxyl value of 43mg KOH/g;
isocyanate curing agent: isocyanate trimer, bayer 3390;
wetting and dispersing agent: from EFKA 4010.
Example 1
A structural schematic diagram of a polyurethane composite cloth with radiation heat resistance is shown in figure 1, and the polyurethane composite cloth comprises a radiation-resistant antibacterial layer 1, a thermoplastic polyurethane layer 2, a base cloth layer 3 and a waterproof layer 4 which are sequentially arranged;
the anti-radiation antibacterial layer 1 is obtained by reacting anti-radiation antibacterial slurry and an isocyanate curing agent, wherein the anti-radiation antibacterial slurry comprises the following components in parts by weight: 8 parts of nano silver, 15 parts of alpha-ionol, 6 parts of aluminum powder, 40 parts of unsaturated polyester resin, 2 parts of a cross-linking agent (cyclohexanone peroxide), 0.3 part of chlorhexidine hydrochloride, 0.02 part of a wetting dispersant and 10 parts of a solvent (dimethylbenzene); the preparation method of the anti-radiation bacteriostatic slurry comprises the following steps: mixing nano silver, ionol and 5 parts of solvent, and ultrasonically dispersing for 10min at 20kHz and 1.5 kW; then adding aluminum powder and a wetting dispersant into the mixture, and performing ultrasonic dispersion for 30min at 20kHz and 1.5kW to obtain a material A; and mixing the material A, unsaturated polyester resin, a cross-linking agent, chlorhexidine hydrochloride and the residual solvent, and mechanically dispersing until the fineness is less than 25 mu m to obtain the anti-radiation antibacterial slurry.
The preparation method of the polyurethane composite cloth comprises the following steps:
(1) coating polyurethane hot melt adhesive on two surfaces of the base fabric, then attaching a polyether type TPU film on one surface of the base fabric, attaching a TPU permeable film on the other surface of the base fabric, and carrying out hot-pressing compounding at 45 ℃, wherein the pressure of a compounded compounding roller is 3.5kg/cm2Fully drying to obtain the pretreated cloth;
(2) spraying a chromic acid solution on the thermoplastic polyurethane membrane surface of the pretreated cloth obtained in the step (1), and washing with water after spraying to ensure that the chromic acid solution stays on the membrane surface for 1min to obtain activated treated cloth;
(3) uniformly mixing the anti-radiation antibacterial sizing agent and an isocyanate curing agent to ensure that the molar ratio of NCO to-OH of unsaturated polyester resin is 1.2:1 to obtain a coating agent; and (3) spraying the coating agent on the activated surface of the activated treatment cloth obtained in the step (2), and curing for 4 hours in a 50 ℃ oven to form a coating (an anti-radiation antibacterial layer 1) with the dry film thickness of 35 mu m, so as to obtain the polyurethane composite cloth.
Example 2
A polyurethane composite cloth with anti-radiation heat has the same structural schematic diagram as that of the embodiment 1, and comprises an anti-radiation antibacterial layer, a thermoplastic polyurethane layer, a base cloth layer and a waterproof layer which are sequentially arranged;
the anti-radiation antibacterial layer is obtained by reacting anti-radiation antibacterial slurry and an isocyanate curing agent, wherein the anti-radiation antibacterial slurry comprises the following components in parts by weight: 6 parts of nano silver, 10 parts of alpha-ionol, 4 parts of aluminum powder, 30 parts of unsaturated polyester resin, 1 part of cross-linking agent (cyclohexanone peroxide), 0.2 part of chlorhexidine hydrochloride, 0.01 part of wetting dispersant and 8 parts of solvent (dimethylbenzene); the preparation method of the anti-radiation bacteriostatic slurry comprises the following steps: mixing nano silver, ionol and 5 parts of solvent, and ultrasonically dispersing for 10min at 15kHz and 1.5 kW; then adding aluminum powder and a wetting dispersant into the mixture, and performing ultrasonic dispersion on the mixture for 30min at 15kHz and 1.5kW to obtain a material A; and mixing the material A, unsaturated polyester resin, a cross-linking agent, chlorhexidine hydrochloride and the residual solvent, and mechanically dispersing until the fineness is less than 25 mu m to obtain the anti-radiation antibacterial slurry.
The preparation method of the polyurethane composite cloth comprises the following steps:
(1) coating polyurethane hot melt adhesive on two surfaces of the base fabric, then attaching a polyether type TPU film on one surface of the base fabric, attaching a TPU permeable film on the other surface of the base fabric, and carrying out hot-pressing compounding at 45 ℃, wherein the pressure of a compounded compounding roller is 3.5kg/cm2Fully drying to obtain the pretreated cloth;
(2) spraying a chromic acid solution on the thermoplastic polyurethane membrane surface of the pretreated cloth obtained in the step (1), and washing with water after spraying to ensure that the retention time of the chromic acid solution on the membrane surface is 30s, thereby obtaining the activated treated cloth;
(3) uniformly mixing the anti-radiation antibacterial sizing agent and an isocyanate curing agent to ensure that the molar ratio of NCO to-OH of unsaturated polyester resin is 1.2:1 to obtain a coating agent; and (3) spraying the coating agent on the activated surface of the activated treatment cloth obtained in the step (2), and curing for 4 hours in a 50 ℃ oven to form a coating (an anti-radiation antibacterial layer) with the dry film thickness of 35 mu m to obtain the polyurethane composite cloth.
Example 3
A polyurethane composite cloth with anti-radiation heat has the same structural schematic diagram as that of the embodiment 1, and comprises an anti-radiation antibacterial layer, a thermoplastic polyurethane layer, a base cloth layer and a waterproof layer which are sequentially arranged;
the anti-radiation antibacterial layer is obtained by reacting anti-radiation antibacterial slurry and an isocyanate curing agent, wherein the anti-radiation antibacterial slurry comprises the following components in parts by weight: 10 parts of nano silver, 20 parts of alpha-ionol, 10 parts of aluminum powder, 50 parts of unsaturated polyester resin, 2.5 parts of a cross-linking agent (cyclohexanone peroxide), 0.5 part of chlorhexidine hydrochloride, 0.05 part of a wetting dispersant and 15 parts of a solvent (dimethylbenzene); the preparation method of the anti-radiation bacteriostatic slurry comprises the following steps: mixing nano silver, ionol and 8 parts of solvent, and ultrasonically dispersing for 15min at 25kHz and 1.5 kW; then adding aluminum powder and a wetting dispersant into the mixture, and performing ultrasonic dispersion on the mixture for 45min at 25kHz and 1.5kW to obtain a material A; and mixing the material A, unsaturated polyester resin, a cross-linking agent, chlorhexidine hydrochloride and the residual solvent, and mechanically dispersing until the fineness is less than 25 mu m to obtain the anti-radiation antibacterial slurry.
The preparation method of the polyurethane composite cloth comprises the following steps:
(1) coating polyurethane hot melt adhesive on two surfaces of the base fabric, then attaching a polyether type TPU film on one surface of the base fabric, attaching a TPU permeable film on the other surface of the base fabric, and carrying out hot-pressing compounding at 45 ℃, wherein the pressure of a compounded compounding roller is 3.5kg/cm2Fully drying to obtain the pretreated cloth;
(2) spraying a chromic acid solution on the thermoplastic polyurethane membrane surface of the pretreated cloth obtained in the step (1), and washing with water after spraying to ensure that the chromic acid solution stays on the membrane surface for 1.5min to obtain activated treated cloth;
(3) uniformly mixing the anti-radiation antibacterial sizing agent and an isocyanate curing agent to ensure that the molar ratio of NCO to-OH of unsaturated polyester resin is 1.2:1 to obtain a coating agent; and (3) spraying the coating agent on the activated surface of the activated treatment cloth obtained in the step (2), and curing for 4 hours in a 50 ℃ oven to form a coating (an anti-radiation antibacterial layer) with the dry film thickness of 35 mu m to obtain the polyurethane composite cloth.
Example 4
A polyurethane composite cloth with anti-radiation heat has the same structural schematic diagram as that of the embodiment 1, and comprises an anti-radiation antibacterial layer, a thermoplastic polyurethane layer, a base cloth layer and a waterproof layer which are sequentially arranged;
the anti-radiation antibacterial layer is obtained by reacting anti-radiation antibacterial slurry and an isocyanate curing agent, wherein the anti-radiation antibacterial slurry comprises the following components in parts by weight: 12 parts of nano silver, 15 parts of alpha-ionol, 6 parts of aluminum powder, 40 parts of unsaturated polyester resin, 2 parts of a cross-linking agent (cyclohexanone peroxide), 0.3 part of chlorhexidine hydrochloride, 0.02 part of a wetting dispersant and 10 parts of a solvent (dimethylbenzene); the preparation method of the anti-radiation bacteriostatic slurry and the preparation method of the polyurethane composite cloth are the same as those in the example 1.
Example 5
A polyurethane composite cloth with radiant heat resistance, which is different from the polyurethane composite cloth in example 1 only in that the preparation method of the polyurethane composite cloth does not include the step (2), namely, the coating agent is directly sprayed on the thermoplastic polyurethane film surface of the pre-treated cloth, so as to obtain the polyurethane composite cloth.
Comparative example 1
A polyurethane composite cloth with anti-radiation heat has the same structural schematic diagram as that of the embodiment 1, and comprises an anti-radiation antibacterial layer, a thermoplastic polyurethane layer, a base cloth layer and a waterproof layer which are sequentially arranged;
the anti-radiation antibacterial layer is obtained by reacting anti-radiation antibacterial slurry and an isocyanate curing agent, wherein the anti-radiation antibacterial slurry comprises the following components in parts by weight: 8 parts of nano silver, 30 parts of alpha-ionol, 6 parts of aluminum powder, 40 parts of unsaturated polyester resin, 2 parts of a cross-linking agent (cyclohexanone peroxide), 0.3 part of chlorhexidine hydrochloride, 0.02 part of a wetting dispersant and 10 parts of a solvent (dimethylbenzene); the preparation method of the anti-radiation bacteriostatic slurry and the preparation method of the polyurethane composite cloth are the same as those in the example 1.
Comparative example 2
A polyurethane composite cloth with anti-radiation heat has the same structural schematic diagram as that of the embodiment 1, and comprises an anti-radiation antibacterial layer, a thermoplastic polyurethane layer, a base cloth layer and a waterproof layer which are sequentially arranged;
the anti-radiation antibacterial layer is obtained by reacting anti-radiation antibacterial slurry and an isocyanate curing agent, wherein the anti-radiation antibacterial slurry comprises the following components in parts by weight: 8 parts of nano silver, 5 parts of alpha-ionol, 6 parts of aluminum powder, 40 parts of unsaturated polyester resin, 2 parts of a cross-linking agent (cyclohexanone peroxide), 0.3 part of chlorhexidine hydrochloride, 0.02 part of a wetting dispersant and 10 parts of a solvent (dimethylbenzene); the preparation method of the anti-radiation bacteriostatic slurry and the preparation method of the polyurethane composite cloth are the same as those in the example 1.
Comparative example 3
A polyurethane composite cloth with anti-radiation heat has the same structural schematic diagram as that of the embodiment 1, and comprises an anti-radiation antibacterial layer, a thermoplastic polyurethane layer, a base cloth layer and a waterproof layer which are sequentially arranged;
the anti-radiation antibacterial layer is obtained by reacting anti-radiation antibacterial slurry and an isocyanate curing agent, wherein the anti-radiation antibacterial slurry comprises the following components in parts by weight: 8 parts of nano silver, 15 parts of PEG-300, 6 parts of aluminum powder, 40 parts of unsaturated polyester resin, 2 parts of a cross-linking agent (cyclohexanone peroxide), 0.3 part of chlorhexidine hydrochloride, 0.02 part of a wetting dispersant and 10 parts of a solvent (dimethylbenzene); the preparation method of the anti-radiation bacteriostatic slurry and the preparation method of the polyurethane composite cloth are the same as those in the example 1.
The performance test of the polyurethane composite cloth provided in the examples 1 to 5 and the comparative examples 1 to 3 is carried out by the following specific method:
(1) air permeability: the test is carried out according to the method in the national standard GB/T5453-1997, and the pressure drop is 100 Pa; the larger the measured air permeability is, the better the air permeability is;
(2) water resistance: the water impermeability is tested according to the method in the national standard GB/T19082-2009 to obtain the hydrostatic pressure of the polyurethane composite cloth, wherein the unit is cm H2O；
(3) And (3) antibacterial property: testing the bacteriostasis rate according to the method in the national standard GB/T20944.2-2007, wherein the experimental strain is gram-positive bacterium staphylococcus aureus (ATCC 6538);
(4) water washing resistance: washing the polyurethane composite cloth to be tested in a drum washing machine for 100 times, and then testing the antibacterial property;
(5) mechanical properties: testing according to the method in the national standard GB/T1732-1993, wherein the weight is 1000g, the polyurethane composite cloth is attached to a tinplate, the weight falls down to be in contact with the anti-radiation antibacterial layer, and the mechanical property of the anti-radiation antibacterial layer is judged according to the impact resistance (unit is cm);
the specific test results are shown in table 1:
TABLE 1
According to the performance data in table 1, the polyurethane composite cloth provided in the embodiments 1 to 4 of the present invention has a bacteriostatic rate of not less than 99%, and is breathableThe amount is 1340-1361, and the hydrostatic pressure is 510-524 cm H2O, has excellent antibacterial property, radiation resistance, air permeability and waterproof property, good impact resistance (especially the impact resistance of the radiation-resistant antibacterial layer), high toughness and high strength; the bacteriostasis rate of the polyurethane composite cloth drum washing machine after 100 times of washing is still more than 99 percent, which shows that the performance stability is good, and the function of the anti-radiation bacteriostasis layer can not be attenuated. In the anti-radiation antibacterial layer, the ionol has good modification and dispersion effects on the nano-silver, so that the antibacterial activity of the nano-silver is ensured; if the dosage of the nano silver is too much (example 4), the agglomeration of the nano particles can occur, and the bacteriostatic performance is further influenced. In addition, after the thermoplastic polyurethane layer in the polyurethane composite cloth is subjected to activation treatment, the thermoplastic polyurethane layer and the anti-radiation antibacterial layer can be subjected to moderate crosslinking to form stable adhesion, so that the water washing resistance of the polyurethane composite cloth is improved; if the thermoplastic polyurethane layer is directly coated with the coating agent without activation (example 5), the resulting polyurethane composite fabric suffers significant property deterioration after washing with water and also suffers a decrease in mechanical strength.
According to the polyurethane composite cloth provided by the invention, the introduction of the functional anti-radiation antibacterial layer is matched with the multi-layer structure, particularly ionol, unsaturated polyester resin, a cross-linking agent and a curing agent in the anti-radiation antibacterial layer are reacted to form a flexible and compact cross-linking system, and nano silver and aluminum powder are fixed in the polymer network structure, so that the polyurethane composite cloth is endowed with excellent comprehensive performance. If the dosage of the ionol in the anti-radiation antibacterial layer is too much (comparative example 1), the mechanical property of the coating is reduced, the water washing resistance is reduced, and the antibacterial activity is seriously attenuated after washing; if the using amount of the ionol is too small (comparative example 2), the nano silver in the composite cloth is agglomerated, the antibacterial performance is poor, the internal crosslinking degree of the coating is insufficient, and the impact performance is poor; the comparative example 3 does not contain ionol, and although the polyethylene glycol PEG-300 can improve the dispersion of nano silver, the initial bacteriostasis rate of the polyurethane composite cloth is higher, the mechanical property of the anti-radiation antibacterial layer is poor, the polyurethane composite cloth is not resistant to washing, and the polyurethane composite cloth cannot be recycled.
The applicant states that the present invention is described by the above examples, but the present invention is not limited to the above process steps, i.e., it does not mean that the present invention must be implemented by relying on the above process steps. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. The polyurethane composite cloth with the radiant heat resistance is characterized by comprising a radiant heat resistance antibacterial layer, a thermoplastic polyurethane layer, a base cloth layer and a waterproof layer which are sequentially arranged;
the anti-radiation antibacterial layer is obtained through the curing reaction of anti-radiation antibacterial slurry and a curing agent, wherein the anti-radiation antibacterial slurry comprises the following components in parts by weight: 5-12 parts of nano silver, 10-20 parts of ionol, 2-10 parts of aluminum powder, 30-50 parts of unsaturated polyester resin and 0.1-5 parts of cross-linking agent.
2. The polyurethane composite cloth according to claim 1, wherein the thickness of the radiation-resistant antibacterial layer is 10-200 μm;
preferably, the thickness of the thermoplastic polyurethane layer is 0.05-2 mm.
3. The polyurethane composite cloth according to claim 1 or 2, wherein the material of the base cloth layer is nylon cloth;
preferably, the nylon cloth is any one of 840D nylon cloth, 420D nylon cloth or 210D nylon cloth;
preferably, the waterproof layer is made of TPU middle permeable membrane;
preferably, the thickness of the waterproof layer is 0.01-0.5 mm;
preferably, the base cloth layer and the thermoplastic polyurethane layer are bonded through an adhesive;
preferably, the base cloth layer and the waterproof layer are bonded through an adhesive;
preferably, the adhesive is a polyurethane hot melt adhesive.
4. The polyurethane composite fabric according to any one of claims 1 to 3, wherein the curing agent is an isocyanate curing agent;
preferably, the molar ratio of NCO groups of the isocyanate curing agent to hydroxyl groups of the unsaturated polyester resin is (1.05-1.3): 1;
preferably, the mass ratio of the nano silver to the ionol is 1 (1.5-3).
5. The polyurethane composite fabric according to any one of claims 1 to 4, wherein the unsaturated polyester resin has a number average molecular weight of 2500 to 6000 g/mol;
preferably, the hydroxyl value of the unsaturated polyester resin is 20-120 mg KOH/g;
preferably, the crosslinking agent is an organic peroxide;
preferably, the organic peroxide is selected from any one of cyclohexanone peroxide, benzoyl peroxide, dicumyl peroxide or tert-butyl peroxybenzoate or a combination of at least two of the above.
6. The polyurethane composite cloth according to any one of claims 1 to 5, wherein the radiation-resistant bacteriostatic slurry further comprises 0.01 to 3 parts by weight of an organic bacteriostatic agent;
preferably, the organic bacteriostatic agent comprises any one or a combination of at least two of chlorhexidine hydrochloride, chlorhexidine acetate, chlorhexidine gluconate or quaternary ammonium salt bacteriostatic agents;
preferably, the anti-radiation bacteriostatic slurry further comprises 0.01-2 parts by weight of a wetting dispersant;
preferably, the anti-radiation bacteriostatic slurry further comprises 2-30 parts by weight of a solvent.
7. The polyurethane composite fabric according to any one of claims 1 to 6, wherein the anti-radiation bacteriostatic slurry is prepared by a method comprising the following steps of: uniformly mixing nano silver, ionol and an optional solvent, adding aluminum powder and an optional wetting dispersant, and performing ultrasonic dispersion to obtain a material A; mixing and mechanically dispersing the material A, the unsaturated polyester resin, the cross-linking agent, the optional organic bacteriostatic agent and the optional solvent to obtain the anti-radiation bacteriostatic slurry;
preferably, the power of the ultrasonic dispersion is 0.5-3 kW;
preferably, the frequency of the ultrasonic dispersion is 15-25 kHz;
preferably, the time of ultrasonic dispersion is 10-60 min.
8. A preparation method of the polyurethane composite cloth as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
(1) coating adhesives on two surfaces of the base cloth, and compounding the base cloth with the thermoplastic polyurethane film and the waterproof film to obtain the pretreated cloth;
(2) activating the thermoplastic polyurethane membrane surface of the pre-treated cloth obtained in the step (1) to obtain activated cloth;
(3) uniformly mixing the anti-radiation antibacterial slurry and the curing agent to obtain a coating agent; and (3) coating the coating agent on the activated surface of the activated treatment cloth obtained in the step (2), and curing to obtain the polyurethane composite cloth.
9. The method for preparing the composite material according to claim 8, wherein the compounding method in the step (1) is hot press compounding;
preferably, the temperature of the hot-pressing compounding is 35-60 ℃;
preferably, the pressure of the hot-pressing compounding is 1-6 kg/cm2；
Preferably, the activating reagent in the step (2) is chromic acid solution;
preferably, the method of the activation treatment in step (2) is: spraying chromic acid solution on the thermoplastic polyurethane membrane surface of the pretreated cloth, and then cleaning with water to finish activation treatment;
preferably, the retention time of the chromic acid solution on the thermoplastic polyurethane membrane surface is 0.2-2 min.
10. The method for preparing the epoxy resin composition according to claim 8 or 9, wherein the curing temperature in the step (3) is 25 to 60 ℃;
preferably, the curing time in the step (3) is 1-6 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109852744A (en) * | 2019-01-24 | 2019-06-07 | 南京天诗蓝盾生物科技有限公司 | A kind of antibacterial treatment process of leather |
| CN111391444A (en) * | 2020-04-26 | 2020-07-10 | 上海玉灵猫服装设计中心 | Protective fabric and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109852744A (en) * | 2019-01-24 | 2019-06-07 | 南京天诗蓝盾生物科技有限公司 | A kind of antibacterial treatment process of leather |
| CN111391444A (en) * | 2020-04-26 | 2020-07-10 | 上海玉灵猫服装设计中心 | Protective fabric and preparation method and application thereof |
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