WO2022111424A1

WO2022111424A1 - Fire-resistant nonwoven fabric

Info

Publication number: WO2022111424A1
Application number: PCT/CN2021/132208
Authority: WO
Inventors: 武庭轩; 高冬燕; 梶山宏史; 二宫有希; 原田大
Original assignee: 东丽纤维研究所（中国）有限公司
Priority date: 2020-11-24
Filing date: 2021-11-23
Publication date: 2022-06-02
Also published as: CN116615585A

Abstract

Disclosed is a fire-resistant nonwoven fabric. The nonwoven fabric contains a non-melting fiber A having a limiting oxygen index of 27% or more and a thermal decomposition temperature of 400 degrees or less, and a thermoplastic fiber B having a limiting oxygen index of 30% or more. The porosity of the nonwoven fabric is less than 98%. The fire-resistant nonwoven fabric of the present invention has good fire resistance and excellent flame-proof performance, is light weight and soft, has low thermal conductivity, and is applicable to battery upper covers, automobile interior decoration, buildings, and the like.

Description

A fire-proof flame-shielding non-woven fabric

technical field

The invention relates to a fireproof flame-shielding nonwoven fabric.

Background technique

Woven fabrics, knitted fabrics or non-woven fabrics made of natural fibers, cotton, linen, silk wool, synthetic fibers in chemical fibers such as polyester fibers, polyamide fibers, viscose fibers of regenerated fibers, and acetate fibers have no resistance. Inflammability, it is necessary to implement some kind of flame retardant modification treatment to obtain the flame retardant effect. For example, flame retardants are added to fibers or fabrics to impart flame retardant effects.

However, the flame retardant fiber products prepared by using flame retardant as a flame retardant modification method do not have a high flame retardant effect. However, it still has the phenomenon of high temperature shrinkage. The part that contacts the flame will melt to form a hole, and the flame will escape from the hole. In addition, for the flame-retardant textiles modified by padding and coating methods, the flame retardants are easy to fall off from the flame-retardant textiles, resulting in poor flame-retardant durability of the non-woven fabric.

For example, Chinese published patent CN101629335A discloses a kind of anti-ultraviolet, antibacterial, flame retardant polyester fiber and its preparation method and application. The melting temperature range of flame retardant polyester fiber is 255-280 ℃. The shrinkage of the fibers is unavoidable, so when the prepared fabric is placed above the flame, the fabric will also have holes due to shrinkage, and the flame will leak from the holes, thereby burning the upper layer of the material.

In addition, there are still cases where high carbon content fibers after heat treatment are used. However, when high carbon content fibers are subjected to long-term roasting and exposure to oxygen, an oxidative decomposition reaction will occur. It will completely decompose and disappear, and the flame retardant effect will naturally cease to exist.

For example, Chinese published patent CN108360147A discloses a method for preparing polyacrylonitrile pre-oxidized felt. Polyacrylonitrile is used as a raw material, and is treated in a high temperature furnace above 200 degrees to introduce oxygen atoms and promote cyclization reaction to obtain flatness High pre-oxygen fiber mat, it is used in the field of heat insulation and fire prevention. However, the thermal decomposition temperature of the pre-oxidized fiber in the air is about 500 ℃, and the temperature of the flame is generally above 500 ℃. When the pre-oxidized fiber mat is burned by the flame, the fiber will slowly decompose and become thinner, and finally completely disappear, thereby losing the effect of fire prevention.

Another example is Chinese published patent CN107636219A, which discloses a flame-blocking non-woven fabric. The flame-blocking non-woven fabric is formed by non-melting fibers A and thermoplastic fibers B with a limiting oxygen index greater than 25%. The non-melting fibers A are Refractory fiber or meta-aramid fiber, although the non-woven fabric has excellent flame blocking performance, the non-woven fabric has only one color of gray because of the fiber characteristics, and because the fiber used is still a polymer fiber, when burning After the burning temperature is too high, aerobic decomposition will still occur, and eventually the ability to block the flame will be lost.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a fireproof flame-shielding non-woven fabric with good flame retardancy, excellent flame resistance, light weight and softness, and low thermal conductivity.

The technical solution of the present invention is as follows: the fireproof flame-shielding non-woven fabric of the present invention contains non-melting fibers A with a limiting oxygen index of more than 27% and a thermal decomposition temperature of less than 400 degrees, and a thermoplastic with a limiting oxygen index of more than 30%. Fiber B, the porosity of the non-woven fabric is less than 98%.

The thickness retention rate of the fireproof flame-shielding nonwoven fabric of the present invention after burning with a flame at 1100° C. for 5 minutes is preferably 20% or more.

It is preferable that the content rate of the said non-melting fiber A is 20 to 80 weight%.

It is preferable that 40 weight% or less of fibers C are contained in the flame-proof flame-shielding nonwoven fabric of this invention.

The above-mentioned non-melting fibers A are preferably regenerated cellulose fibers or polyacrylonitrile fibers containing an inorganic flame retardant.

After heating at 500° C. for 10 minutes, the remaining weight ratio of the above-mentioned non-melting fibers A is preferably 27% or more.

The above-mentioned thermoplastic fibers B are preferably made of polyphenylene sulfide, anisotropic molten polyester, flame-retardant poly(alkylene terephthalate), flame-retardant poly(acrylonitrile-butadiene-styrene) ), flame retardant polysulfone, poly(ether-ether-ketone), poly(ether-ketone-ketone), polyethersulfone, polyarylate, polyphenylsulfone, polyetherimide, polyamideimide Fibers formed from resins and their mixtures.

The effective thermal conductivity at room temperature of the fireproof flame-shielding nonwoven fabric of the present invention is preferably 0.020 to 0.045 W/(m·K).

Beneficial effects of the present invention: the fire-proof flame-shielding non-woven fabric of the present invention can effectively block a certain high-temperature flame within a certain period of time, and the non-woven fabric containing a pore structure has excellent heat insulation effect and excellent light weight. . The fire-proof flame-shielding non-woven fabric of the present invention can be used as a heat-insulating and fire-proof material for the upper cover plate of a power battery, and can be applied to car seats, ceilings and other parts; it can also be used as a surface layer or filling layer of various beds, sofas and other fabric products. Flame retardant material; can also be used in various types of buildings such as wall insulation and other occasions.

Description of drawings

Fig. 1 is the schematic diagram of the fireproof flame-shielding non-woven fabric of the present invention, in the figure, A is non-melting fiber, B is thermoplastic fiber, non-melting fiber A and thermoplastic fiber B are randomly arranged to form a non-woven fabric structure.

Fig. 2 is the schematic diagram of the flame-proof non-woven fabric of the present invention, in the figure, A is non-melting fiber, B is thermoplastic fiber, C is other fiber, non-melting fiber A, thermoplastic fiber B and other fiber C are randomly arranged to form non-woven cloth structure.

Detailed ways

The flameproof flame-proof nonwoven fabric of the present invention contains non-melting fibers A with a limiting oxygen index of 27% or more and a thermal decomposition temperature of 400 degrees or less, and thermoplastic fibers B with a limiting oxygen index of more than 30%. The porosity is less than 98%. The so-called non-melting fiber A refers to a fibrous material that decomposes or degrades without softening and melting after being heated. The material has a certain ratio of length to diameter, such as cotton fiber, flax fiber, ramie fiber in natural fibers, and chemical fiber viscose fiber, meta-aramid fiber and carbon fiber. Among them, flame-retardant regenerated cellulose fibers are preferred from the viewpoint of the ease of fiber acquisition and cost. Non-melting fiber A is a fiber with a limiting oxygen index of more than 27% and a thermal decomposition temperature of less than 400 degrees. The limiting oxygen index refers to the minimum amount of oxygen required by the polymer to maintain the combustion of the substance in a mixed gas of oxygen and nitrogen. Volume percentage is an indicator to characterize the flammability of materials. The higher the limiting oxygen index, the more difficult it is to burn; the lower the limiting oxygen index, the easier it is to burn and produce flames, so that the effect of fire prevention and flame shielding cannot be achieved. Therefore, the limiting oxygen index of the non-melting fibers A is 27% or more, preferably 30% or more. Thermal decomposition temperature refers to the temperature at which macromolecules begin to crack under heat, and is an index to measure the thermal stability of macromolecules. The higher the thermal decomposition temperature, the better the thermal stability of the polymer material, but because the flame temperature during combustion is at least 600 degrees, which exceeds the thermal decomposition temperature of most organic fibers, if the thermal decomposition temperature of non-melting fibers is greater than At 400 degrees, the higher the thermal stability of the material is not only the higher cost, but also the better the thermal stability of the fiber due to the high thermal decomposition temperature. carbonized. The thermal decomposition temperature of the non-melting fibers is preferably 270 to 360 degrees in consideration of the easiness of carbonization of the non-melting fibers and the thermal stability.

The thermoplastic fiber B of the present invention is a thermoplastic fiber B having a limiting oxygen index of 30% or more, and as a specific example, it can be selected from polyphenylene sulfide, anisotropic molten polyester, flame-retardant poly(alkylene terephthalate) ester), flame retardant poly(acrylonitrile-butadiene-styrene), flame retardant polysulfone, poly(ether-ether-ketone), poly(ether-ketone-ketone), polyethersulfone, polyarylate , polyphenylsulfone, polyetherimide, polyamideimide and resin-formed fibers in their mixtures. These may be used alone, or two or more of them may be used simultaneously. Among them, the polyphenylene sulfide fiber contains sulfur element, which can release sulfur dioxide gas when heated, which has an inhibitory effect on combustion, and can promote carbonization and further improve fire resistance. Therefore, the thermoplastic fibers B are preferably polyphenylene sulfide fibers (hereinafter referred to as PPS fibers). The limiting oxygen index of thermoplastic fiber B is more than 30%, and the use of non-melting fiber A also requires a high limiting oxygen index. The obtained non-woven fabric has high flame retardant performance. It only melts without burning, and the molten thermoplastic fibers will form a liquid film, completely wrapping the non-melting fibers, so that the non-melting fibers cannot contact with air, so as to carry out oxygen-free carbonization. At the same time, because of the high limit oxygen index, the part in contact with the air will not burn, which can prevent the flame from spreading. With the increase of the burning time, the molten fiber will form a carbonized film, which will not continue to oxidize and provide flame shielding ability. From the viewpoint of preventing flame spread and forming a carbonized film, the limiting oxygen index of the thermoplastic fiber B is preferably 32-40%.

The porosity of the fire-proof flame-shielding nonwoven fabric of the present invention is lower than 98%. Porosity refers to the ratio of pore volume to total volume, which is an indicator to measure the size of pore volume. The greater the porosity, the greater the air content inside, the higher the oxygen content, and the easier it is to burn. If the porosity of the fire-proof flame-shielding non-woven fabric is higher than 98%, the air content inside is high, the oxygen content as a combustion aid in combustion will be high, and the flow of air during combustion will be more convenient, so that no Woven fabrics are more likely to burn, resulting in deterioration or even loss of fire and flame shielding properties. However, if the porosity of the non-woven fabric is too low, that is, if the air contained in the non-woven fabric is too small, the thermal insulation properties of the entire non-woven fabric will be deteriorated. Therefore, the porosity of the nonwoven fabric of the present invention is preferably 70 to 95%, more preferably 80 to 93%, in consideration of the porosity of the nonwoven fabric against fire resistance and its own heat insulation properties.

The thickness retention rate of the fireproof flame-shielding nonwoven fabric of the present invention after burning with a flame at 1100° C. for 5 minutes is preferably 20% or more. The thickness retention rate here refers to the percentage of the thickness of the burned part to the thickness of the part before burning when the fireproof flame-shielding non-woven fabric is burned in a flame of 1100 degrees for 5 minutes. When the non-woven fabric of the present invention is applied to the upper cover plate of the power battery of an electric vehicle, it has the effect of fire prevention. Of course, when the flame temperature is lower, the fire-proof flame-shielding non-woven fabric of the present invention will also play a better fire-proof effect, for example, it can be combined with a wooden door or used as a carpet for an ordinary car passenger compartment to prevent the flame. intrusion. At present, the power batteries in electric vehicles on the market have a trend of increasing energy density. While the battery life of electric vehicles is gradually increasing, it also brings serious safety problems. When batteries with high energy density are used, because they do not Stability is more prone to thermal runaway, and when a ternary lithium battery occurs thermal runaway, the flame temperature generated can reach more than 1000 degrees. If the protective material on the cover cannot withstand this high temperature during thermal runaway, it will burn quickly. create holes. However, the melting point of the aluminum cover plate on the upper layer is only 660 degrees. Although the surface of the aluminum product has an alumina layer with a thickness of 0.01-0.1 microns and a melting point temperature of several thousand degrees, the aluminum inside will also be melted after being heated. Droplets fall off, forming holes. The fire-proof flame-shielding non-woven fabric of the present invention can play a fire-proof effect, and the thickness retention rate is preferably more than 20% even after 5 minutes of flame burning at 1100 °C. The non-woven fabric can effectively block the flame, prevent the flame from burning to the cover, and the flame will not directly burn the passenger compartment. If the non-woven fabric does not have a certain thickness after being burned in a flame of 1100°C for 5 minutes, it means that the thickness of the non-woven fabric at the burned part is too thin. The flames penetrated into the passenger compartment, causing damage to life and property. Considering the flame resistance, high temperature resistance and relative heat insulation performance of the non-woven fabric, the thickness retention rate of the fire-proof flame-shielding non-woven fabric of the present invention after being burned by a 1100-degree flame is preferably 20-60%, more preferably 40-60%. %.

It is preferable that the content rate of the said non-melting fiber A is 20 to 80 weight%. The flame-shielding function of the fire-proof flame-shielding non-woven fabric of the present invention is achieved by the combination of non-melting fibers with A and thermoplastic fibers B, wherein the non-melting fibers A will not melt and shrink when the flame burns, which is the most important part of the non-woven fabric. When heated, the molten droplets of thermoplastic fiber B can spread between the fibers to form a film, and wrap the fiber A itself to block oxygen and promote carbonization, thereby improving the flame retardant performance of the flame retardant non-woven fabric. If the content of the non-melting fibers A is too low, the support function as a skeleton material becomes insufficient, and the thermoplastic fibers B are melted to form shrinkage holes, and the obtained non-woven fabric will lose the flame shielding function. On the other hand, if the content of the non-melting fibers A is too high, the thermoplastic fibers B cannot be sufficiently spread into a film, and the non-melting fibers A can be fully wrapped and sealed, so that the oxygen cannot be blocked, and the decomposition will be accelerated. Therefore, the content of the non-melting fibers A is more preferably 30 to 70%, considering that the non-melting fibers A serving as skeletons can sufficiently support the molten thermoplastic fibers B when exposed to flame.

It is preferable that 40 weight% or less of fibers C are contained in the flame-proof flame-shielding nonwoven fabric of this invention. The fibers C are fibers other than the non-melting fibers A and thermoplastic fibers B, and the weight ratio of the fibers C is preferably 40% by weight or less. In order to further impart specific properties to the flame-proof flameproof nonwoven fabric of the present invention, fibers C other than non-melting fibers A and thermoplastic fibers B may be contained. For example, in order to improve the compactness of the product and reduce the thickness, it is necessary to apply a moderate heat treatment. Polyethylene terephthalate fibers (polyester) and polyamide fibers (nylon) with lower glass transition temperature and softening temperature can be used. , polyethylene, polypropylene fibers and vinylon fibers. At the same time, adding the above several kinds of fibers can also improve the softness, strength, abrasion resistance and other properties of the non-woven fabric material of the present invention. The content of fiber C is not particularly limited as long as it does not impair the effect of the present invention, and the content of fiber C is preferably 40% or less, more preferably 15% or less, based on the weight of the fireproof flameproof nonwoven fabric.

The above-mentioned non-melting fibers A are preferably regenerated cellulose fibers or polyacrylonitrile fibers containing inorganic flame retardants, the regenerated cellulose fibers containing inorganic flame retardants are preferably regenerated cellulose fibers containing silica flame retardants, polypropylene The acrylic fiber is preferably a flame-retardant polyacrylonitrile fiber modified with a silicon-nitrogen flame retardant. Flame retardant regenerated cellulose fibers include flame retardant viscose fiber and flame retardant copper amine fiber. From the viewpoint of fiber melt shrinkage, flame-retardant viscose fibers are more preferable. Since regenerated cellulose fibers and flame retardant polyacrylonitrile fibers are white fibers and are easy to dye, these fibers can be dyed in various colors according to needs, so the obtained fireproof flame-proof non-woven fabric can have various colors, including white .

After contact with the fire source, the fiber does not burn, or the combustion is insufficient, only a small flame burns. After the fire source is removed, the flame can be extinguished as soon as possible. The fiber is called flame-retardant fiber. According to the limiting oxygen index value of the fiber, it is generally considered that the oxygen index below 22% is flammable fiber; the oxygen index is more than 22% and less than 27% is a combustible fiber; the oxygen index is more than 27% is a flame retardant or flame retardant fiber.

After heating at 500° C. for 10 minutes, the remaining weight ratio of the above-mentioned non-melting fibers A is preferably 27% or more. The remaining weight ratio of the non-melting fibers A refers to the ratio of the mass of the remaining fibrous residues after the non-melting fibers A are heated at a temperature of 500 degrees for 10 minutes to the mass of the non-melting fibers A before treatment. Although non-melting fibers will not liquefy when heated, thermal decomposition is unavoidable, and the organic components in the fibers are transformed into combustible gases, combustible liquids, carbonized solids and inorganic residues. The higher the weight residual rate of the non-melting fiber after heating, the higher the shape retention rate of the residue, and the better the flame-shielding durability of the non-woven fabric at high temperature. The weight ratio of the fibrous residue remaining after the non-melting fiber A is heated at 400 degrees for 30 minutes is more preferably 30 to 50%.

The effective thermal conductivity at room temperature of the fireproof flame-shielding nonwoven fabric of the present invention is preferably 0.020 to 0.045 W/(m·K). The manufacturing method of the fireproof flame-shielding nonwoven fabric of the present invention may be a dry method or a wet method. The consolidation method of the fibers can be thermal bonding, needle punching, or hydroentangling. However, considering the application in power batteries, it is necessary to fully consider the problem of thermal management during operation, and the non-woven fabric layer needs to have a certain heat insulation effect. Acupuncture method, the fire-proof flame-shielding non-woven fabric with fluffy structure is prepared as the upper cover plate protective material, which can give full play to the advantages of its low thermal conductivity and prevent the heat of the battery from dissipating to the outside. If the effective thermal conductivity at room temperature of the fireproof flame-shielding non-woven fabric is too low, it will be difficult for the heat transferred upward from the battery pack to pass through the upper cover, resulting in easier accumulation of heat in the battery pack, increasing the workload of the cooling system, resulting in higher energy consumption; if the effective thermal conductivity at room temperature of the fireproof flame-shielding non-woven fabric is too high, when the battery is thermally out of control, the heat will be quickly conducted through the non-woven fabric to the upper cover and even the passenger compartment, resulting in Dangerous occurrence.

When the non-woven fabric of the present invention is prepared by wet papermaking, the lengths of the non-melting fibers A, thermoplastic fibers B, and fibers C are all preferably 2 to 38 mm, more preferably 2 to 10 mm. The thermoplastic fiber B is preferably a PPS fiber, and the fineness of the single fiber is preferably 0.1 to 7D from the viewpoint of the dispersibility of the fiber in the undiluted solution.

When the non-woven fabric of the present invention is prepared by dry needling consolidation, the lengths of the non-melting fibers A, thermoplastic fibers B and C are preferably 42-76 mm in terms of cardability and formability of fibers. More preferably, it is 48-60 mm. The fineness of each fiber is preferably 0.8 to 10D, and more preferably 1.5 to 6D.

When the non-woven fabric of the present invention is prepared by spunlace consolidation, the lengths of the non-melting fibers A, thermoplastic fibers B and C are preferably 42-76 mm, more preferably 48-60 mm. The fineness of each fiber is preferably 1 to 3D, and more preferably 1.5 to 2.5D.

The present invention is further illustrated by the following examples, but the protection scope of the present invention is obviously not limited to the examples, and the physical parameters in the examples are determined by the following methods.

【Limiting oxygen index】

The limiting oxygen index refers to the volume percentage of the minimum amount of oxygen required by the polymer to maintain the combustion of the substance in a mixed gas of oxygen and nitrogen, and the unit is %. The fiber limiting oxygen index can be tested by the following method: according to the limiting oxygen index instrument specified in GB/T 5454-1997, the obtained fiber is made into non-woven fabric or fabric, and the sample is tested after adjusting the humidity for 8-24 hours. Take the average value of five tests as the limiting oxygen index % of the fiber.

【Thermal decomposition temperature】

Thermal decomposition temperature °C refers to the temperature at which the material is thermally decomposed. The specific definition and measurement method are based on the provisions of the national standard GB/T 37631-2019. Use a thermogravimetric analyzer, the heating range is from room temperature to 1000 °C, and the maximum heating rate is not less than 50 °C/min; the sample mass is 5 to 10 mg, the gas atmosphere is nitrogen, the purge flow rate is 100 ml/min, and the heating rate is 15 °C/min. , the starting temperature is 50 °C, and the ending temperature is 800 °C. The mass fraction change and temperature curve (hereinafter referred to as the TG curve) are obtained through the instrument's supporting analysis software. The temperature corresponding to the intersection of the tangent at the initial stage of the curve and the tangent at the maximum slope on the curve is the thermal decomposition temperature. Test five times, and take the average value _TA as the thermal decomposition temperature.

【Porosity】

Porosity refers to the pore volume in a bulk material as a percentage of the total volume of the material in its natural state. Sample thickness: stack 5 layers of samples, measure the stacking height, measure 5 times, and take the average value as the thickness δ of the sample. Weight per square meter of sample: According to JIS L 1096-1999, using an electronic balance, weigh the mass of the sample of 10cm×10cm, multiply the obtained data by 100, and obtain the converted weight per square meter of fabric. Measure 5 times, and take the average value as the final test result M; Fiber density: refer to the data to obtain the density of this kind of fiber, when multiple fibers are involved, take the density ρ as the sum of the products of several fiber densities and their proportions. The calculation formula of porosity is as follows: porosity η(%)={1-[M/(ρ×δ)]}×100%.

【Thickness retention rate】

According to JIS L 1096-1999 8.5, use a hand-held thickness meter to test the thickness of the samples before burning for 5 times, and take the average value, which is recorded as D1. The specific combustion method is: take an A4 size sample, fix it on a metal frame, place it vertically, use a butane spray gun to face the fixed sample, adjust the distance between the spray gun mouth and the sample to 8cm, turn on the gas switch to 3/5 After 5 minutes, turn off the gas switch, measure the thickness after five times of burning after the sample is cooled to room temperature, take the average value, and record it as D2. The calculation formula of the non-woven thickness retention rate is as follows: thickness retention rate K=(D1/D2)×100%.

[Remaining weight ratio of non-melting fibers]

The test method for the remaining weight ratio of non-melting fibers is as follows:

1. When two kinds of fibers can be directly determined from the appearance of the non-woven fabric, take 5 parts of each of the two kinds of fibers, take the average value as M1 (mg level), and carry out the TGA test respectively. The conditions are: heating at 25 degrees to 800 degree, the heating rate is 20 degrees/min, the larger remaining mass is the flame retardant non-melting fiber, and the average value of the remaining mass is M2;

2. When the different fibers cannot be determined from the appearance of the non-woven fabric, 10 fibers are randomly selected, and the average value is M1, and the TGA test is carried out. The larger ones are flame-retardant non-melting fibers, and the average value of the remaining parts with larger mass is M2. The formula for calculating the remaining weight ratio of non-melting fibers is as follows:

The remaining weight ratio of the non-melting fibers is L=M2/M1×100%.

[Content rate of non-melting fiber A]

Grind the non-woven fabric sample into powder, take 5 parts of a certain amount of powder sample for TGA test, record the average weight as M1, and take the average weight of the sample after weighing the test as M2, because the weight of the residue is not The weight of the inorganic components in the molten fibers, so the remaining weight ratio L of the non-melting fibers can be used to calculate the content of the non-melting fibers A. The specific formula is as follows:

Content of non-melting fiber A: C=(M1·M2/L)×100%.

【Thermal Conductivity】

According to GB/T 10295-2008 test standard, heat flow test method, measure the thermal conductivity of the sample at 25℃. Test five times and take the average value as thermal conductivity.

Example 1

26% by weight of flame-retardant viscose fibers with a limiting oxygen index of 30% and a thermal decomposition temperature of 275° C. and 74% by weight of polyphenylene sulfide fibers with a limiting oxygen index of 34% are mixed, and then open and open. Loosening and carding to obtain a fiber web, and then through pre-needling and main needling, a non-woven fabric with a porosity of 97% was finally obtained. 23%, and the remaining weight ratio of flame retardant viscose fiber is 32%. See Table 1 for the physical properties of the fire-proof flame-shielding nonwoven fabric of the present invention.

Example 2

45% by weight of flame-retardant viscose fibers with a limiting oxygen index of 30% and a thermal decomposition temperature of 275 ° C, and 55% by weight of polyphenylene sulfide fibers with a limiting oxygen index of 34% are mixed, and then open and open. Loosening and carding to obtain a fiber web, and then through pre-needling and main needling, a non-woven fabric with a porosity of 96% was finally obtained. 43%, and the remaining weight ratio of flame retardant viscose fiber is 32%. See Table 1 for the physical properties of the fire-proof flame-shielding nonwoven fabric of the present invention.

Example 3

73% by weight of flame-retardant viscose fibers with a limiting oxygen index of 30% and a thermal decomposition temperature of 275 ° C, and 27% by weight of polyphenylene sulfide fibers with a limiting oxygen index of 34% are mixed, and then open and open. Loosening and carding to obtain a fiber web, and then through pre-needling and main needling, a non-woven fabric with a porosity of 95% was finally obtained. 38%, and the remaining weight ratio of flame retardant viscose fiber is 32%. See Table 1 for the physical properties of the fire-proof flame-shielding nonwoven fabric of the present invention.

Example 4

Mix 50% by weight of flame-retardant viscose fibers with a limiting oxygen index of 30% and a thermal decomposition temperature of 275 ° C, and 50% by weight of polyphenylene sulfide fibers with a limiting oxygen index of 34%, and then go through cotton opening, opening Loosen and carded to obtain a fiber web, and then pre-needled, and then processed by a spunlace process to finally obtain a non-woven fabric with a porosity of 91%. After burning in a flame at 1100 ° C for 5 minutes, the non-woven fabric The thickness retention rate of 45%, and the remaining weight ratio of flame-retardant viscose fiber is 32%. See Table 1 for the physical properties of the fire-proof flame-shielding nonwoven fabric of the present invention.

Example 5

Mix 45% by weight of flame-retardant acrylic fibers with a limiting oxygen index of 31% and a thermal decomposition temperature of 250 ° C, and 55% by weight of polyphenylene sulfide fibers with a limiting oxygen index of 34%, and then go through cotton opening and opening. , carding to obtain a fiber web, and then through pre-needling and main needling, a non-woven fabric with a porosity of 95% is finally obtained. %, and the remaining weight ratio of flame retardant acrylic fiber is 25%. See Table 1 for the physical properties of the fire-proof flame-shielding nonwoven fabric of the present invention.

Example 6

46% by weight of flame-retardant viscose fibers with a limiting oxygen index of 27% and a thermal decomposition temperature of 275 ° C, and 54% by weight of polyphenylene sulfide fibers with a limiting oxygen index of 34% were mixed and then subjected to cotton opening and opening. Loosening and carding to obtain a fiber web, and then through pre-needling and main needling, a non-woven fabric with a porosity of 95% was finally obtained. 34%, and the remaining weight ratio of flame retardant viscose fiber is 31%. See Table 1 for the physical properties of the fire-proof flame-shielding nonwoven fabric of the present invention.

Example 7

Mix 45% by weight of flame-retardant viscose fibers with a limiting oxygen index of 30% and a thermal decomposition temperature of 275 ° C, and 55% by weight of flame-retardant nylon fibers with a limiting oxygen index of 30%, and then go through cotton opening and opening. , carding to obtain a fiber web, and then through pre-needling and main needling, a non-woven fabric with a porosity of 97% is finally obtained. %, the remaining weight ratio of flame retardant viscose fiber is 32%. See Table 2 for the physical properties of the fire-proof flame-shielding nonwoven fabric of the present invention.

Example 8

40% by weight of flame-retardant viscose fibers with a limiting oxygen index of 30% and a thermal decomposition temperature of 275°C, 40% by weight of polyphenylene sulfide fibers with a limiting oxygen index of 34%, and 20% by weight of acrylic fibers. Mixing and then opening, opening and carding to obtain a fiber web, and then through pre-needling and main needling to finally obtain a non-woven fabric with a porosity of 97%. After burning in a flame at 1100 ° C for 5 minutes, the The thickness retention rate of the woven fabric is 38%, the remaining weight ratio of the flame-retardant viscose fiber is 32%, and the non-woven fabric is softer and has better hand feeling. See Table 2 for the physical properties of the fire-proof flame-shielding nonwoven fabric of the present invention.

Example 9

Mix 15% by weight of flame-retardant viscose fibers with a limiting oxygen index of 30% and a thermal decomposition temperature of 275 ° C, and 85% by weight of flame-retardant nylon fibers with a limiting oxygen index of 30%, and then go through cotton opening and opening. , carding to obtain a fiber web, and then through pre-needling and main needling, a non-woven fabric with a porosity of 97% is finally obtained. %, the remaining weight ratio of flame retardant viscose fiber is 32%. See Table 2 for the physical properties of the fire-proof flame-shielding nonwoven fabric of the present invention.

Example 10

Mix 25% by weight of flame-retardant viscose fiber with a limiting oxygen index of 30% and a thermal decomposition temperature of 275 ° C, and 75% by weight of polyphenylene sulfide fiber with a limiting oxygen index of 34%, and then go through cotton opening, opening Loosening and carding to obtain a fiber web, and then through pre-needling and main needling, a non-woven fabric with a porosity of 96% was finally obtained. 20%, and the remaining weight ratio of flame-retardant viscose fiber is 25%. See Table 2 for the physical properties of the fire-proof flame-shielding nonwoven fabric of the present invention.

Example 11

Mix 45% by weight of flame-retardant cupro fibers with a limiting oxygen index of 28% and a thermal decomposition temperature of 230°C, and 55% by weight of polyphenylene sulfide fibers with a limiting oxygen index of 34%, and then go through cotton opening, Opening and carding to obtain a fiber web, and then through pre-needling and main needling, a non-woven fabric with a porosity of 96% is finally obtained. After burning in a flame at 1100 ° C for 5 minutes, the thickness retention rate of the non-woven fabric It is 31%, and the remaining weight ratio of the flame-retardant cupro fiber is 29%. See Table 2 for the physical properties of the fire-proof flame-shielding nonwoven fabric of the present invention.

Example 12

Mix 51% by weight of flame-retardant viscose fibers with a limiting oxygen index of 30% and a thermal decomposition temperature of 275°C, and 49% by weight of flame-retardant nylon fibers with a limiting oxygen index of 30%, and then go through cotton opening and opening. , carding to obtain a fiber web, and then through pre-needling and main needling, a non-woven fabric with a porosity of 97% is finally obtained. %, the remaining weight ratio of flame retardant viscose fiber is 39%. See Table 2 for the physical properties of the fire-proof flame-shielding nonwoven fabric of the present invention.

Comparative Example 1

Mix 45% by weight of acrylic fibers with a limiting oxygen index of 18% and a thermal decomposition temperature of 275°C, and 55% by weight of polyphenylene sulfide fibers with a limiting oxygen index of 34%, and then open, open and card , to obtain a fiber web, and then through pre-needling and main needling, a non-woven fabric with a porosity of 97% is finally obtained. The remaining weight proportion of acrylic fibers is 0%. The physical properties of the nonwoven fabric are shown in Table 3.

Comparative Example 2

Mix 45% by weight of flame-retardant viscose fiber with a limiting oxygen index of 31% and a thermal decomposition temperature of 275 ° C, and 55% by weight of polyester fiber with a limiting oxygen index of 20%, and then open, open and card , the fiber web was obtained, and then through pre-needling and main needling, a non-woven fabric with a porosity of 96% was finally obtained. The remaining weight proportion of flame retardant viscose fiber is 32%. The physical properties of the nonwoven fabric are shown in Table 3.

Comparative Example 3

Mix 45% by weight of flame-retardant viscose fibers with a limiting oxygen index of 31% and a thermal decomposition temperature of 275 ° C, and 55% by weight of polyphenylene sulfide fibers with a limiting oxygen index of 34%, and then go through the process of opening, Opening and carding to obtain a fiber web, and then through pre-needling and main needling, a non-woven fabric with a porosity of 99% is finally obtained. After burning in a flame at 1100 ° C for 5 minutes, the thickness retention rate of the non-woven fabric It is 10%, and the remaining weight proportion of flame-retardant viscose fiber is 32%. The physical properties of the nonwoven fabric are shown in Table 3.

Table 1

Table 2

table 3

According to the above table:

(1) It can be seen from Examples 1-3 that under the same conditions, the ratio of non-melting fiber A to thermoplastic fiber B in Example 2 is within a more preferred range. Compared with Examples 1 and 3, the obtained fireproof flame-shielding nonwoven The thickness retention rate of the cloth after being burned in a flame at 1100°C for 5 minutes is higher, that is, the flame shielding performance of the non-woven fabric is better.

(2) It can be seen from Example 2 and Example 6 that under the same conditions, the limiting oxygen index of the former non-melting fiber A is within the preferred range, and compared with the latter, the fireproof flame-proof nonwoven obtained by the former is in a 1100-degree flame. The thickness retention rate after burning for 5 minutes is higher, that is, the flame shielding performance of the non-woven fabric is better.

(3) It can be seen from Example 2 and Example 5 that under the same conditions, the remaining weight ratio of the non-melting fibers A of the former is within the preferred range, and compared with the latter, the fire-proof flame-shielding nonwoven obtained by the former is in a 1100-degree flame. The thickness retention rate after burning for 5 minutes is higher, that is, the flame shielding performance of the non-woven fabric is better.

(4) It can be seen from Example 2 and Example 7 that under the same conditions, the limiting oxygen index of thermoplastic fiber B of the former is within the preferred range, and compared with the latter, the fireproof flame-shielding non-woven fabric obtained by the former burns in a flame of 1100 degrees The thickness retention rate after 5 minutes is higher, that is, the flame shielding performance of the non-woven fabric is better.

(5) It can be seen from Example 2 and Example 8 that under the same conditions, the latter is added with other fibers C. Compared with the former, although the flexibility of the non-woven fabric obtained by the latter is good, the fire-proof flame-shielding non-woven fabric obtained is After burning in a flame of 1100 degrees for 5 minutes, the thickness retention rate was slightly lower, that is, the flame shielding property of the non-woven fabric decreased.

(6) It can be seen from Example 7 and Example 9 that under the same conditions, the thickness retention rate of the former non-woven fabric is within the preferred range, and compared with the latter, the flame-shielding performance of the fire-proof flame-shielding non-woven fabric obtained by the former is better. it is good.

(7) It can be seen from Example 1 and Example 10 that under the same conditions, the remaining weight ratio of the former non-melting fiber A after heat treatment is within the preferred range, and compared with the latter, the fireproof flame-proof nonwoven fabric obtained by the former has a temperature of 1100 degrees. The thickness retention rate after burning in the flame for five minutes is higher, that is, the flame shielding performance of the non-woven fabric is better.

(8) It can be seen from Example 6 and Example 11 that under the same conditions, the former non-melting fiber A is the preferred flame-retardant viscose, and compared with the latter, the non-woven fabric obtained by the former burns in a flame of 1100 degrees for 5 The thickness retention rate after minutes is higher, that is, the flame shielding performance of the non-woven fabric is better.

(9) It can be seen from Example 2 and Comparative Example 1 that under the same conditions, the limiting oxygen index of the latter fiber A is too low, the thickness retention rate of the obtained non-woven fabric is too low, and the fireproof and flame-shielding performance is completely lost.

(10) It can be seen from Example 2 and Comparative Example 2 that under the same conditions, the limiting oxygen index of the latter fiber B is too low, even if there is fiber A residue, the fire resistance is greatly reduced, resulting in poor flame shielding.

(11) It can be seen from Example 2 and Comparative Example 3 that under the same conditions, the porosity of the non-woven fabric obtained by the latter is too high, and the flame easily penetrates the fabric when encountering a flame, and the protective performance is lost.

Claims

A fireproof flame-shielding non-woven fabric is characterized in that: the non-woven fabric contains non-melting fibers A with a limiting oxygen index of more than 27% and a thermal decomposition temperature of less than 400 degrees, and a limiting oxygen index of more than 30%. Thermoplastic fiber B, the porosity of the non-woven fabric is less than 98%.
The fire-proof flame-shielding non-woven fabric according to claim 1, wherein the thickness retention rate of the non-woven fabric after being burned in a flame at 1100° C. for 5 minutes is more than 20%.
The fireproof flame-shielding nonwoven fabric according to claim 1, wherein the content of the non-melting fibers A is 20 to 80% by weight.
The fireproof flame-shielding non-woven fabric according to claim 1, wherein the non-woven fabric contains 40% by weight or less of fibers C.
The fireproof flame-shielding non-woven fabric according to claim 1, wherein the non-melting fibers A are regenerated cellulose fibers or polyacrylonitrile fibers containing inorganic flame retardants.
The fireproof flame-shielding non-woven fabric according to claim 1, characterized in that: after heating at 500° C. for 10 min, the remaining weight ratio of the non-melting fibers A is more than 27%.
The fireproof flame-shielding non-woven fabric according to claim 1, wherein the thermoplastic fiber B is selected from the group consisting of polyphenylene sulfide, anisotropic molten polyester, flame retardant poly(alkylene terephthalate) base ester), flame retardant poly(acrylonitrile-butadiene-styrene), flame retardant polysulfone, poly(ether-ether-ketone), poly(ether-ketone-ketone), polyethersulfone, polyarylene Fibers formed from resins in esters, polyphenylsulfones, polyetherimides, polyamideimides, and mixtures thereof.
The fireproof flame-shielding non-woven fabric according to claim 1, wherein the non-woven fabric has an effective thermal conductivity at room temperature of 0.020-0.045 W/(m·K).