CN111136968A

CN111136968A - Waterproof anti ultraviolet textile fabric

Info

Publication number: CN111136968A
Application number: CN201910794660.4A
Authority: CN
Inventors: 白朋
Original assignee: Shenzhen Daimaoniu New Material Technology Co Ltd
Current assignee: Shenzhen Daimaoniu New Material Technology Co Ltd
Priority date: 2019-08-27
Filing date: 2019-08-27
Publication date: 2020-05-12
Anticipated expiration: 2039-08-27
Also published as: CN111136968B

Abstract

The invention relates to a textile fabric, in particular to a waterproof and ultraviolet-proof textile fabric. A waterproof and ultraviolet-proof textile fabric comprises an outer layer, a middle layer and an inner layer, wherein the outer layer is subjected to organic silicon plasma treatment and ultraviolet-proof treatment, and the middle layer is subjected to pore treatment and oxygen plasma treatment; the middle layer is formed by blending acrylic fibers and fibrilia, and the blending ratio of the acrylic fibers to the fibrilia is (1-5): 1; the thickness of the inner layer is 0.1-0.5 mm. The waterproof and ultraviolet-proof textile fabric prepared by the invention has the advantages that by adopting a special process and fabric, the fabric has the functions of moisture resistance and sun protection, and the heat conductivity of the fabric is reduced; in addition, the pores, the pits and the micropores in the fabric can be closed through the contraction action in the drying process of the fabric fibers, so that the wind resistance of the fabric is improved, and in the presence of liquid, the fibers absorb water and expand to open the closed pores, the pits and the micropores again, so that the waterproof and moisture permeable functions of the fabric are realized.

Description

Waterproof anti ultraviolet textile fabric

Technical Field

The invention relates to the technical field of textile fabrics, in particular to a waterproof and ultraviolet-proof textile fabric.

Background

With the development of social economy and the improvement of national living standard, people's requirements for textile fabrics tend to be ' people oriented ' more and more, and the aim of the method is to constantly develop new products around the health and comfort of people and the protection of ecological environment. Along with the leisure and the liberalization of clothes, people require softer clothes fabric, absorb moisture and ventilate, have different functional requirements on clothes or decorative fabrics with different purposes, and various protective or health-care textiles and clothes are produced at the same time.

In the prior art, a functionalized reagent or high-tech equipment is usually adopted to treat textile fabric, so that the textile fabric is endowed with a specific function, a consumer can enjoy comfortable, healthy and safe textiles, and the urgent demand of wearing comfort of the consumer is met to a certain extent. However, in the process of developing multifunctional fabrics, contradictory functional combinations such as waterproofness and moisture permeability, moisture permeability and windproof performance often exist, so that the textile fabrics prepared in the prior art cannot meet the requirements of people on waterproofness, moisture permeability, ultraviolet protection, windproof performance and warmth of the fabrics at the same time.

Disclosure of Invention

In order to solve the above problems, a first aspect of the present invention provides a waterproof and ultraviolet-proof textile fabric, comprising an outer layer, a middle layer and an inner layer;

the outer layer is subjected to organic silicon plasma treatment and ultraviolet-proof treatment; the middle layer is subjected to pore treatment and oxygen plasma treatment;

the middle layer is formed by blending acrylic fibers and fibrilia;

the blending ratio of the acrylic fibers to the fibrilia is (1-5): 1;

the thickness of the inner layer is 0.1-0.5 mm.

As a preferred technical solution of the present invention, the conditions of the organosilicon plasma treatment are as follows: the discharge voltage is 2-4 kV, and the discharge time is 45-55 s.

As a preferable technical scheme of the invention, the treating agent in the ultraviolet-proof treatment comprises modified nano zinc oxide.

As a preferable technical scheme, the preparation raw material of the modified nano zinc oxide comprises alkyl sulfonate with 10-18 carbon atoms.

As a preferable technical scheme of the invention, the alkyl sulfonate with 10-18 carbon atoms is one or a combination of several of n-undecyl sodium sulfonate, sodium dodecyl sulfonate, sodium tridecyl sulfonate, sodium hexadecyl sulfonate, sodium dodecyl benzene sulfonate, sodium tridecyl benzene sulfonate, sodium tetradecyl benzene sulfonate and sodium octadecyl benzene sulfonate.

In a preferred embodiment of the present invention, the treating agent in the pore treatment comprises a modified polyurethane resin.

As a preferable technical scheme of the invention, the preparation raw materials of the modified polyurethane resin comprise polytetrahydrofuran diol, adipic acid polyester and diphenylmethane diisocyanate.

As a preferred embodiment of the present invention, the conditions of the oxygen plasma treatment are: the discharge voltage is 3-5 kV, and the discharge time is 60-80 s.

As a preferred technical solution of the present invention, the volume ratio of the oxygen to the silicone gas is 1: (4-6).

The invention provides a preparation method of a waterproof and ultraviolet-proof textile fabric in a second aspect, which at least comprises the following steps: and (3) bonding the outer layer, the middle layer and the inner layer through a bonding agent to obtain the waterproof and ultraviolet-proof textile fabric.

Has the advantages that: according to the waterproof and ultraviolet-proof textile fabric prepared by the invention, by adopting a special process and the fabric, on one hand, the inherent problems of poor waterproof and ultraviolet-proof performance of the textile fabric are solved, so that the fabric has the functions of moisture prevention and sun protection, and under a specific treatment condition, the modified nano zinc oxide particles can be rapidly adsorbed on pores and pits formed by organic silicon plasma treatment, and due to the mutual entanglement of long chains, the modified nano zinc oxide particles can play a role in sealing the pores and the pits with the same particle size as the pores, so that the content of static air in the fabric is increased, and the thermal conductivity of the fabric is reduced; on the other hand, the pores, the pits and the micropores are formed in the fabric through the treatment of the modified polyurethane resin and the oxygen plasma, so that the moisture permeability function is endowed to the fabric, and in a specific condition, the pores, the pits and the micropores in the fabric can be closed through the contraction action in the drying process of fabric fibers, so that the wind resistance of the fabric is improved, and in the presence of liquid, the fibers absorb water and expand, and the closed pores, the pits and the micropores are opened again, so that the waterproof moisture permeability function is exerted.

Detailed Description

The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The words "preferred," "more preferred," "most preferred," and the like in this disclosure mean embodiments of the invention that may, in some instances, provide some benefit. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

In order to solve the above problems, a first aspect of the present invention provides a waterproof and ultraviolet-proof textile fabric, which includes an outer layer, a middle layer and an inner layer.

Outer layer

In a preferred embodiment, the thickness of the outer layer is 0.6-0.8 mm.

The thickness of the outer layer fabric is measured according to the national standard GB/T3820 1997 determination of the thickness of textiles and textile products.

In a more preferred embodiment, the outer layer according to the invention has a thickness of 0.7 mm.

In a preferred embodiment, the outer layer of the invention is formed by blending polyester and fluorine.

The blending of the invention is to blend and weave different types of fibers, and the blending of common chemical fibers and natural fibers or different chemical fibers can improve the yarn quality, save raw materials, increase varieties and the like.

The blended yarn has the advantages that through the organic combination of two or more different types of fibers, the advantages of the blended yarn are made up for the deficiencies of the fibers, the advantages of the blended yarn coexist, and different requirements of people on clothes are met. For example, the blended fabric of cotton and bamboo fiber has the advantages of heat preservation and comfort of cotton, sterilization, ventilation and coolness of bamboo fiber, no defect of easy wrinkle of cotton, no defect of bamboo fiber, hard hand feeling and the like.

The terylene of the invention, also called Terylene or Dacron, is an important variety in synthetic fiber, is the trade name of polyester fiber in China, and is fiber made by taking Poly Terephthalic Acid (PTA) or dimethyl terephthalate (DMT) and ethylene glycol (MEG) as raw materials, through esterification or ester exchange and polycondensation, to form fiber-forming high polymer, polyethylene terephthalate (PET), through spinning and post-treatment, and has the advantages of high strength and toughness, good elasticity, good thermoplasticity, good wear resistance, good light resistance, corrosion resistance and the like, and is widely used for manufacturing clothing and products in industry.

The terylene of the invention is composed of short aliphatic hydrocarbon chains, ester groups, benzene rings and terminal alcoholic hydroxyl groups from the aspect of molecular composition, and the terylene molecules have no other polar groups except for the two terminal alcoholic hydroxyl groups, so the hydrophilicity of the terylene fiber is very poor.

The invention relates to a polyfluorene fiber, also called a Teflon or polytetrafluoroethylene fiber, which is a polyolefin fiber prepared by spinning or preparing a film from polytetrafluoroethylene and then cutting or fibrillating. The strength and the elongation are high, the chemical stability is good, and the corrosion resistance is better than other synthetic fibers; the surface has wax feel, the friction coefficient is small (0.01-0.05), the actual use temperature is-180-260 ℃, and the strength is remarkably reduced when the material is heated to 300 ℃. Has better weatherability and flexibility resistance. However, they are inferior in dyeability and thermal conductivity, poor in abrasion resistance, large in expansion coefficient, and liable to generate static electricity. The high-temperature dust filter belt is mainly used as a high-temperature dust filter belt, a strong-corrosiveness filter material for filtering gas or liquid, a valve filler, a sealing belt, a self-lubricating bearing, bitter cloth of a rocket launching pad, an artificial blood vessel, a military coat and the like. The production method comprises the following steps: emulsion spinning, paste extrusion spinning, melt spinning, and the like.

The fluorine fiber is a highly symmetrical high molecular compound without polarity on the whole, and analysis shows that the fluorine fiber is a linear high molecular compound without any branched chain. Because the C-F bond, which is very strong, is difficult to open. The fluorine atoms have a large radius of action (0.72nm), so that the molecular chain has a helical structure in its stable configuration. Since the teflon has good non-tackiness, the filter material and the conveying device are relatively easy to clean.

In a preferred embodiment, the blending ratio of the terylene and the fluorine fiber is (2-5): 1.

the blending ratio of the invention is the proportion of blended yarn calculated by the dry weight of blended fiber, such as 10g of wool, 5g of acrylic fiber and 5g of polyester fiber in a piece of fabric, the blending ratio is 50%: 25%: 25% ═ 2: 1: 1.

in a most preferred embodiment, the blend ratio of the polyester and the fluorine fiber is 3: 1.

in a preferred embodiment, the outer layer according to the invention is subjected to a silicone plasma treatment and a uv protection treatment.

Organosilicon plasma treatment

The plasma (plasma) is an ionized gaseous substance consisting of atoms after partial electrons are deprived and positive and negative ions generated after atomic groups are ionized, and a macroscopic electrically neutral ionized gas with the dimension larger than the Debye length has the movement mainly dominated by electromagnetic force and shows remarkable collective behavior. It is widely present in the universe and is often considered to be the fourth state in which substances exist in addition to solids, liquids and gases. The plasma is a good electric conductor, and the plasma can be captured, moved and accelerated by utilizing a magnetic field which is skillfully designed. The development of plasma physics provides new technology and process for the further development of science such as materials, energy, information, environmental space, space physics, geophysical and the like. When heated to a sufficiently high temperature or for other reasons, the outer electrons become free electrons free of nuclei, and the electrons leave the nuclei, a process known as "ionization", in which the material becomes a homogeneous mass of "paste" consisting of positively charged nuclei and negatively charged electrons, and is thus called a plasma, which is a clever ion paste in which the total amount of positive and negative charges are equal and is therefore nearly electrically neutral.

The plasma of the present invention can be divided into high temperature plasma (or thermal plasma) and low temperature plasma (or cold plasma).

In a preferred embodiment, the plasma of the present invention is a low temperature plasma.

Although the electron temperature of the low-temperature plasma is high in the discharge process, the heavy particle temperature is low, and the whole system is in a low-temperature state, so that the low-temperature plasma is called as low-temperature plasma and is also called as non-equilibrium plasma.

The energy transfer in the low-temperature plasma according to the present invention is substantially: the electrons get energy from the electric field, the energy is converted into the internal energy and kinetic energy of molecules through collision, the molecules with the energy are excited, meanwhile, part of the molecules are ionized, and the activated particles collide with each other to cause a series of complex physicochemical reactions. Because a large amount of active particles such as ions, electrons, excited atoms and molecules, free radicals and the like are rich in the plasma, the plasma processing method provides conditions for processing the odor substances through chemical reaction by using the plasma technology.

The invention in the application discovers that after low-temperature plasma treatment, the modification effect of the textile material has a great relationship with the type of plasma gas, a plasma treatment device, plasma treatment conditions (gas pressure, discharge power and discharge time) and the surface performance of the treated object. The chemical reaction induced by the low-temperature plasma is an interfacial reaction between gas phases or between a gas phase and a solid phase, and the mechanism thereof is very complicated. In particular, different kinds of plasma reaction gases cause great differences in the surface modification effects of the processing materials.

In a preferred embodiment, the low temperature plasma gas of the present invention is a silicone gas.

The organosilicon gas described herein is provided by a siloxane.

The siloxane provided by the invention is one or a combination of several of linear chain or cyclic, volatile or nonvolatile, arylate or nonarylate siloxane.

In a preferred embodiment, the siloxane of the present invention is 2,4,6, 8-tetrabutyl-2, 4,6, 8-tetramethylcyclotetrasiloxane having a CAS of 14685-29-1.

In a preferred embodiment, the organosilicon plasma treatment process of the invention is: connecting a conical flask filled with 2,4,6, 8-tetrabutyl-2, 4,6, 8-tetramethylcyclotetrasiloxane to a plasma vacuum chamber, and heating to 80-90 ℃ for later use; putting the fabric into a low-temperature plasma vacuum chamber, vacuumizing, opening a switch to introduce standby gas when the pressure is reduced to 8-12 Pa, adjusting and controlling the pressure to a set value of 10-20 Pa after gas circulation, then opening a plasma radio frequency discharge button, setting the gas flow to be 12-16L/min, closing a gas valve after treating for a certain time, introducing air to normal pressure, and taking out a sample.

In a more preferred embodiment, the conditions of the organosilicon plasma treatment according to the invention are: the discharge voltage is 2-4 kV, and the discharge time is 45-55 s.

In a most preferred embodiment, the conditions of the organosilicon plasma treatment according to the invention are: discharge voltage 3kV, discharge time 50 s.

In a preferred embodiment, the outer layer according to the invention is subjected to a uv protection treatment after the silicone plasma treatment.

Anti-ultraviolet treatment

The ultraviolet-proof treatment is to add substances capable of shielding the ultraviolet effect, and to mix and treat the substances so as to improve the absorption and reflection capability of the fabric on ultraviolet rays. The ultraviolet shielding substance herein refers to two types, namely: substances that have a strong selective absorption of ultraviolet rays and perform energy conversion to reduce the transmittance thereof, are conventionally called ultraviolet absorbers; the substance which functions to reflect ultraviolet rays is conventionally called an ultraviolet screening agent.

The ultraviolet absorbent is usually an organic substance, and the currently commonly used organic ultraviolet absorbent comprises benzotriazoles, benzophenones, salicylic acids and triazines, wherein the benzotriazoles are widely applied, and are widely used as light stabilizers for plastics at present.

The ultraviolet screening agent is usually inorganic substance, and the ultraviolet screening effect is that the fine powder or the ultrafine powder of the ultraviolet screening agent is combined with the fiber or the fabric to reflect or refract the ultraviolet ray incident to the fabric. At present, zinc oxide, titanium dioxide, silicon dioxide, nano zinc oxide, nano titanium dioxide, nano silicon dioxide and the like are applied to more inorganic ultraviolet screening agents. Compared with nanoscale ultraviolet-resistant effect, the nanometer ultraviolet-resistant fabric has better ultraviolet-resistant effect and smaller influence on the style of the fabric, but the nanoscale specific surface area and specific surface energy are larger, so that the function energy among particles is enhanced, the nanometer ultraviolet-resistant fabric is easy to agglomerate and aggregate, and the dispersion uniformity of the inorganic ultraviolet screening agent in a system is reduced.

In a preferred embodiment, the treating agent in the ultraviolet ray prevention treatment comprises modified nano zinc oxide.

(modified Nano zinc oxide)

The nano zinc oxide (ZnO) has the particle size of 1-100nm, is a high-end high-function fine inorganic product, shows a plurality of special properties such as non-migration property, fluorescence property, piezoelectricity, ultraviolet ray absorption and scattering ability and the like, and can be used for manufacturing gas sensors, fluorescent bodies, varistors, ultraviolet ray shielding materials, image recording materials, piezoelectric materials, piezoresistors, high-efficiency catalysts, magnetic materials, plastic films and the like by utilizing the wonderful properties of the nano zinc oxide (ZnO) in the aspects of light, electricity, magnetism, sensitivity and the like. The excellent characteristics of the nano material cannot be seen by many people due to microscopic changes, and the nano zinc oxide is widely applied in various fields such as rubber and the like at present due to the excellent characteristics.

The nanometer zinc oxide has the outstanding characteristics that the product particles are nanometer, and simultaneously, the nanometer zinc oxide has the double characteristics of nanometer materials and the traditional zinc oxide. Compared with the traditional zinc oxide product, the zinc oxide has the advantages of large specific surface area, high chemical activity, adjustable product fineness, chemical purity and particle shape according to requirements, photochemical effect and good ultraviolet shielding performance, and the ultraviolet shielding rate is as high as 98%; meanwhile, the product also has a series of unique performances of resisting and inhibiting bacteria, removing odor, preventing enzyme and the like. However, the nano zinc oxide has the characteristics of large specific surface area, large specific surface energy and the like, and is easy to agglomerate; on the other hand, the surface polarity of the nano zinc oxide is strong, and the nano zinc oxide is not easy to be uniformly dispersed in an organic medium, so that the exertion of the nano effect is greatly limited. Therefore, the dispersion and surface modification of the nano zinc oxide powder become necessary treatment means before the nano material is applied to a matrix.

In a preferred embodiment, the raw material for preparing the modified nano zinc oxide comprises alkyl sulfonate with 10-18 carbon atoms.

In a preferred embodiment, the alkyl sulfonate with 10 to 18 carbon atoms is one or a combination of several of n-undecyl sodium sulfonate, sodium dodecyl sulfonate, sodium tridecyl sulfonate, sodium hexadecyl sulfonate, sodium dodecyl benzene sulfonate, sodium tridecyl benzene sulfonate, sodium tetradecyl benzene sulfonate, and sodium octadecyl benzene sulfonate.

In a more preferred embodiment, the alkylsulfonic acid salt having 10 to 18 carbon atoms according to the present invention is sodium hexadecyl sulfonate or sodium dodecyl benzene sulfonate.

In a preferred embodiment, the preparation steps of the modified nano zinc oxide of the invention comprise:

1) putting zinc nitrate and sodium hydroxide into a mortar according to the mass ratio of 1: 1-3, and fully grinding for 8-12 min;

2) adding sodium hexadecyl sulfonate and sodium dodecyl benzene sulfonate into the substance obtained in the step 1), and fully grinding for 35-45 min;

3) washing and filtering the substance obtained in the step 2), and drying at 80-90 ℃ for 2-3 h to obtain modified Zn (OH)₂；

4) The resulting modified Zn (OH)₂Roasting for 2.5-3.5 h, and controlling the roasting temperature at 320-380 ℃ to obtain the modified nano zinc oxide powder.

The weight ratio of the zinc nitrate in the step 1) to the sodium dodecyl benzene sulfonate in the step 2) is (100-130): 1.

in a preferred embodiment, the weight ratio of the zinc nitrate in step 1) to the sodium dodecylbenzenesulfonate in step 2) is 115: 1.

the CAS of the sodium hexadecyl sulfonate in the step 2) is 15015-81-3; the CAS of the sodium dodecyl benzene sulfonate is 25155-30-0.

The weight ratio of the sodium hexadecyl sulfonate to the sodium dodecyl benzene sulfonate in the step 2) is (2-4): 1.

in a preferred embodiment, the weight ratio of the sodium hexadecyl sulfonate to the sodium dodecyl benzene sulfonate is 3: 1.

in a preferred embodiment, the ultraviolet screening treatment of the present invention is a dipping method.

The impregnation method of the present invention is to soak solid powder or shaped solid with certain shape and size in soluble compound solution containing active component, and to contact for certain time to separate residual liquid. The active ingredient is thus attached to the solid in the form of ions or compounds, which is known as impregnation.

The basic principle of the impregnation method is that, on one hand, when the pores of the solid are contacted with the liquid, capillary pressure is generated due to the action of surface tension, so that the liquid permeates into the capillary; another aspect is the adsorption of the active ingredient on the surface of the carrier.

In a preferred embodiment, the step of the dipping treatment of the ultraviolet ray shielding treatment of the present invention comprises:

i) adding water into the modified nano zinc oxide powder to uniformly disperse the modified nano zinc oxide powder;

II) adding the water-based rosin resin emulsion and the amino silicon emulsion, and uniformly mixing to prepare a treating agent;

III) soaking the outer-layer fabric in the treating agent for 3-6 h, and drying at 125-135 ℃ after soaking is finished.

The weight ratio of the modified nano zinc oxide and water in the step I) is 1: (2-6).

The dispersion method in the step I) is mechanical stirring, the stirring speed is 550-650 r/min, and the stirring time is 5-15 min.

The weight ratio of the modified nano zinc oxide in the step I) to the water-based rosin resin emulsion in the step II) is 1: (2-4).

The weight ratio of the water-based rosin resin emulsion to the amino silicon emulsion in the step II) is 1: (1-3).

In a preferred embodiment, the aqueous rosin resin emulsion of the present invention is commercially available, for example, commercially available aqueous rosin resin emulsion includes, but is not limited to, model 780, available from Shanghai Sangon chemical Co.

In a preferred embodiment, the aminosilicone emulsion of the present invention is commercially available, for example commercially available aminosilicone emulsions include, but are not limited to, those available from Tengtian chemical technology (Shanghai) Inc. under the model number Tt-F430.

And the mixing mode in the step II) is mechanical stirring, the stirring speed is 700-800 r/min, and the stirring time is 10-20 min.

Due to the sputtering etching effect of high-energy particles in the plasma, the surface layer of the fiber in the outer fabric is subjected to crosslinking and molecular chain cutting, so that chemical active points are generated, the main chain of the organic silicon is very flexible, and the acting force between molecules of the organic silicon is much weaker than that of hydrocarbon, so that the organic silicon plasma can form hydrophobic substances on the surface of the fiber, the penetration of liquid water drops into the fabric is effectively prevented, and the waterproofness of the fabric is improved. In addition, the polyester fibers in the outer-layer fabric have no other polar groups except for the two terminal alcoholic hydroxyl groups, so that the polyester fibers have better hydrophobicity; on the other hand, the surface of the fluorine fiber in the outer layer fabric has a wax feeling, so that the fluorine fiber has an extremely low friction coefficient, and liquid water drops are difficult to stably stay on the outer layer fabric, therefore, the outer layer fabric is made of a blended fabric of polyester and fluorine, and the water resistance of the fabric can be effectively improved through organosilicon plasma treatment.

The zinc oxide has good ultraviolet shielding effect, and can reflect most of light radiated on the fabric, or selectively absorb and convert the energy into low energy to release, thereby blocking ultraviolet rays. And after the zinc oxide is made into nano powder, the size of the particles is equal to or smaller than the wavelength of light waves, and the shielding is obviously enhanced due to the small size effect. However, the nano zinc oxide has huge surface energy, so that particles are easy to agglomerate together, the dispersibility of the nano zinc oxide in a system is poor, the original superiority of the nano zinc oxide is even completely lost in actual use, and the using effect is opposite. The inventor adds alkyl sulfonate with 10-18 carbon atoms to coat the surface of newly generated particles, so that the coating effect inhibits the growth rate of the particles, namely the size of the particles is controlled; on the other hand, the newly generated particles have higher surface activity, so that the particles are easy to interact and agglomerate, the generated particles are mutually isolated due to the existence of the coating film, the agglomeration phenomenon is inhibited, the dispersibility of the nano zinc oxide in the system is improved, and the ultraviolet resistance of the fabric is improved.

However, the inventor of the present application has surprisingly found that when the outer fabric is subjected to the treatment with the organosilicon plasma, the discharge voltage is controlled to be 2-4 kV, the discharge time is 45-55 s, and then the ultraviolet-proof treatment is performed with the treating agent containing the modified nano zinc oxide, and in the process of preparing the modified nano zinc oxide, the hexadecyl sodium sulfonate and the dodecyl benzene sulfonate are selected, and the weight ratio of the hexadecyl sodium sulfonate to the dodecyl benzene sulfonate is controlled to be (2-4): 1, simultaneously controlling the weight ratio of zinc nitrate to sodium dodecyl benzene sulfonate to be (100-130): 1, the heat conductivity of the fabric can be reduced while the waterproofness and the ultraviolet resistance of the fabric are improved. Probably, when the outer-layer fabric is treated by adopting the organic silicon plasma, under a specific treatment condition, a certain degree of etching action can be generated on the surface of the fiber to form pores and pits; in the process of preparing the modified nano zinc oxide, when sodium hexadecyl sulfonate and sodium dodecyl benzene sulfonate are selected, anionic groups in the sodium hexadecyl sulfonate and the sodium dodecyl benzene sulfonate follow Zn⁺The modified nano zinc oxide particles are combined together to be coated on the surfaces of the particles, and meanwhile, the introduction of the benzene ring increases the steric hindrance effect, so that the entanglement of long chains of the sodium hexadecyl sulfonate is avoided, and the coating film has enough strength, thereby effectively regulating and controlling the particle size of the modified nano zinc oxide particles. Therefore, in the ultraviolet ray-proof immersion treatment, pores and pits are formed in advance by the treatment with the silicone plasma, and the macromolecular chains on the surface layer of the fiber are cut to modify the nano-oxidationThe surface of zinc particle has hydrophobic long chain for modified nanometer zinc oxide particle can adsorb on hole and pit rapidly, and because the mutual entanglement between the long chain, make modified nanometer zinc oxide more firm with the combination of hole, pit, can play the closure effect to those holes and pits rather than the particle size, make the content of quiescent air in the surface fabric increase, finely divide the air simultaneously, the convection current of air has been inhibited, thereby the heat conductivity of surface fabric has been reduced.

Intermediate layer

In a preferred embodiment, the thickness of the intermediate layer is 0.7 to 0.9 mm.

The thickness of the middle layer fabric is measured according to the national standard GB/T3820 1997 determination of the thickness of textiles and textile products.

In a more preferred embodiment, the intermediate layer according to the invention has a thickness of 0.8 mm.

In a preferred embodiment, the intermediate layer of the present invention is blended from acrylic fiber and hemp fiber.

The acrylic fiber is a fiber which is obtained by copolymerizing acrylonitrile serving as a main monomer (the content is more than 85%) and a small amount of other monomers and spinning. It is mainly characterized by that its appearance, hand feeling, elasticity and heat-insulating property are similar to those of wool, so that it is called "synthetic wool". The acrylic fiber has wide application, rich raw materials and fast development speed, is one of three synthetic fibers at present, and has the output second to that of terylene and nylon.

The macromolecule of the acrylon is in irregular spiral conformation, does not have strict crystal region, and belongs to a quasicrystal structure. Pure polyacrylonitrile can form a good crystalline structure, cyano groups with strong molecular lateral action form stable interaction and arrangement, so that fibers become brittle and hard, the dyeing property is poor, and a second monomer and a third monomer must be added. The macromolecular structure of the material is softened by adding the second monomer, and the axial ordering of the molecules and the lateral ordering among the molecules are weakened, so that the elasticity and the hand feeling of the material are improved; about 1% of a third monomer is added to improve the dyeability of the fiber. The acrylic fibers have unsmooth surfaces and bark-shaped groove and groove channels. The acrylic fiber has certain micropores inside, the section is basically circular or waist-circular, and the section is different according to different spinning methods. The strength of the acrylic fiber is 1.76-3.08cN/dex, the elongation at break is 25% -46%, and the elongation elasticity is similar to that of wool. The acrylic fiber has an insignificant melting point, does not undergo thermal decomposition or discoloration at 200 ℃ but begins to soften and approaches the decomposition point at 300 ℃. The acrylic fiber has particularly good sunlight resistance and weather resistance, and the strength loss is 10 to 25 percent after being exposed to the sun for 800 hours. The moisture regain of the acrylic fiber under the standard atmospheric condition is 2%. The acrylic fiber is resistant to worm-eating and mildew, and has good stability to common chemicals.

The fibrilia of the invention refers to fibers obtained from various bast plants, including bast fibers of annual or perennial herbaceous dicotyledonous plant cortex and leaf fibers of monocotyledonous plants. Bast fiber crops mainly include ramie, jute, ramie, hemp, flax, kendir, kenaf and the like. The basic chemical components of fibrilia are cellulose, and other non-fibrous substances (collectively called "gums") such as pectic substances, hemicellulose, lignin, fatty waxes, and the like, which are associated with cellulose. To remove the usable fiber, it is first separated from the gums (known as degumming). The content of cellulose in the chemical components of various fibrilia is about 75 percent, and the proportion of the content of the cellulose in the chemical components of the fibrilia is similar to that of the content of the fiber in the silk fiber.

The fibrilia of the invention is basically characterized in that: the discrete fiber is characterized in that except the ramie fiber is long fiber, other hemp fibers are short fibers; the shape characteristics of the fiber section, single fibers of all bast fibers are single cells, the shape is slender, two ends are closed, the bast fibers are provided with cells, the thickness and the length of the wrapping wall are different due to different varieties and maturity, the sections are mostly elliptical or polygonal, the bast fibers are in a laminated structure in the radial direction, and the orientation degree and the crystallinity degree are higher than those of cotton fibers, so that the strength of the hemp fibers is high and the elongation is small; the high-strength low-elongation fiber is characterized in that the fibrilia is a high-strength low-elongation fiber, the breaking strength of the fibrilia is 5.0-7.0 cN/dtex, mainly because the fibrilia is mainly bast fiber, the bast fiber is a basic skeleton of a plant, the crystallinity and the orientation degree are higher, and the fibril is distributed in a layered structure along the radial direction of the fiber.

In a preferred embodiment, the blending ratio of the acrylic fiber and the fibrilia is (1-5): 1.

in a more preferred embodiment, the blending ratio of the acrylic fiber and the fibrilia is (2-4): 1.

in a most preferred embodiment, the blend ratio of acrylic fiber and hemp fiber in the invention is 3: 1.

in a preferred embodiment, the intermediate layer according to the invention is subjected to a pore treatment and an oxygen plasma treatment.

Treatment of pores

The pore treatment is to construct a microporous structure, so that the fabric does not allow liquid such as water drops to permeate, and meanwhile, the free permeation of water vapor is ensured, so that the textile fabric is endowed with a waterproof and moisture permeable function.

The commonly used treating agents for the construction of the microporous structure include: polyacrylate (PA), polyurethane resin (PU), silicone, Polytetrafluoroethylene (PTFE), polyvinyl chloride resin (PVC), natural rubber, synthetic rubber, and the like. With the pursuit of consumers for the environmental protection, comfort, aesthetic property and functionality of textiles, the application of polyvinyl chloride resin, natural rubber and synthetic rubber to the textiles is less and less; the organic silicon and the polytetrafluoroethylene are mainly used for some high-grade coating products due to higher price; current textile pore treatment applications are therefore predominantly polyacrylate and polyurethane resins.

In a preferred embodiment, the treating agent in the pore treatment according to the present invention comprises a modified polyurethane resin.

(modified polyurethane resin)

The polyurethane resin is a polymer with a main chain having a repeated-NHCOO-structural unit, wherein an isocyanate group is used as a hard segment to control wear resistance, waterproofness, strength and the like, and an ester group or an ether group is used as a soft segment to control elasticity, low-temperature performance, hydrolysis resistance and the like of the polyurethane resin; the water pressure resistance and tensile strength generally decrease with the increase of the molecular weight of the hard segment, and the moisture permeability and the elongation at break generally increase with the increase of the molecular weight of the soft segment.

The mechanism of the polyurethane of the invention which can exert the waterproof and moisture permeable functions can be divided into microporous polyurethane, hydrophilic polyurethane and shape memory polyurethane.

In the microporous type, the diameter of the pores is very small, only 10-50 mu m, the diameter is between the water vapor with the diameter of 0.0004 mu m and the water drop with the diameter of about 100-300 mu m, the water vapor can permeate the microporous film, and the water drop can not permeate, so that the waterproof and moisture permeable effects are achieved.

In the hydrophilic type, the surface and the body are both uniform and compact structures, the waterproofness is caused by the continuity of materials and larger surface tension, the moisture permeability is determined by hydrophilic groups in polymers, the hydrophilic type is realized by a complex molecular diffusion mechanism (according to an adsorption-diffusion-desorption mode), and the micro-phase separation structure of polyurethane provides possibility for the complex molecular diffusion. Water molecules and hydrophilic groups in the polyurethane material form hydrogen bonds, and are transmitted along molecular chain gaps, so that moisture is absorbed from the high-humidity side and is transmitted to the low-humidity side, and the moisture permeability is realized, but the moisture permeability is generally poorer than that of a microporous structure.

In the shape memory polyurethane, the glass transition temperature (called memory temperature) of the material is controlled through molecular design, and the moisture permeability of the material is obviously different above and below the memory temperature. When the polymer is heated to exceed the memory temperature, micro-Brownian motion becomes very active, so that the intermolecular distance is increased, water vapor molecules can easily penetrate through the polymer film, but the intramolecular motion is not so large as to allow a large number of water drops to pass through, and therefore, the functions of water resistance and moisture permeation can be simultaneously achieved.

In a preferred embodiment, the mechanism of the waterproof and moisture permeable functions of the invention is mainly microporous, and the waterproof and moisture permeable functions are realized by constructing a plurality of pore structures.

In a preferred embodiment, the raw materials for preparing the modified polyurethane of the invention comprise polytetrahydrofuran diol, adipic acid polyester and diphenylmethane diisocyanate.

In a preferred embodiment, the preparation process of the modified polyurethane of the present invention comprises:

a) adding polytetrahydrofuran diol, adipic acid polyester and diphenylmethane diisocyanate into a three-necked bottle provided with a stirrer, a thermometer and nitrogen protection, uniformly mixing, heating to 80-90 ℃, and reacting for 1-2 h to obtain a mixture;

b) cooling the mixture to 50-60 ℃, adding a certain amount of dimethylolpropionic acid, and reacting for 1-2 h to obtain a prepolymer;

c) adding diethylene glycol and a proper amount of acetone into the prepolymer, reacting until the content of the isocyanic acid radical is not changed, cooling to 35-45 ℃, and removing the acetone through reduced pressure distillation to obtain the modified polyurethane resin.

The CAS of the polytetrahydrofurandiol obtained in the step a) is 25190-06-1; CAS for adipic acid polyester is 30376-45-5; the CAS number for diphenylmethane diisocyanate is 101-68-8.

The weight ratio of the polytetrahydrofuran diol, the adipic acid polyester and the diphenylmethane diisocyanate in the step a) is (1-3): 1: 1.

the mixing mode in the step a) is mechanical stirring, the stirring speed is 400-500 r/min, and the stirring time is 8-15 min.

The weight ratio of the diphenylmethane diisocyanate in the step a) to the dimethylolpropionic acid in the step b) is (4-10): 1.

the weight ratio of the dimethylolpropionic acid in the step b) to the diethylene glycol and acetone in the step c) is (1-3): 1: (3-10).

The method for measuring the content of the isocyanic acid radical in the step c) comprises the following steps: according to GB/T3186-1988, the content of isocyanic acid radical in the reaction process is determined by a di-n-butylamine-hydrochloric acid titration method after sampling.

In a preferred embodiment, the intermediate layer according to the invention is apertured by means of an impregnation process.

In a preferred embodiment, the pore treatment of the present invention comprises the following impregnation process: modified polyurethane resin, toluene and trimethylolpropane are mixed according to the weight ratio of (6-17): (3-8): 1, and uniformly mixing to prepare a treating agent; and (3) soaking the fabric of the middle layer in the treating agent for 5-15 min, and drying at 35-45 ℃ after soaking.

In a preferred embodiment, the intermediate layer of the present invention is subjected to an oxygen plasma treatment after the pore treatment.

Oxygen plasma treatment

In a more preferred embodiment, the low temperature plasma gas of the present invention is oxygen.

In a preferred embodiment, the oxygen plasma treatment process of the present invention is: connecting a high-purity oxygen cylinder to a plasma vacuum cavity for later use; putting the fabric into a low-temperature plasma vacuum chamber, vacuumizing, opening a switch to introduce standby gas when the pressure is reduced to 8-12 Pa, adjusting and controlling the pressure to a set value of 10-20 Pa after gas circulation, then opening a plasma radio frequency discharge button, setting the gas flow to be 1-3L/min, closing a gas valve after treating for a certain time, introducing air to normal pressure, and taking out a sample.

In a more preferred embodiment, the oxygen plasma treatment conditions of the present invention are: the discharge voltage is 3-5 kV, and the discharge time is 60-80 s.

In a most preferred embodiment, the oxygen plasma treatment conditions of the present invention are: discharge voltage 4kV, discharge time 70 s.

In a preferred embodiment, the volume ratio of oxygen to silicone gas in the present invention is 1: (4-6).

The regulation and control of the volumes of the oxygen and the organosilicon gases are realized by controlling the gas flow and the discharge time.

The gas flow rate in the invention refers to the volume value of gas passing through in unit time.

The inventors found that when the outer layer fabric was treated with a low temperature silicone plasma and the middle layer fabric was treated with a low temperature oxygen plasma, and when the volume ratio of oxygen to silicone gas was 1: (4-6), the water resistance of the fabric can be improved. However, the inventors have found that when the volume ratio of oxygen to silicone gas is not properly selected, the water resistance of the fabric is rather lowered. Probably, when the volume ratio of oxygen to organic silicon gas is too high, hydrophilic groups introduced on the fiber surface of the fabric in the middle layer are too much, and hydrophobic substances on the fiber surface of the fabric in the outer layer are too little, so that the water resistance of the fabric is reduced; and when the volume ratio of oxygen and organosilicon gas is low excessively, on the one hand, the etching on the surface of the outer fabric fiber is too strong, so that the formed pores and pits are large, and the waterproofness of the fabric can be reduced, and on the other hand, because the hydrophilic groups on the surface of the middle layer fabric fiber are too few, the adsorption of the middle layer fabric fiber on the liquid water drops in the inner layer fabric is too small, and the moisture permeability of the fabric can be reduced.

In a more preferred embodiment, the volume ratio of oxygen to silicone gas in the present invention is 1: 5.

inner layer

In a preferred embodiment, the thickness of the inner layer is 0.1-0.5 mm.

The thickness of the lining fabric is measured according to the national standard GB/T3820 1997 determination of the thickness of textiles and textile products.

In a more preferred embodiment, the thickness of the inner layer is 0.2 to 0.4 mm.

In a most preferred embodiment, the inner layer of the present invention has a thickness of 0.3 mm.

In a preferred embodiment, the lining layer is formed by blending cotton fibers and modal fibers.

The cotton fiber is the fiber coated on the seeds of malvaceae cotton plants, also called cotton, short for cotton, the cotton fiber product has good moisture absorption and air permeability, is soft and warm, most of the cotton is annual plants, and is developed by epidermal cells bred on the cotton seeds. Cotton fiber is the main raw material of textile industry in China, and the cotton fiber occupies an important position in textile fiber.

The main component of the cotton fiber is cellulose, the polymerization degree ranges from 6000 to 11000, the cotton fiber is a porous substance, and a plurality of hydrophilic groups (-OH) exist on cellulose macromolecules, so the moisture absorption of the cotton fiber is good, and the moisture regain of the cotton fiber can reach about 8.5% under the common atmospheric condition. When the mature cotton fiber is observed in a microscope, many spiral twists can be observed on the flat ribbon fiber, and the twists are naturally formed in the growth process of the cotton fiber and are called natural twists. The natural twist enables the cotton fiber to have good cohesion performance and spinnability, and the more the natural twist, the better the quality of the cotton fiber.

The modal fiber is a cellulose fiber, belongs to the same cellulose fiber as artificial cotton, and is a pure artificial fiber. The modal product is prepared by preparing wood pulp from shrub forest produced in Europe and then carrying out a special spinning process, and is mostly used for producing underwear at present because the modal product has the characteristics of good softness and excellent hygroscopicity but poor fabric stiffness. The Modal woven fabric can also show the weavability in the weaving process, can be blended with other fibers and can achieve good effect, and the blended fabric obtained by blending with the cotton fibers can lead the cotton fibers to be more smooth and improve the appearance of the fabric.

The modal fiber is soft, smooth, bright in color, particularly soft in fabric hand feeling, bright in cloth cover luster, better in drapability than existing cotton, polyester and rayon, glossy and hand feeling, and is a natural mercerized fabric; the composite fiber has the strength and toughness of the synthetic fiber, the dry strength is 3.56cn/tex, the wet strength is 2.56cn/tex, the strength is higher than that of pure cotton and polyester cotton, and the phenomenon of end breakage in processing is reduced; the moisture absorption capacity is higher than that of cotton fiber by 50 percent, so that the modal fiber fabric can keep dry and breathable, is an ideal close-fitting fabric and a health-care clothing product, and is beneficial to the physiological circulation and health of human bodies; compared with cotton fiber, the fabric has good shape and size stability, so that the fabric has natural wrinkle resistance and non-ironing property, and is more convenient and natural to wear.

In a preferred embodiment, the blending ratio of the cotton fibers and the modal fibers is (1-3): 1.

in a more preferred embodiment, the blend ratio of the cotton fibers and the modal fibers according to the invention is 2: 1.

the polyurethane consists of soft and hard sections, and the compatibility of the soft and hard sections can be adjusted by adjusting the components and the proportion of the soft section and the hard section, so that the phase separation of different degrees is realized, and the microporous structures with different sizes can be obtained. The inventor selects polytetrahydrofuran diol and adipic acid polyester to provide a soft segment part, adopts diphenylmethane diisocyanate to provide a hard segment part, and forms a certain amount of micropore structures in the middle layer fabric through screening and controlling the proportion conditions. In addition, the surface layer of the fiber in the middle layer fabric is subjected to crosslinking and molecular chain cutting due to the treatment of the low-temperature oxygen plasma, so that chemical active points are generated, and the oxygen plasma can form hydrophilic groups on the surface of the fiber, so that the adsorption of liquid water drops is facilitated; meanwhile, due to the etching effect of the low-temperature oxygen plasma, a large number of pores and pits are generated on the surface of the fiber, so that a channel is widened for the propagation of liquid water drops. Therefore, when the thin lining fabric contacts with liquid water drops, the liquid water drops are transmitted to the middle layer fabric through the water absorption effect, the hydrophilic groups on the fiber surface of the middle layer fabric can absorb the liquid water drops and permeate into the pores and the pits, the liquid water drops have high energy per se and are limited by the volumes of the pores and the pits, so that the liquid water drops are cracked into smaller liquid drops and can permeate into the microporous structure, the water vapor can be further converted into the water vapor in the microporous structure and can permeate into the lower outer layer fabric, and the water vapor can be distributed out through the small gaps among the fibers, so that the moisture permeability of the fabric is improved.

Due to the construction of pores, pits and a microporous structure, although the waterproof and moisture permeability of the fabric is improved, under dry conditions, the inventor is concerned about reducing the windproof performance of the fabric. However, the inventor of the present application has unexpectedly found that when the impregnation liquid containing the modified polyurethane resin is used to perform the pore treatment on the middle layer fabric, and the weight ratio of the polytetrahydrofuran diol, the adipic acid polyester and the diphenylmethane diisocyanate is controlled to be (1-3): 1: 1, performing oxygen plasma treatment, controlling the discharge voltage to be 3-5 kV, the discharge time to be 60-80 s, and controlling the blending ratio of the acrylic fibers and the fibrilia to be (2-4): 1, when the thickness of the inner layer is 0.2-0.4 mm, the windproof performance of the fabric can be improved. Probably because when polytetrahydrofuran diol and adipic acid polyester are selected as the soft segment of the modified polyurethane, under the condition of a specific proportion, the content of a polar bond in the soft segment is moderate, so that certain intermolecular force is formed between the hard segment and the soft segment, the phase separation in the hard segment is inhibited, and the size of a microporous structure is limited; in the oxygen plasma treatment, pores and pits having a certain size can be formed under specific treatment conditions. In addition, because the outer layer fabric is subjected to waterproof treatment, liquid water drops are difficult to directly contact fabric fibers, so that the shrinkage of the fabric is small in the drying process; although the cotton fibers and the modal fibers in the lining fabric shrink in the drying process, when the thickness of the lining is controlled to be 0.2-0.4 mm by the inventor in the application, the influence of the shrinkage of the lining fabric fibers on the whole fabric is not obvious; and the fibrilia in the middle layer fabric can shrink greatly in the drying process, and the inventor adopts the acrylic fiber and the fibrilia for blending, and controls the blending ratio of the acrylic fiber and the fibrilia to be (2-4): 1, the fibers of the fabric in the middle layer shrink to a certain extent, and pores, pits and micropores in the fabric can be closed through the shrinking action in the drying process, so that the wind resistance of the fabric is improved; under the condition of liquid existence, the fiber absorbs water to expand, and the closed pores, pits and micropores are opened again to play the waterproof and moisture permeable functions.

The invention provides a preparation method of a waterproof and ultraviolet-proof fabric in a second aspect, which at least comprises the following steps: and (3) bonding the inner layer, the middle layer and the outer layer through a bonding agent to obtain the waterproof and ultraviolet-proof textile fabric.

In a preferred embodiment, the adhesive of the present invention is a hot melt adhesive stick.

The present invention will now be described in detail by way of examples, and the starting materials used are commercially available unless otherwise specified.

Examples

Example 1

Embodiment 1 provides a waterproof ultraviolet protection textile fabric, including nexine, intermediate level and skin.

The thicknesses of the outer layer fabric, the middle layer fabric and the inner layer fabric are measured according to the national standard GB/T3820-1997 for measuring the thicknesses of textiles and textile products.

The thickness of the outer layer is 0.7 mm.

The outer layer is formed by blending polyester and fluorine, and the blending ratio is 3: 1.

the outer layer is subjected to organosilicon plasma treatment and ultraviolet-proof treatment.

The organosilicon plasma treatment process comprises the following steps: connecting the conical flask filled with the 2,4,6, 8-tetrabutyl-2, 4,6, 8-tetramethylcyclotetrasiloxane to a plasma vacuum chamber, and heating to 85 ℃ for later use; putting the fabric into a low-temperature plasma vacuum chamber, vacuumizing, opening a switch to introduce standby gas when the pressure is reduced to 10Pa, adjusting and controlling the pressure to a set value of 15Pa after gas circulation, then opening a plasma radio frequency discharge button, setting the gas flow to be 14L/min, closing a gas valve after treating for a certain time, introducing air to normal pressure, and taking out a sample.

The CAS of the 2,4,6, 8-tetrabutyl-2, 4,6, 8-tetramethylcyclotetrasiloxane is 14685-29-1.

The conditions of the organosilicon plasma treatment are as follows: discharge voltage 3kV, discharge time 50 s.

The outer layer is subjected to ultraviolet-proof treatment after being subjected to organic silicon plasma treatment.

The treating agent in the ultraviolet-proof treatment comprises modified nano zinc oxide.

The preparation method of the modified nano zinc oxide comprises the following steps:

1) putting zinc nitrate and sodium hydroxide into a mortar according to the mass ratio of 1: 2, and fully grinding for 10 min;

2) adding sodium hexadecyl sulfonate and sodium dodecyl benzene sulfonate into the substances obtained in the step 1), and fully grinding for 40 min;

3) washing and filtering the substance obtained in the step 2), and drying at 85 ℃ for 2.5h to obtain modified Zn (OH)₂；

4) The resulting modified Zn (OH)₂Roasting for 3h, and controlling the roasting temperature at 350 ℃ to obtain the modified nano zinc oxide powder.

The weight ratio of the zinc nitrate in the step 1) to the sodium dodecyl benzene sulfonate in the step 2) is 115: 1.

the sodium hexadecylsulfonate CAS in the step 2) is CAS: 15015-81-3; the CAS of the sodium dodecyl benzene sulfonate is 25155-30-0.

The weight ratio of the sodium hexadecyl sulfonate to the sodium dodecyl benzene sulfonate in the step 2) is 3: 1.

the ultraviolet-proof treatment adopts an immersion method.

The dipping treatment step of the ultraviolet-proof treatment comprises the following steps:

III) soaking the outer layer fabric in the treating agent for 4.5h, and drying at 130 ℃ after soaking is finished.

The weight ratio of the modified nano zinc oxide and water in the step I) is 1: 4.

the dispersion mode in the step I) is mechanical stirring, the stirring speed is 600r/min, and the stirring time is 10 min.

The weight ratio of the modified nano zinc oxide in the step I) to the water-based rosin resin emulsion in the step II) is 1: 3.

the weight ratio of the water-based rosin resin emulsion to the amino silicon emulsion in the step II) is 1: 2.

the purchasing merchant of the water-based rosin resin emulsion is Shanghai Sangjing chemical industry Co., Ltd, and the model is 780.

The buying trade company of the amino silicon emulsion is Tantan chemical technology (Shanghai) Co., Ltd, and the model is Tt-F430.

The mixing mode in the step II) is mechanical stirring, the stirring speed is 750r/min, and the stirring time is 15 min.

The thickness of the intermediate layer is 0.8 mm.

The middle layer is formed by blending acrylic fibers and fibrilia, and the blending ratio is 3: 1.

the intermediate layer is subjected to a pore treatment and an oxygen plasma treatment.

The treating agent in the pore treatment of the invention comprises modified polyurethane resin.

The preparation raw materials of the modified polyurethane comprise polytetrahydrofuran diol, adipic acid polyester and diphenylmethane diisocyanate.

The preparation method of the modified polyurethane comprises the following steps:

a) adding polytetrahydrofuran diol, adipic acid polyester and diphenylmethane diisocyanate into a three-necked bottle provided with a stirrer, a thermometer and nitrogen protection, uniformly mixing, heating to 85 ℃, and reacting for 1.5h to obtain a mixture;

b) cooling the mixture to 55 ℃, adding a certain amount of dimethylolpropionic acid, and reacting for 1.5h to obtain a prepolymer;

c) adding diethylene glycol and a proper amount of acetone into the prepolymer, reacting until the content of the isocyanic acid radical is not changed, cooling to 40 ℃, and removing the acetone by reduced pressure distillation to obtain the modified polyurethane resin.

The weight ratio of polytetrahydrofuran diol, adipic acid polyester and diphenylmethane diisocyanate in step a) is 2: 1: 1.

the mixing mode of the step a) is mechanical stirring, the stirring speed is 450r/min, and the stirring time is 10 min.

The weight ratio of the diphenylmethane diisocyanate of step a) to the dimethylolpropionic acid of step b) is 7: 1.

the weight ratio of the dimethylolpropionic acid in the step b) to the diethylene glycol and acetone in the step c) is 2: 1: 7.

The intermediate layer is subjected to pore treatment by an impregnation method.

The impregnation treatment process of the pore treatment comprises the following steps: modified polyurethane resin, toluene and trimethylolpropane are mixed according to the weight ratio of 14: 6: 1, and uniformly mixing to prepare a treating agent; and (3) soaking the fabric of the middle layer in the treating agent for 10min, and drying at 40 ℃ after soaking.

The intermediate layer is subjected to oxygen plasma treatment after the pore treatment.

The oxygen plasma treatment process comprises the following steps: connecting a high-purity oxygen cylinder to a plasma vacuum cavity for later use; putting the fabric into a low-temperature plasma vacuum chamber, vacuumizing, opening a switch to introduce standby gas when the pressure is reduced to 10Pa, adjusting and controlling the pressure to a set value of 15Pa after gas circulation, then opening a plasma radio frequency discharge button, setting the gas flow to be 2L/min, closing a gas valve after treating for a certain time, introducing air to normal pressure, and taking out a sample.

The conditions of the oxygen plasma treatment are as follows: discharge voltage 4kV, discharge time 70 s.

The volume ratio of oxygen to organic silicon gas is 1: 5.

the thickness of the inner layer is 0.3 mm.

The inner layer is formed by blending cotton fibers and modal fibers, and the blending ratio is 2: 1.

the preparation method of the waterproof ultraviolet-proof textile fabric comprises the following steps: and (3) bonding the inner layer, the middle layer and the outer layer through a bonding agent to obtain the waterproof and ultraviolet-proof textile fabric.

The adhesive is a hot melt adhesive rod.

Example 2

Embodiment 2 provides a waterproof ultraviolet protection textile fabric, including nexine, intermediate level and skin.

The thickness of the outer, middle and inner fabrics was measured in the same manner as in example 1.

The thickness of the outer layer is 0.6 mm.

The outer layer is formed by blending polyester and fluorine, and the blending ratio is 2: 1.

The organosilicon plasma treatment and the UV protection treatment were the same as in example 1.

The thickness of the intermediate layer is 0.7 mm.

The middle layer is formed by blending acrylic fibers and fibrilia, and the blending ratio is 2: 1.

The process of the invention for pore treatment and oxygen plasma treatment was the same as in example 1.

The thickness of the inner layer is 0.2 mm.

The inner layer is formed by blending cotton fibers and modal fibers, and the blending ratio is 1: 1.

the preparation method of the waterproof and ultraviolet-proof textile fabric is the same as that of the example 1.

Example 3

Embodiment 3 provides a waterproof ultraviolet protection textile fabric, including nexine, intermediate level and skin.

The thickness of the outer layer is 0.8 mm.

The outer layer is formed by blending polyester and fluorine, and the blending ratio is 5: 1.

The thickness of the intermediate layer is 0.9 mm.

The middle layer is formed by blending acrylic fibers and fibrilia, and the blending ratio is 4: 1.

The thickness of the inner layer is 0.4 mm.

The inner layer is formed by blending cotton fibers and modal fibers, and the blending ratio is 3: 1.

Example 4

Example 4 provides a waterproof and ultraviolet-proof textile fabric, which is specifically implemented in the same manner as in example 1, except that the conditions of the silicone plasma treatment are replaced by: the discharge voltage was 0.5kV and the discharge time was 30 s.

Example 5

Example 5 provides a waterproof and ultraviolet-proof textile fabric, which is specifically implemented in the same manner as in example 1, except that the conditions of the silicone plasma treatment are replaced by: discharge voltage 6kV and discharge time 70 s.

Example 6

Example 6 provides a waterproof and ultraviolet-proof textile fabric, which is the same as example 1 in the specific implementation manner, except that the content of sodium dodecylbenzenesulfonate is replaced with 0.

Example 7

Example 7 provides a waterproof and ultraviolet-proof textile fabric, which is the same as example 1 in the specific implementation manner, except that sodium hexadecylbenzene sulfonate is replaced by sodium n-undecyl sulfonate with CAS of 5838-34-6.

Example 8

Embodiment 8 provides a waterproof and ultraviolet-proof textile fabric, which is the same as embodiment 1 in specific implementation, except that the weight ratio of sodium hexadecyl sulfonate to sodium dodecyl benzene sulfonate is replaced by 1: 2.

example 9

Embodiment 9 provides a waterproof and ultraviolet-proof textile fabric, which is the same as embodiment 1 in specific implementation, except that the weight ratio of sodium hexadecyl sulfonate to sodium dodecyl benzene sulfonate is replaced by 6: 1.

example 10

Example 10 provides a waterproof ultraviolet-proof textile fabric, which is the same as example 1 in the specific implementation manner, except that the weight ratio of zinc nitrate to sodium dodecylbenzenesulfonate is replaced with 140: 1.

example 11

Embodiment 11 provides a waterproof and ultraviolet-proof textile fabric, which is the same as embodiment 1 in specific implementation, except that the weight ratio of zinc nitrate to sodium dodecylbenzenesulfonate is replaced with 90: 1.

example 12

Embodiment 12 provides a waterproof and ultraviolet-proof textile fabric, which is prepared in the same manner as in embodiment 1, except that the weight ratio of polytetrahydrofuran diol to adipic acid polyester is replaced by 1: 3.

example 13

Example 13 provides a waterproof and ultraviolet-proof textile fabric, which is specifically implemented in the same manner as in example 1, except that the weight ratio of polytetrahydrofuran diol to adipic acid polyester is replaced by 5: 1.

example 14

Example 14 provides a waterproof and ultraviolet-proof textile fabric, which is the same as in example 1 except that the weight ratio of polytetrahydrofuran diol, adipic acid polyester and diphenylmethane diisocyanate is replaced by 4: 2: 1.

example 15

Example 15 provides a waterproof and ultraviolet-proof textile fabric, which is the same as example 1 in the specific embodiment except that the weight ratio of polytetrahydrofuran diol, adipic acid polyester and diphenylmethane diisocyanate is replaced by 2: 1: 6.

example 16

Example 16 provides a waterproof and ultraviolet-proof textile fabric, which is specifically implemented in the same manner as in example 1, except that the oxygen plasma treatment conditions are replaced with: discharge voltage 1kV and discharge time 40 s.

Example 17

Example 17 provides a waterproof and ultraviolet-proof textile fabric, which is specifically implemented in the same manner as in example 1, except that the oxygen plasma treatment conditions are replaced with: discharge voltage 7kV and discharge time 100 s.

Example 18

Embodiment 18 provides a waterproof and ultraviolet-proof textile fabric, which is the same as embodiment 1 in the specific implementation manner, and is characterized in that the blending ratio of acrylic fibers and fibrilia in the middle layer is replaced by 6: 1.

example 19

Embodiment 19 provides a waterproof and ultraviolet-proof textile fabric, which is the same as embodiment 1 in the specific implementation manner, and is different in that the blending ratio of acrylic fibers and fibrilia in the middle layer is replaced by 1: 2.

example 20

Example 20 provides a waterproof and ultraviolet-proof textile fabric, which is the same as example 1 in the specific embodiment except that the thickness of the inner layer is replaced with 0.1 mm.

Example 21

Example 21 provides a waterproof and ultraviolet-proof textile fabric, which is the same as in example 1 except that the thickness of the inner layer is replaced with 0.6 mm.

Example 22

Example 22 provides a waterproof and ultraviolet-proof textile fabric, which is implemented in the same manner as in example 1, except that the gas flow rate of the oxygen plasma treatment is replaced by 5L/min.

Example 23

Example 23 provides a waterproof and ultraviolet-proof textile fabric, which is the same as example 1 in the specific embodiment except that the gas flow rate of the silicone plasma is changed to 28L/min.

Evaluation of Performance

1. Water repellency: the water repellency rating is determined and assessed by reference to the standard GB/T14577-1993 Bundis door rain test for Fabric Water repellency. The relationship between the water repellency grade value and the wetting condition of the showered surface of the corresponding fabric is as follows: 5, quickly dripping small water drops; 4, forming large water drops; 3, dipping a part of samples with water drops; stage 2, partial wetting; level 1, whole surface wetting.

2. Ultraviolet resistance: and the ultraviolet resistance performance is tested and evaluated according to the standard GB/T18830-2009 evaluation of ultraviolet resistance performance of textiles. The ultraviolet protection coefficient UPF is a more index for evaluating the ultraviolet protection performance of the fabric at home and abroad at present, represents the ultraviolet protection capability of the fabric, and is the ratio of the average radiation quantity of ultraviolet to unprotected skin to the ultraviolet radiation energy after the tested fabric is shielded. The method for judging the uvioresistant performance of the fabric comprises the following steps: UPF is less than or equal to 14, poor; UPF is not less than 15 and not more than 24, preferably; UPF is more than or equal to 25 and less than or equal to 39, preferably; UPF is 40 or more, very good.

3. Thermal conductivity: the thermal conductivity is tested and evaluated according to the standard GB/T11048 and 1989, test method for thermal insulation performance of textiles. The heat transfer coefficient refers to the heat flow per unit area when the temperature difference on the surface of the textile is 1 ℃, and the unit is W/m²Temperature. The lower the heat transfer coefficient is, the better the heat preservation performance of the fabric is.

The calculation formula of the heat transfer coefficient is as follows: u shape₂＝U_bp×U₁/(U_bp-U₁)；

In the formula of U₂: heat transfer coefficient of sample, W/m²·℃；U_bp: test board transmission without fabricThermal coefficient, W/m²·℃；U₁: test plate Heat transfer coefficient with Fabric, W/m²·℃。

4. Moisture permeability: the moisture permeability of the fabric is tested and calculated by referring to a method A wet absorption method in GB/T12704 and 1991 moisture permeability cup method for measuring the moisture permeability of the fabric. The larger the moisture permeability, the better the moisture permeability of the fabric.

Calculation formula of moisture permeability: WVT ═ (24 × Δ m)/(s × t);

in the formula, WVT: moisture permeability per square meter per day (24h), g/m²24 h; Δ m: the difference between two weighing times, g, of the same test assembly; s: test area of Fabric, m²(ii) a t: test time, h.

5. Wind resistance: the windbreak test and assessment is carried out according to the standard GB/T5453-1997 determination of the air permeability of textile fabrics. Air permeability refers to the rate at which gas passes perpendicularly through the sample, expressed as R, under specified test area, pressure and time conditions. The smaller the R value is, the better the windproof performance of the fabric is. The method for judging the windproof performance comprises the following steps: r is less than or equal to 30, preferably; r is more than or equal to 31 and less than or equal to 60, and is general; r is greater than or equal to 61, poor.

Table 1 characterization of performance tests

As can be seen from table 1, the waterproof and ultraviolet-proof textile fabric of the present invention can satisfy the requirements of people for the waterproof property, moisture permeability, ultraviolet resistance, wind resistance and heat retention of the fabric.

The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims

1. A waterproof and ultraviolet-proof textile fabric is characterized by comprising an outer layer, a middle layer and an inner layer;

the middle layer is formed by blending acrylic fibers and fibrilia;

the blending ratio of the acrylic fibers to the fibrilia is (1-5): 1;

the thickness of the inner layer is 0.1-0.5 mm.

2. The waterproof ultraviolet-proof textile fabric as claimed in claim 1, wherein the conditions of the organosilicon plasma treatment are as follows: the discharge voltage is 2-4 kV, and the discharge time is 45-55 s.

3. The waterproof ultraviolet-proof textile fabric as claimed in claim 1, wherein the treatment agent in the ultraviolet-proof treatment comprises modified nano zinc oxide.

4. The waterproof ultraviolet-proof textile fabric according to claim 3, wherein the modified nano zinc oxide is prepared from alkyl sulfonate with 10-18 carbon atoms.

5. The waterproof ultraviolet-proof textile fabric according to claim 4, wherein the alkyl sulfonate with 10-18 carbon atoms is one or a combination of several of n-undecyl sodium sulfonate, dodecyl sodium sulfonate, tridecyl sodium sulfonate, hexadecyl sodium sulfonate, dodecyl benzene sodium sulfonate, tridecyl benzene sodium sulfonate, tetradecyl benzene sodium sulfonate and octadecyl benzene sodium sulfonate.

6. The waterproof ultraviolet-proof textile fabric as claimed in claim 1, wherein the treating agent in the pore treatment comprises a modified polyurethane resin.

7. The waterproof ultraviolet-proof textile fabric as claimed in claim 6, wherein the modified polyurethane resin is prepared from polytetrahydrofuran diol, adipic acid polyester and diphenylmethane diisocyanate.

8. The waterproof ultraviolet-proof textile fabric according to claim 1, wherein the oxygen plasma treatment conditions are as follows: the discharge voltage is 3-5 kV, and the discharge time is 60-80 s.

9. The waterproof ultraviolet-proof textile fabric as claimed in claim 1, wherein the volume ratio of oxygen to silicone gas is 1: (4-6).

10. The preparation method of the waterproof ultraviolet-proof textile fabric according to any one of claims 1 to 9, characterized by comprising at least the following steps: and (3) bonding the inner layer, the middle layer and the outer layer through a bonding agent to obtain the waterproof and ultraviolet-proof textile fabric.