CN105734968A - Method for preparing natural cellulose non-woven fabric having flame retardant function in spunbond mode - Google Patents
Method for preparing natural cellulose non-woven fabric having flame retardant function in spunbond mode Download PDFInfo
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Abstract
The invention relates to a method for preparing a natural cellulose non-woven fabric having the flame retardant function in a spunbond mode. A paper pulp is mixed with an N-methylmorpholine N-oxide (NMMO) solvent to form a slurry. A vacuum thin film evaporator (TFE) is used to remove water in the slurry to form mucus. The mucus is extruded from a spinning outlet in the spunbond mode to form a natural cellulose filament bundle. The natural cellulose non-woven fabric is prepared by carrying out solidification, regeneration, water washing, water needle rolling and drying on the natural cellulose fabric. Dip padding is carried out on the natural cellulose non-woven fabric and an N-hydroxymethyl-3-(dimethoxy phosphoryl)propionyl amide flame retardant agent, and the natural cellulose non-woven fabric having the flame retardant function according with American ASTM D 6413-1999 and ASTM D 2863-1995 test standards are prepared by carrying out roasting, alkali washing, water washing, drying and reeling in turn.
Description
Technical field
The present invention relates to a kind of method prepared in used for spunbond mode and there is resistance to combustion function native cellulose adhesive-bonded fabric, be belonging in environmental protection processing procedure manufacture native cellulose adhesive-bonded fabric technical field, it is that the native cellulose adhesive-bonded fabric prepared with N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant and used for spunbond mode in same processing procedure pads, after making active N-methylol in this N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant produce interlink with native cellulose adhesive-bonded fabric and react, sequentially impose baking again, alkali cleaning, washing, after drying and batching, and make the native cellulose adhesive-bonded fabric with the resistance to combustion function of long-acting type.
Background technology
At present in adhesive-bonded fabric manufacturing technology, direct extrusion molding (the polymerlaid of macromolecule, spunlaid) there is the advantages such as processing procedure is simple, economic benefit is high, it is that melted macromolecule passes through extrusion, the step extended, after forming continuous print long fibre, long fibre is stacked into net and forms adhesive-bonded fabric；Owing to this long fibre gives the physical property that adhesive-bonded fabric is good so that this type of adhesive-bonded fabric is widely used in the fields such as hygienic article, wiping material, medical protection and filter material, and becomes the fastest field of growing up in adhesive-bonded fabric manufacturing technology.
nullAdhesive-bonded fabric manufactured by the direct extrusion molding of aforementioned macromolecule，Before its amount of employing up to, four kinds of raw materials are sequentially polypropylene (PP)、Polyester (PET)、Polyethylene (PE) and nylon (Nylon)，Account for altogether and always make the 96% of consumption，When namely these adhesive-bonded fabrics become garbage after using，And can not be decomposed by natural environment，And according to the statistics of adhesive-bonded fabric TIA of the U.S. (INDA) and prediction，The occupation rate of the produced adhesive-bonded fabric yield of net method it is extruded into macromolecule，Grow to 43.7% (first) of 2009 from 33.5% (second) of 1994 and reach annual 2700000 tons，And within 2012, more reach 3,500,000 tons (within 2012, global adhesive-bonded fabric production has reached 8,000,000 tons)，Therefore environment is also relatively produced more huge impact and burden by so surprising growth amount more.
In addition, complete to work out the regulation of textile combustion technology successively along with various countries, as fruit product does not meet the requirement of these regulations, this state market will be prevented from entering, therefore, the adhesive-bonded fabric of the resistance to combustion textile demand with fire resistance is be constantly increasing therewith, except wiping adhesive-bonded fabric, many industrial, the industrial adhesive-bonded fabric used in home decoration, household decorating cloth and curtain etc. all must possess suitable fire resistance to avoid accidents, but, with above-mentioned polypropylene (PP), polyester (PET), the adhesive-bonded fabric textile of the fiber of the resistance to combustion processing procedure gained such as polyethylene (PE) and nylon (Nylon) is but all belonging to non-decomposability fiber, its use after garbage certainly also cannot natural degradation, therefore natural environment still can be caused bigger harmful burden.
In view of this, such as the native cellulose fibre (i.e. disappearing fibre) of how not present environmental risks, reach and produce the native cellulose adhesive-bonded fabric with the resistance to combustion function of long-acting type, just seem anxious for urgent with needs.
Summary of the invention
The main purpose of the present invention be to provide a kind of prepare in used for spunbond mode there is resistance to combustion function native cellulose adhesive-bonded fabric method its be that the native cellulose adhesive-bonded fabric prepared with N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant and used for spunbond mode in same processing procedure pads, after making active N-methylol in this N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant produce interlink with native cellulose adhesive-bonded fabric and react, sequentially impose baking again, alkali cleaning, washing, after drying and batching, and make the native cellulose adhesive-bonded fabric with the resistance to combustion function of long-acting type.
The technical scheme is that a kind of method prepared in used for spunbond mode and there is resistance to combustion function native cellulose adhesive-bonded fabric, it is characterised in that step comprises: a. is with paper pulp for raw material；Selecting α-the paper cellulose of the content of cellulose long and short fiber more than 65%, its cellulosic degree of polymerization (degreeofpolymerization is called for short DP) is between 450～1050；B. size mixing；Oxidation methyl agate beautiful jade (N-methylmorpholineN-oxide is called for short NMMO) solvent is added paper pulp and is mixed into serosity (slurry), and uses horizontal paste mixer to carry out blending together sizing mixing with 50 DEG C～80 DEG C low temperature；Wherein, the concentration of this oxidation methyl agate beautiful jade (NMMO) is 45%～78%；C. mucus it is dissolved into；Use Vacuum film evaporation device (ThinFilmEvaporator, TFE) with 80 DEG C～120 DEG C heating, in 10 minutes, get rid of moisture to 5%～13%, mucus (dope) can be formed；D. in used for spunbond mode (spunbond), mucus is squeezed out and forms the right cellulose tow of the vast of heaven after extruder extrudes and by spinning mouth；This mucus through extruder extrude after, gear pump squeeze into spin mouth die tool in, then through spin mouth outwards with air space (airgap) type of cooling carry out stretch formed the right cellulose tow of the vast of heaven；Wherein, this spins the outside air of mouth distance of spacing is 0.5 centimeter～30 centimeters, and the temperature of this use cooling air is 5 DEG C～35 DEG C, and its relative humidity is 60%～99%；E. will cooling stretch after the right cellulose tow of the vast of heaven enter solidification regeneration in solidification liquid, and after carrying out high-voltage high-speed stretching with air drafting machine, collecting net is stacked into net form adhesive-bonded fabric；Wherein, the temperature of this solidification liquid is 5 DEG C～30 DEG C, and the concentration of its internal oxidation methyl agate beautiful jade is 0～30wt%, is injected with gases at high pressure in this air drafting machine, and its draft speed is 20m/min～3000m/min；F. net form adhesive-bonded fabric rolls via washing, liquid drugs injection and dries and make native cellulose adhesive-bonded fabric；G. native cellulose adhesive-bonded fabric and N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant being padded, the concentration of this N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant is 200g/L～500g/L；And h. pad after native cellulose adhesive-bonded fabric sequentially impose baking, alkali cleaning, washing, dry and after batching, can be prepared by that there is resistance to combustion function native cellulose adhesive-bonded fabric；Wherein, the temperature of this baking is 130 DEG C～180 DEG C, and the baking time is 120 seconds～240 seconds, and the alkali liquor that this alkali cleaning uses is sodium hydroxide (NaOH), and its concentration is 50g/L, and this coiling speed is 2～200 meters per minute.
nullThe invention have the benefit that offer is a kind of and prepare the method with resistance to combustion function native cellulose adhesive-bonded fabric in used for spunbond mode，It is by paper pulp and oxidation methyl agate beautiful jade (N-methylmorpholineN-oxide，It being called for short NMMO) solvent is mixed into serosity (slurry)，And use Vacuum film evaporation device (ThinFilmEvaporator，TFE) moisture content removed in serosity forms spinning mucus (dope)，With used for spunbond mode (spunbond) by this mucus through extruder extrude after，Squeezed into by gear pump and spin in mouth die tool，Then through spin mouth outwards with air space (airgap) type of cooling carry out stretch formed native cellulose tow，Through solidification regeneration、Washing、Liquid drugs injection rolls and dries and make native cellulose adhesive-bonded fabric，Then itself and N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant are padded，And sequentially impose baking、Alkali cleaning、Washing、After drying and batching，Can be prepared by the native cellulose adhesive-bonded fabric with the resistance to combustion function of long-acting type；The special reaction that interlinks is produced with N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant by native cellulose adhesive-bonded fabric in preceding process; this is made to have the resistance to combustion function native cellulose adhesive-bonded fabric functional effect of resistance to combustion after the washing process of 20 times; still can maintain the effect before originally not washing and possess the resistance to combustion function of long-acting type; and comply fully with the testing standard requirement of the U.S. ASTMD6413-1999 and ASTMD2863-1995; and by natural decomposition, and the environment-friendly materials of harmless natural environment can be become again after it is abandoned by use.In addition, prepare this raw material with resistance to combustion function native cellulose adhesive-bonded fabric because being not from oil and spin-off thereof, therefore do not have the known staple fibre high dependency to oil and spin-off thereof, more do not have in production process the disappearance producing high carbon emission and injury ecological, environmental protective.
The additionally solvent recovery regeneration in the processing procedure of the present invention, it is simplify effective equipment and through four main programs such as decolouring, filter, concentrate, be refining, and water lotion is reclaimed oxidation methyl agate beautiful jade (NMMO) solvent becoming suitable with fresh solvent quality, its proportion of goods damageds are below 0.5%, and make overall recovery reach more than 99.5%, except environment is not resulted in pollution, the cost of more effective reduction solvent recovery, and there is the economic volume production benefit that cleaning produces and reaches resource regeneration.
Accompanying drawing explanation
Fig. 1 is the manufacturing flow chart of the present invention.
Fig. 2 is the chemical structural drawing using oxidation methyl agate beautiful jade (N-methylmorpholineN-oxide is called for short NMMO) solvent in the present invention.
Fig. 3 is the illustrative view of used for spunbond native cellulose tow in the present invention.
Fig. 4 is the chemical structural drawing using N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant in the present invention.
In figure, concrete label is as follows:
1-mucus 2-gear pump
3-spins mouth die tool 4-and spins mouth
The right cellulose tow 6-solidification liquid of the 5-vast of heaven
7-gases at high pressure 8-air drafting machine
9-collecting net 10-net form adhesive-bonded fabric
S-extruder
Detailed description of the invention
For further illustrating Making programme and effect of the present invention, Zi Zuo describes in detail as rear with diagram and each test examples:
Referring to shown in Fig. 1 to Fig. 4, the present invention prepares the method with resistance to combustion function native cellulose adhesive-bonded fabric in used for spunbond mode, and its step comprises:
A. with paper pulp for raw material；Selecting α-the paper cellulose of the content of cellulose long and short fiber more than 65%, its cellulosic degree of polymerization (degreeofpolymerization is called for short DP) is between 450～1050；
B. size mixing；Oxidation methyl agate beautiful jade (N-methylmorpholineN-oxide is called for short NMMO) solvent is added paper pulp and is mixed into serosity (slurry), and uses horizontal paste mixer to carry out blending together sizing mixing with 50 DEG C～80 DEG C low temperature；Wherein, the concentration of this oxidation methyl agate beautiful jade (NMMO) is 45%～78%, and its chemical structural drawing is as shown in Figure 2；
C. mucus it is dissolved into；Use Vacuum film evaporation device (ThinFilmEvaporator, TFE) with 80 DEG C～120 DEG C heating, in 10 minutes, get rid of moisture to 5%～13%, mucus (dope) can be formed；
D. in used for spunbond mode (spunbond), mucus is squeezed out and forms the right cellulose tow of the vast of heaven after extruder extrudes and by spinning mouth；As shown in Figure 3, this mucus 1 is after extruder S extrudes, squeezed into by gear pump 2 and spin in mouth die tool 3, outwards carry out stretching and form the right cellulose tow 5 of the vast of heaven with air (airgap) type of cooling of spacing then through spinning mouth 4, wherein, the distance that air spaces is 0.5 centimeter～30 centimeters, and the temperature using cooling air is 5 DEG C～35 DEG C, and its relative humidity is 60%～99%；
E. will cooling stretch after the right cellulose tow of the vast of heaven enter solidification regeneration in solidification liquid, and after carrying out high-voltage high-speed stretching with air drafting machine, collecting net stacks into net form adhesive-bonded fabric；As shown in Figure 3, the right cellulose tow 5 of this vast of heaven enters solidification regeneration in solidification liquid 6, and inject gases at high pressure 7 in air drafting machine 8, for 20m/min～3000m/min, the right cellulose tow 5 of the vast of heaven is carried out high-voltage high-speed stretching with draft speed, after making this long native cellulose fibre form the fiber of uniformity, collecting net 9 stacks into net form adhesive-bonded fabric 10, wherein, the temperature of this solidification liquid 6 is 5 DEG C～30 DEG C, and the concentration of its internal oxidation methyl agate beautiful jade is 0～30wt%；
F. net form adhesive-bonded fabric rolls via washing, liquid drugs injection and dries and make native cellulose adhesive-bonded fabric；
G. native cellulose adhesive-bonded fabric and N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant are padded; the concentration of this N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant is 200g/L～500g/L, and its chemical structural drawing is as shown in Figure 4；And
H. the native cellulose adhesive-bonded fabric after padding sequentially imposes baking, alkali cleaning, washing, dry and after batching, can be prepared by that there is resistance to combustion function native cellulose adhesive-bonded fabric；Wherein, the temperature of this baking is 130 DEG C～180 DEG C, and the baking time is 120 seconds～240 seconds, and the alkali liquor that this alkali cleaning uses is NaOH or Na2CO3, its concentration is 50g/L, and this coiling speed is 2～200 meters per minute.
Wherein, in above-mentioned steps b, the content of cellulose of this mucus is 6wt%～15wt%, and the viscosity of its mucus is 1000～20000 (poise), and the printing opacity index of mucus is 1.470～1.495, and the melt index of mucus is 200～1000.
Having resistance to combustion function native cellulose adhesive-bonded fabric obtained by above-mentioned steps g again, the basic weight of its cellulose adhesive-bonded fabric is 10g/m2～300g/m2, fibre number is 1～50um, and operating direction (MD) hot strength of adhesive-bonded fabric is 5～20kgf, and the hot strength of its vertical direction (CD) is then 5～15kgf.
In another above-mentioned steps e, in this solidification liquid, the concentration of methyl morpholine oxide (NMMO) is 0～30wt%, and the temperature of solidification liquid is 5 DEG C～35 DEG C.
Furthermore, in the invention described above processing procedure, its primary solvent oxidation methyl agate beautiful jade (NMMO) can disengage during net form adhesive-bonded fabric regeneration washing in step f, because high number must all be reclaimed fully to recycle, the step of this solvent recovery is as it is shown in figure 1, it comprises:
A. decolouring: be with activated carbon suspended pattern adsorption bleaching, no bleaching liquid adds 0.05%～0.10% adsorptivity and the good active carbon powder of suspension, by air blast mixing and absorption and multiple and standing Suspension adsorption alternate treatment, the process time scale of both is 1:3 to 1:6, more than 8 hours process time can complete decolouring, and which and program can simplify equipment, save the energy and improve adsorption bleaching effect.
B. filter: be adopt the two-stage to filter, first stage coarse filtration uses general filter cartridge type filter to simplify equipment, but the speed slowing down filtration at filter element outermost layer for avoiding activated carbon to build up, therefore filter aid is except being distributed in cartridge surface in advance, also in non-filtrate, 0.03%～0.05% is added, non-filtrate is made to contain a small amount of bulk filter aid, then the rate of filtration is greatly improved and can keep not going down, the composition of this filter aid is with kieselguhr: the ratio effect of cellulose=4:1 is best, filtering residue residual liquid is centrifuged after completing by coarse filtration, dehydration, reclaim, and the filtering residue filter aid after dehydration still has drainage effect and can recycling use once.Its second stage fine straining uses accurate filter UF, and after fine straining, filtrate cleanliness factor is identical with fresh solvent, the advantage that the coarse filtration of employing the manner and fine straining have low installation cost, low-loss rate, format high throughput, high cleanliness factor.
C. concentration: processing procedure of the present invention because of water lotion reclaim time, its solvent strength need to be concentrated to 50%～55% by 6.5%～8.0%, and fiber per ton about needs concentration to dewater 90 tons, concentration load very big；When fiber production is less: being adopt triple effect condensing mode, it dewaters and per ton about needs steam consumption 0.5 ton (though steam consumption is high, but power consumption is less)；When fiber production is slightly larger: then adopt MVR condensing mode, it dewaters and per ton about needs steam 0.003～0.03 ton (though steam consumption is low, but power consumption is slightly larger), these two kinds of condensing mode are respectively applicable to different output, but produced concentrated solution and condensed water all can all reclaim；Wherein, concentrated solution is available for the use of processing procedure solvent, and condensed water is then available for the use of precursor washing.
D. refine: be adopt 80 DEG C of low-temperature oxidations and neutralize reduction, use 35%H2O2For oxidant, 85%N2H4·H2O is for neutralizing reducing agent, and by the redox result of potentiometric determination, its oxidation methyl agate beautiful jade (NMMO) content can drop to below 10ppm, and can improve oxidation methyl agate beautiful jade (NMMO) purity and reduce loss.
For proving the feature of the present invention further and implementing effect, it is carried out every test examples and illustrated as rear:
Embodiment one (inventive samples numbering S1～S6 and F1～F6):
nullThe paper cellulose that the degree of polymerization is 650 is mixed into serosity with oxidation methyl agate beautiful jade (NMMO) solvent，And utilize Vacuum film evaporation device to evaporate unnecessary moisture content，With 80 DEG C～120 DEG C heating，Moisture is got rid of to 5%～13% in 5 minutes，Cellulose dissolution can be become mucus (dope)，Its mucus composition table is in [table one] shown in sample number into spectrum S1～S6，Then with used for spunbond mode (spunbond) by this mucus through extruder extrude after，Squeezed into by gear pump and spin in mouth die tool，Then through spin mouth outwards with air space (airgap) type of cooling carry out stretch formed native cellulose tow，And after entering in solidification liquid solidification regeneration，High-voltage high-speed stretching is carried out with air drafting machine，Then through washing、Liquid drugs injection rolls and dries and make native cellulose adhesive-bonded fabric，Finally，This native cellulose adhesive-bonded fabric and N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant are padded，And sequentially impose baking、Alkali cleaning、Washing、After drying and batching，What can be prepared by different basic weight has resistance to combustion function native cellulose adhesive-bonded fabric sample in [table two] shown in sample number into spectrum F1～F6，Wherein，This N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant concentration is 0g/L～450g/L，Baking temperature is 180 DEG C，The time of baking is 240 seconds.
Embodiment two (inventive samples numbering S7～S12 and F7～F12):
nullThe paper cellulose that the degree of polymerization is 1050 is mixed into serosity with oxidation methyl agate beautiful jade (NMMO) solvent，And utilize Vacuum film evaporation device to evaporate unnecessary moisture content，With 80 DEG C～120 DEG C heating，Moisture is got rid of to 5%～13% in 5 minutes，Cellulose dissolution can be become mucus (dope)，Its mucus composition table is in [table one] shown in sample number into spectrum S7～S12，Then with used for spunbond mode (spunbond) by this mucus through extruder extrude after，Squeezed into by gear pump and spin in mouth die tool，Then through spin mouth outwards with air space (airgap) type of cooling carry out stretch formed native cellulose tow，And after entering in solidification liquid solidification regeneration，High-voltage high-speed stretching is carried out with air drafting machine，Then through washing、Liquid drugs injection rolls and dries and make native cellulose adhesive-bonded fabric，Finally，This native cellulose adhesive-bonded fabric and N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant are padded，And sequentially impose baking、Alkali cleaning、Washing、After drying and batching，What can be prepared by different basic weight has resistance to combustion function native cellulose adhesive-bonded fabric sample in [table two] shown in sample number into spectrum F7～F12，Wherein，This N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant concentration is 0g/L～450g/L，Baking temperature is 180 DEG C，The time of baking is 240 seconds.
The mucus composition table of [table one] each sample used for spunbond
The native cellulose adhesive-bonded fabric physical property table that [table two] different flame retardant concentration processes
Embodiment three (resistance to combustion function test):
nullThe paper cellulose that the degree of polymerization is 650 and 1050 is mixed into serosity with oxidation methyl agate beautiful jade (NMMO) solvent，Horizontal paste mixer is used to carry out blending together sizing mixing with 50 DEG C～80 DEG C low temperature，And utilize Vacuum film evaporation device to evaporate unnecessary moisture content，With 80 DEG C～120 DEG C heating，Moisture is got rid of to 5%～13% in 5 minutes，Cellulose dissolution can be become mucus (dope)，Then with used for spunbond mode (spunbond) by this mucus through extruder extrude after，Squeezed into by gear pump and spin in mouth die tool，Then through spin mouth outwards with air space (airgap) type of cooling carry out stretch formed native cellulose tow，And after entering in solidification liquid solidification regeneration，High-voltage high-speed stretching is carried out with air drafting machine，Then through washing、Liquid drugs injection rolls and dries and make native cellulose adhesive-bonded fabric，Finally this native cellulose adhesive-bonded fabric and N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant are padded，And sequentially impose baking、Alkali cleaning、Washing、After drying and batching，What can be prepared by different basic weight has resistance to combustion function native cellulose adhesive-bonded fabric，Wherein，This N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant concentration is 0g/L～450g/L，Baking temperature is 180 DEG C，The time of baking is 240 seconds.Each fiber sample (F1～F12) obtained as above carries out every flame resistance test according to U.S.'s ASTMD6413-1999 testing standard again.
This test adopts vertical combustion.Take and there is obtained by the aforementioned present invention each three pieces of resistance to combustion function native cellulose adhesive-bonded fabric sample, every piece 1.5 centimeters × 24.5 centimeters, sample is fixed on Fire Test instrument, make 19 millimeters away from socket be, sample lower end, and regulate flame height 38 millimeters, contact sample 12 seconds, remove flame, press stopwatch until ashes all extinguish stopwatch again, the residual flame time of record afterflame and glow time on cloth specimen simultaneously.
Carbonization range measurement；After flame resistance test terminates, take off sample, doubling, press the weight matched with sample unit are in side, sample lower end, slowly mention sample lower end opposite side with hands, allow weight overturn, measure sample uninterrupted length.Obtained as above go out various result of the tests respectively according to shown in sample number into spectrum F1～F12 in [table three] and according to shown in sample number into spectrum T1～T12 in [table four].
The resistance to combustion function test of native cellulose adhesive-bonded fabric that [table three] different flame retardant concentration (stoving temperature is homogeneously all 180 DEG C, and the baking time is homogeneously all 240 seconds) processes
[table four] different flame retardant baking temperature and bake the resistance to combustion function test of native cellulose adhesive-bonded fabric that the time (flame retardant concentration is homogeneously all 450g/L) processes
Embodiment four (the resistance to combustion function test of limited oxygen index):
nullThe wood pulp cellulose that the degree of polymerization is 650 and 1050 is mixed into serosity with oxidation methyl agate beautiful jade (NMMO) solvent respectively，Horizontal paste mixer is used to carry out blending together sizing mixing with 50 DEG C～80 DEG C low temperature，Then the moisture content that the evaporation of Vacuum film evaporation device is unnecessary is utilized，With 80 DEG C～120 DEG C heating，Moisture is got rid of to 5%～13% in 5 minutes，Cellulose dissolution can be become mucus (dope)，Then with used for spunbond mode (spunbond) by this mucus through extruder extrude after，Squeezed into by gear pump and spin in mouth die tool，Then through spin mouth outwards with air space (airgap) type of cooling carry out stretch formed native cellulose tow，And after entering in solidification liquid solidification regeneration，High-voltage high-speed stretching is carried out with air drafting machine，Then through washing、Liquid drugs injection rolls and dries and make native cellulose adhesive-bonded fabric，Finally，This native cellulose adhesive-bonded fabric and N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant are padded，And sequentially impose baking、Alkali cleaning、Washing、After drying and batching，What can be prepared by different basic weight has resistance to combustion function native cellulose adhesive-bonded fabric，Each fiber sample obtained as above carries out limited oxygen index (L.O.I) flame resistance test according to U.S.'s ASTMD2863-1995 testing standard again.
The value of the minimum oxygen concentration that this limited oxygen index (LimitofOxygenIndex, L.O.I) value is fiber or fabric sample is positioned in combustion barrel needed for sustained combustion, its computing formula is as follows:
Fiber that above-mentioned limited oxygen index is more high or fabric need the oxygen of high concentration when burning, are in other words less susceptible to burning.
Obtained as above go out various result of the tests respectively according to shown in sample number into spectrum F1～F12 in [table five] and according to shown in sample number into spectrum T1～T12 in [table six].
The resistance to combustion function test of native cellulose adhesive-bonded fabric limited oxygen index (L.O.I) that [table five] different flame retardant concentration (stoving temperature is homogeneously all 180 DEG C, and the baking time is homogeneously all 240 seconds) processes
| Sample | Cellulosic degree of polymerization | Flame retardant concentration (g/L) | Limited oxygen index (L.O.I) | Test effect (with/without) |
| F1 | 650 | 0 | 17 | Nothing |
| F2 | 650 | 100 | 23 | Nothing |
| F3 | 650 | 200 | 27 | Slightly |
| F4 | 650 | 300 | 30 | Have |
| F5 | 650 | 400 | 35 | Have |
| F6 | 650 | 450 | 37 | Have |
| F7 | 1050 | 0 | 17 | Nothing |
| F8 | 1050 | 100 | 24 | Nothing |
| F9 | 1050 | 200 | 27 | Slightly |
| F10 | 1050 | 300 | 33 | Have |
| F11 | 1050 | 400 | 36 | Have |
| F12 | 1050 | 450 | 37 | Have |
[table six] different flame retardant baking temperature and bake the resistance to combustion function test of native cellulose adhesive-bonded fabric limited oxygen index (L.O.I) that the time (flame retardant concentration is homogeneously all 450g/L) processes
Embodiment five (washing the resistance to combustion function test after 20 times):
nullThe wood pulp cellulose that the degree of polymerization is 650 and 1050 is mixed into serosity with oxidation methyl agate beautiful jade (NMMO) solvent respectively，Horizontal paste mixer is used to carry out blending together sizing mixing with 50 DEG C～80 DEG C low temperature，Then the moisture content that the evaporation of Vacuum film evaporation device is unnecessary is utilized，With 80 DEG C～120 DEG C heating，Moisture is got rid of to 5%～13% in 5 minutes，Cellulose dissolution can be become mucus (dope)，Then with used for spunbond mode (spunbond) by this mucus through extruder extrude after，Squeezed into by gear pump and spin in mouth die tool，Then through spin mouth outwards with air space (airgap) type of cooling carry out stretch formed native cellulose tow，And after entering in solidification liquid solidification regeneration，High-voltage high-speed stretching is carried out with air drafting machine，Then through washing、Liquid drugs injection rolls and dries and make native cellulose adhesive-bonded fabric，Finally，This native cellulose adhesive-bonded fabric and N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant are padded，And sequentially impose baking、Alkali cleaning、Washing、After drying and batching，What can be prepared by different basic weight has resistance to combustion function native cellulose adhesive-bonded fabric，Each adhesive-bonded fabric sample obtained as above is first according to the method for washing of AATCC135-2004Option1 (2) v1A (i) 4LbLoad，Carry out washing 20 times after，Every flame resistance test is carried out again according to U.S.'s ASTMD6413-1999 testing standard，These various result of the tests drawn are respectively according to shown in sample number into spectrum F1～F12 in [table seven] and according to shown in sample number into spectrum T1～T12 in [table eight].
The native cellulose adhesive-bonded fabric that [table seven] different flame retardant concentration (stoving temperature is homogeneously all 180 DEG C, and the baking time is homogeneously all 240 seconds) processes is through washing the resistance to combustion function test after 20 times
[table eight] different flame retardant baking temperature and bake native cellulose adhesive-bonded fabric that the time (flame retardant concentration is homogeneously all 450g/L) processes resistance to combustion function test after washing 20 times
Embodiment six (washing the resistance to combustion function test of limited oxygen index after 20 times):
nullThe wood pulp cellulose that the degree of polymerization is 650 and 1050 is mixed into serosity with oxidation methyl agate beautiful jade (NMMO) solvent respectively，Horizontal paste mixer is used to carry out blending together sizing mixing with 50 DEG C～80 DEG C low temperature，Then the moisture content that the evaporation of Vacuum film evaporation device is unnecessary is utilized，With 80 DEG C～120 DEG C heating，Moisture is got rid of to 5%～13% in 5 minutes，Cellulose dissolution can be become mucus (dope)，Then with used for spunbond mode (spunbond) by this mucus through extruder extrude after，Squeezed into by gear pump and spin in mouth die tool，Then through spin mouth outwards with air space (airgap) type of cooling carry out stretch formed native cellulose tow，And after entering in solidification liquid solidification regeneration，High-voltage high-speed stretching is carried out with air drafting machine，Then through washing、Liquid drugs injection rolls and dries and make native cellulose adhesive-bonded fabric，Finally，This native cellulose adhesive-bonded fabric and N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant are padded，And sequentially impose baking、Alkali cleaning、Washing、After drying and batching，What can be prepared by different basic weight has resistance to combustion function native cellulose adhesive-bonded fabric，Each adhesive-bonded fabric sample obtained as above is first according to the method for washing of AATCC135-2004Option1 (2) v1A (i) 4LbLoad，Carry out washing 20 times after，Limited oxygen index (L.O.I) flame resistance test is carried out again according to U.S.'s ASTMD2863-1995 testing standard，This result of the test drawn is respectively according to shown in sample number into spectrum F1～F12 in [table nine] and according to shown in sample number into spectrum T1～T12 in [table ten].
The native cellulose adhesive-bonded fabric that [table nine] different flame retardant concentration (stoving temperature is homogeneously all 180 DEG C, and the baking time is homogeneously all 240 seconds) processes carries out the resistance to combustion function test of limited oxygen index (L.O.I) after washing 20 times
[table ten] different flame retardant baking temperature and bake native cellulose adhesive-bonded fabric that the time (flame retardant concentration is homogeneously all 450g/L) processes and carry out the resistance to combustion function test of limited oxygen index (L.O.I) after washing 20 times
By above-listed [table three], [table four], in [table five] and [table six], every resistance to combustion function test result shows, the native cellulose of the resistance to combustion adhesive-bonded fabric of the present invention, limited oxygen index (L.O.I) value more than 25 can be reached when the content of N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant reaches more than 200g/L, to meet the testing standard requirement of the U.S. ASTMD6413-1999 and ASTMD2863-1995, then the content of N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant to reach more than 350g/L, namely limited oxygen index (L.O.I) value to reach more than 32；Therefore example by this [table three], [table four], [table five] and [table six] is provable, the present invention can reach effect of resistance to combustion really.
Again by [table seven], [table eight], [table nine] and [table ten] carries out through washing 20 times after resistance to combustion function test result show, the present invention is after the washing process of 20 times, the functional effect of resistance to combustion of adhesive-bonded fabric still maintains the effect before originally not washing, and the testing standard requirement of the U.S. ASTMD6413-1999 and ASTMD2863-1995 can be met equally, thus provable according to obtained by the inventive method, there is resistance to combustion function native cellulose adhesive-bonded fabric, it is belonging to the resistance to combustion function native cellulose adhesive-bonded fabric of long-acting type, its resistance to fuel efficiency fruit exceeds well over generally to be sold on the market and is coated with flame retardant with surface or adds the adhesive-bonded fabric of resistance to combustion of flame retardant.
nullIn sum，According to the native cellulose of resistance to combustion adhesive-bonded fabric prepared by the spunbond mode of the present invention，Because in its processing procedure, N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant produces the special reaction that interlinks with native cellulose adhesive-bonded fabric，Therefore it is after 20 times are washed，Remain to meet the requirement of resistance to combustion，And resistance to fuel efficiency fruit all meets the testing standard requirement of the U.S. ASTMD6413-1999 and ASTMD2863-1995，Furthermore，The present invention separately can according to the adding proportion of N-methylol-3-(dimethoxy phosphoryl) propionic acid amide. flame retardant，Make the native cellulose of the resistance to combustion adhesive-bonded fabric of different size，The rate of descent 10% of its fibre strength and ideal，And this native cellulose of resistance to combustion adhesive-bonded fabric use abandon after again can by natural decomposition，And the material meeting environmental requirement can be become，Really there is high industrial usability，Also the important document of patent of invention is met，File an application in whence in accordance with the law.
Claims (12)
1. prepare the method with resistance to combustion function native cellulose adhesive-bonded fabric in used for spunbond mode for one kind, it is characterised in that step comprises:
A. with paper pulp for raw material；A-the paper cellulose of the content of cellulose long and short fiber more than 65%, its cellulosic degree of polymerization is between 4501050 in selection；
B. size mixing；Oxidation methyl agate beautiful jade solvent is added paper pulp and is mixed into serosity, and use horizontal paste mixer to carry out blending together sizing mixing with 50 DEG C of 80 DEG C of low temperature；Wherein, the concentration of this oxidation methyl agate beautiful jade is 45%78%；
C. mucus it is dissolved into；Use Vacuum film evaporation device with 80 DEG C 120 DEG C heating, in 10 minutes, get rid of moisture to 5%～13%, mucus can be formed；
D. in used for spunbond mode, mucus is squeezed out and forms the right cellulose tow of the vast of heaven after extruder extrudes and by spinning mouth；This mucus through extruder extrude after, gear pump squeeze into spin mouth die tool in, then through spin mouth outwards with air space the type of cooling carry out stretch formed the right cellulose tow of the vast of heaven；Wherein, this spins the outside air of mouth distance of spacing is 0.5 centimeter～30 centimeters, and the temperature of this use cooling air is 5 DEG C～35 DEG C, and its relative humidity is 60%～99%；
E. will cooling stretch after the right cellulose tow of the vast of heaven enter solidification regeneration in solidification liquid, and after carrying out high-voltage high-speed stretching with air drafting machine, collecting net is stacked into net form adhesive-bonded fabric；Wherein, the temperature of this solidification liquid is 5 DEG C～30 DEG C, and the concentration of its internal oxidation methyl agate beautiful jade is 0～30wt%, is injected with gases at high pressure in this air drafting machine, and its draft speed is 20m/min～3000m/min；
F. net form adhesive-bonded fabric rolls via washing, liquid drugs injection and dries and make native cellulose adhesive-bonded fabric；
G. native cellulose adhesive-bonded fabric and N-methylol-3-propionic acid amide. flame retardant being padded, the concentration of this N-methylol-3-propionic acid amide. flame retardant is 200g/L500g/L；And
H. the native cellulose adhesive-bonded fabric after padding sequentially imposes baking, alkali cleaning, washing, dry and after batching, can be prepared by that there is resistance to combustion function native cellulose adhesive-bonded fabric；Wherein, the temperature of this baking is 130 DEG C 180 DEG C, and the baking time is 120 seconds 240 seconds, and the alkali liquor that this alkali cleaning uses is sodium hydroxide, and its concentration is 50g/L, and this coiling speed is 2200 meters per minute.
2. according to claim 1 prepare the method with resistance to combustion function native cellulose adhesive-bonded fabric in used for spunbond mode, it is characterised in that: in this step b, the content of cellulose of mucus is 6wt%～15wt%.
3. according to claim 1 prepare the method with resistance to combustion function native cellulose adhesive-bonded fabric in used for spunbond mode, it is characterised in that: in this step b, the viscosity of mucus is 1000～20000.
4. according to claim 1 prepare the method with resistance to combustion function native cellulose adhesive-bonded fabric in used for spunbond mode, it is characterised in that: in this step b, the printing opacity index of mucus is 1.470～1.495.
5. according to claim 1 prepare the method with resistance to combustion function native cellulose adhesive-bonded fabric in used for spunbond mode, it is characterised in that: in this step b, the melt index of mucus is 200～1000.
6. according to claim 1 prepare the method with resistance to combustion function native cellulose adhesive-bonded fabric in used for spunbond mode, it is characterised in that: having resistance to combustion function native cellulose adhesive-bonded fabric obtained by step g, the basic weight of its cellulose adhesive-bonded fabric is 10g/m2～300g/m2。
7. according to claim 1 prepare the method with resistance to combustion function native cellulose adhesive-bonded fabric in used for spunbond mode, it is characterised in that: having resistance to combustion function native cellulose adhesive-bonded fabric obtained by step g, its fibre number is 1～50um.
8. according to claim 1 prepare the method with resistance to combustion function native cellulose adhesive-bonded fabric in used for spunbond mode, it is characterized in that: obtained by step g, there is resistance to combustion function native cellulose adhesive-bonded fabric, the operating direction hot strength of its adhesive-bonded fabric is 5 ~ 20kgf, and the hot strength of its vertical direction is 5 ~ 15kgf.
9. according to claim 1 prepare the method with resistance to combustion function native cellulose adhesive-bonded fabric in used for spunbond mode, it is characterised in that: in step e, in this solidification liquid, the concentration of methyl morpholine oxide is 0 ~ 30wt%, and the temperature of solidification liquid is 5 DEG C ~ 35 DEG C.
10. according to claim 1 prepare the method with resistance to combustion function native cellulose adhesive-bonded fabric in used for spunbond mode, it is characterised in that: the alkali liquor that in this step h, alkali cleaning uses changes into sodium carbonate, and its concentration is 50g/L.
The method with resistance to combustion function native cellulose adhesive-bonded fabric is prepared in used for spunbond mode 11. according to claim 1, it is characterized in that: the paper pulp raw material of this step a, variable more long fibre wood pulp or chopped fiber wood pulp, and its a-content of cellulose is more than 65%, and its cellulosic degree of polymerization is between 500 ~ 1500.
The method with resistance to combustion function native cellulose adhesive-bonded fabric is prepared in used for spunbond mode 12. according to claim 1, it is characterised in that: in its processing procedure, the step of solvent recovery comprises:
A. decolouring: be decolour with activated carbon suspended pattern suction, no bleaching liquid adds 0.05%～0.10% adsorptivity and the good active carbon powder of suspension, again and Suspension adsorption alternate treatment is stood by air blast mixing and absorption, the process time scale of both is 1:3 to 1:6, more than the 8 hours time of process；
B. filter: be adopt the two-stage to filter, the general filter cartridge type filter of first stage coarse filtration, and by filter aid except being distributed in cartridge surface in advance, another addition 0.03%～0.05% in non-filtrate, promoting non-filtrate to contain a small amount of bulk filter aid, the proportion of composing of this filter aid is kieselguhr: cellulose=4:1, by centrifugal for filtering residue residual liquid, dehydration, recovery after coarse filtration completes, filtering residue filter aid recycling after its dehydration use once, and second stage fine straining is to use accurate filter UF for it；
C. concentration: when fiber production is less: being adopt triple effect condensing mode, it dewaters and per ton about needs steam consumption 0.5 ton, and its steam consumption is high, but power consumption is less；When fiber production is slightly larger: then adopting MVR condensing mode, it dewaters and per ton about needs steam 0.003～0.03 ton, and its steam consumption is low, but power consumption is slightly larger, and produced by these two kinds of condensing mode, concentrated solution and condensed water all reclaim；Wherein, concentrated solution is available for the use of processing procedure solvent；Condensed water is available for the use of precursor washing；And
D. refine: be adopt 80 DEG C of low-temperature oxidations and neutralize reduction, use 35%H2O2For oxidant, 85%N2H4·H2O is for neutralizing reducing agent, then by the redox result of potentiometric determination, its NMM content can drop to below 10ppm, and can improve NMMO purity and minimizing loss.
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