The present invention relates to a “meltblown wetlaid method for producing non-woven fabrics with anti-mildew, anti-bacteria and deodorizing capabilities from natural cellulose”, particularly for one with environment protective process that not only has advantages in low manufacturing cost without environmental pollution but also features good anti-mildew, anti-bacteria and deodorizing capabilities so that it meet medical and industrial application requirements such as apparels, sanitary and medical materials, filtrating materials, wiping materials for biomedical and optoelectronic wafers and the like.
Currently, most nonwoven fabrics of chemical synthetic fiber are produced from melted macromolecule polymers and made by spunlaid process through extrusion and stretch to form continuous filaments as well as stacking laying for web formation so that the nonwoven fabrics of such filaments feature in good physical properties of air permeability and water absorption. Thus, such nonwoven fabrics of chemical synthetic fiber are prevalently used in application fields of medical, sanitary, wiper, filters and so on. According to the survey and statistics of Association of the Nonwoven Fabrics Industry USA (INDA), the marketing share for the nonwoven fabrics of chemical synthetic produced spunlaid process already from 33.5% in 1994 (second) leaps up to 43.7% in 2009 (first) with total annual yield of 2.7 million tons. Wherein, main raw materials are from polypropylene (PP), polyester (PET), polyethylene (PE) and Nylon in quantity order with overall consumed quantity 96%. However, the wasted nonwoven fabric of chemical synthetic fiber after having been used incurs a malignant impact to the environment because they are indissoluble by natural environment.
Chitin and Chitosan are linear polymers (namely linear-chained macromolecule polymers) produced from N-acetyl Glucosamine monomer and Glucosamine monomer by β-1,4 bond. Materials containing chitin widely distributes in the natural world such as horny shells of shrimps and crabs in crustaceans, etc. From viewpoint in food processing of waste recycling, Chitin and Chitosan are worthwhile to capitalize on exploitation. Moreover, the yield and output value for crustacean processing of shrimp and crabs is a primary project of aquatic product processing in Taiwan for quite a long time. However, the processing wastes, which abundantly contain protein, astaxanthin, chitin and the like, might become an ecologic and environmental burden if they have not been well treated. On the other hand, if they can be well exploited to process into chitin/chitosan, they may not only solve the waste issue but also create economical value with multiple beneficiary effects such as anti-mildew, bacteriostatic and deodorizing functions owing to their intrinsic biodegradibility and bio-compatibility. For processing horny shells of shrimp and crab in crustacean, 20˜30% of chitin therein can be obtained by proper purification while various chitosan with different degree of de-acetylating can be obtained via de-acetylating process under high temperature with hot alkali.
Therefore, how to produce nonwoven fabrics of continual filament with excellent anti-mildew, bacteriostatic and deodorizing functions by short eco-friendly process of low manufacturing cost from natural fiber material becomes an urgent and critical issue. Having realized and addressed above issue, the inventor of the present invention has been enthusiastically performing study and research in painstaking manner for quite a long time. Eventually, a satisfactory nonwoven fabric of continual filament with excellent anti-mildew, bacteriostatic and deodorizing functions is successfully worked out as disclosed in this specification.
The primary object of the present invention is to provide a “meltblown wetlaid method for producing non-woven fabrics with anti-mildew, anti-bacteria and deodorizing capabilities from natural cellulose”. The method is to select wood pulp as raw material and use N-methylmorpholine N-oxide (NMMO) as dissolving solvent and 1,3-phenylene-bis 2-oxazoline (BOX) as stabilizer to form mixed cellulose mucilage as well as use modified and nano-miniaturized natural chitosan as additive for blending and dissolution to form cellulose dope. By meltblown method, the dope is extruded out of spinnerets to form filament bundle; and by ejecting mist aerosol of water, the filament bundle is coagulated with regeneration; After post treatments of water rinsing, hydro-entangled needle punching, drying, winding-up and the like have been orderly applied, then final product for nonwoven fabric of continuous filament with anti-mildew, anti-bacteria and deodorizing capabilities is produced. Accordingly, the present invention becomes an environment protective process with advantages in low manufacturing cost due to short process and solvent adequately recycle without environmental pollution due to nontoxic N-methylmorpholine N-oxide (NMMO). Besides, even after 10 times laundering in 70° C. hot water with 5 g/L detergent for 45 minutes, the nonwoven fabric of natural cellulose produced by the method of the present invention can still keep anti-mildew, anti-bacteria and deodorizing capability as that before laundering.
The other object of the present invention is to provide a “meltblown wetlaid method for producing non-woven fabrics with anti-mildew, anti-bacteria and deodorizing capabilities from natural cellulose” to produce nonwoven fabrics with anti-mildew, anti-bacteria and deodorizing capability from natural cellulose so that it not only has advantages in low manufacturing cost without environmental pollution but also features good degree of air permeability and degree of water absorption. Thereby, it meet medical and industrial application requirements such as apparels, sanitary and medical materials, filtrating materials, wiping materials for biomedical and optoelectronic wafers and the like because its waste is biodegradable without any harmful effect in environment.
For further disclose the fabricating process and efficacy, detailed description for some preferred exemplary embodiments with associated drawings is presented below. Please refer to
a. Material Selection and Preparation: Select wood pulp as raw material, preferably pulp cellulose of staple or filament with cellulose content being over 85% and degree of polymerization (DP) being between 500˜1200;
b. Solvent adding and Mucilage Formation: Put N-methylmorpholine N-oxide (NMMO) (whose chemical structure as shown in
c. Dope Blending and Dissolution: Put and blend modified and nano-miniaturized natural chitosan (whose chemical structure as shown in
d. Meltblown and Filament Formation: By meltblown method, the dope D is extruded out of spinnerets 3 to form filament bundle as shown in
e. Coagulation, Web and Fabric Formation: By means of ejecting mist aerosol of water, the filament bundle is coagulated with regeneration; After post treatments of water rinsing, hydro-entangled needle punching, drying, winding-up and the like have been orderly applied (as shown in
Wherein, for the N-methylmorpholine N-oxide (NMMO) in above step b, the concentration thereof is 50%˜75% with nontoxic nature so that it can be recycled with low consumption rate via filtration, decolor, and condensation under low pressure distillation after having been drained out in water rinse process with rate of recovery up to over 99.5%. Thereby, it completely complies with the criteria of the environmental protection because it not only can reduce the manufacturing cost but also will not incur any harmful pollution to the environment.
Wherein, for the natural chitosan of macromolecule in above step c, the primary material source thereof is wasted horny shells of shrimp and crab by chemical treatment with following steps: firstly, by acid and alkali treatment to separate chitin out, then purify it; secondly, by hot alkali treatment for excluding N-acetyl group to form chitosan; and finally, by NaOH treatment with suitably controlled concentration, heating temperature and time to perform deacetylation on the chitosan in range of 50%˜99% so that final chitosan product with molecular weight in range of 10,000˜520,000 is produced.
Moreover, for the dope D in above step c, the content percentage of cellulose thereof is 6 wt %˜15 wt %, the viscosity thereof is 300˜3000 poise, the light transmittance index thereof is 1.470˜1.495, and the melting Index thereof is 400˜1000 while the content percentage of chitosan in cellulose fiber is 0.1 wt %˜7.0 wt %.
In the above step c, for the acid and alkali treatment, the acid is hydrochloric acid (HCl), sulfuric acid (H2SO4) and the like of strong acid while the alkali is sodium hydroxide (NaOH), potassium hydroxide (KOH) and the like of strong base.
Besides, in the above step c, the method for the property modification and nano-miniaturization of the natural chitosan generally comprises following steps: firstly, by molecular weight control technique, degrade the chitosan to obtain the interim chitosan of middle and low molecular weight; secondly, by quaternary ammonium salt/synthesis, further modify the interim chitosan of middle and low molecular weight to perform preliminary property modification; and finally, by sol-gel method, directly modify chitosan to finish the property modification and nano-miniaturization so that final chitosan product features in excellent bio-compatibility and bio-activity.
Furthermore, in the above step e, the winding-up speed is 2˜200 meters per minute.
For further proving the features and efficacy of the present invention, some exemplary experimental cases having been performed with measured data are described as following.
a. Select pulp with degree of polymerization for the cellulose thereof being 650 as raw material;
b. Select chitosan with range in degree of deacetylation for chitin being 87%˜95% such that range in mixing percentage thereof being 0.1 wt %˜5.0 wt % after property modification and nano-miniaturization; then, add the chitosan with solvent N-methylmorpholine N-oxide (NMMO) of suitable content percentage into prepared pulp to form mixed cellulose mucilage;
c. Dehydrate the dope via heating up to temperature between 80 degree of Celsius and 120 degree of Celsius (80° C.˜120° C.) by vacuum thin film evaporator for 5 minutes to decrease water content thereof down to 5˜13% so that a homogenized mucilaginous dope is formed with composition of dope shown as in TABLE 1;
d. By meltblown method, the dope is fed into a meltblown machine via a measuring pump then extruded out of spinnerets to form filament bundle then web of nonwoven; and
e. By coagulation with regeneration of ejecting mist aerosol of water as well as applying post treatments of water rinsing, hydro-entangled needle punching, drying, winding-up and the like, then final products with composition of dope for samples 1 through 12 shown as in TABLE 1 are produced.
a. Select pulp with degree of polymerization for the cellulose thereof being 1050 as raw material;
b. Select chitosan with range in degree of deacetylation for chitin being 87%˜95% such that range in mixing percentage thereof being 0.1 wt %˜5.0 wt % after property modification and nano-miniaturization; then, add the chitosan with solvent N-methylmorpholine N-oxide (NMMO) of suitable content percentage into prepared pulp to form mixed cellulose mucilage;
c. Dehydrate the dope via heating up to temperature between 80 degree of Celsius and 120 degree of Celsius (80° C.˜120° C.) by vacuum thin film evaporator for 5 minutes to decrease water content thereof down to 5˜13% so that a homogenized mucilaginous dope is formed with composition of dope shown as in TABLE 1;
d. By meltblown method, the dope is fed into a meltblown machine via a measuring pump then extruded out of spinnerets to form filament bundle then web of nonwoven; and
e. By coagulation with regeneration of ejecting mist aerosol of water as well as applying post treatments of water rinsing, hydro-entangled needle punching, drying, winding-up and the like, then final products with composition of dope for samples 13 through 24 shown as in TABLE 2 are produced.
Testing fungus (or microorganism specimen):
Adopt Staphylococcus aureus subsp. Aureus10451 as experiment fungus.
Reagent:
Take 0.2 ml of testing fungus solution, which incubate said fungus up to 5˜70E+5 (number/ml), to mix with sterilized buffer saline for violently shaking 30 times so that the testing fungi spread over the solution, which is properly diluted into reagent.
Experiment:
Take 1 ml of foregoing reagent for agar broth incubation under temperature condition of 35 degree of Celsius (35° C.) for 48 hours.
Calculation:
Count the growth number of the incubated fungi aforesaid to figure out the actual fungus number on the sample by calculation of the dilution multitude and volume.
Assay:
Repeat above experiment for 6 times and average the total fungus number for each experiment. The resulting Increment or decrement, which is calculated by following formula, can be used for evaluating the antifungal effect of each sample:
Where,
According to the experiment results, the sample has antifungal effect if the increment exceeds 1.6. The assay results for each sample (namely samples 1 through 24) are shown in the TABLE 3 below.
Testing bacteria:
Adopt type (A) bacteria: Methicillin Resistant Staphyloccous Aureus (MRSA) (ATCC 6538P) and type (B) bacteria: Klebsiella pheumoniae (ATCC 4352) as two experiment bacteria.
Principle:
The ordinary chitosan is the derivative of the chitin through deacetylation. The chitosan is a natural non-toxic high polymer with bacteriostatic and biodegradable feature to defend against the fungi and microbes because it is positively charged to readily bind with negatively charged surfaces such as protein. The suppressing ability to the bacteria and fungi of the chitosan comes from its molecular weight and functional radical, which will bond with aluminate acid or silicic acid on the phospholipid substance, so that the activity of the microbe is curbed. The oligmer of chitosan can penetrate the biological cell membrane to repress the duplicating of the RNA.
Testing object:
Take modified chitosan of the present invention as anti-bacteria sample to test whether it has anti-bacteria function of bacteriostatic capability and bactericidal capability.
TABLES 4 and 5 list testing results in anti-bacteria capability of cellulose nonwoven, wherein chitosan is contained therein while the anti-bacteria capability includes bacteriostatic capability and bactericidal capability.
Foundation:
The experiment is in accordance with JIS L1902-1998 Quantitative Method.
Testing bacteria:
Adopt type (A) bacteria: Methicillin Resistant Staphyloccous Aureus (MRSA) (ATCC 6538P) and type (B) bacteria: Klebsiella Pheumoniae (ATCC 4352) as two experiment bacteria.
Experiment:
The incubated bacteria concentration within 1.0±0.3 E+5 (number/ml) means valid for the experiment.
Ma denotes bacteria number of un-processed sample in immediate count upon cleansing without incubation.
Mb denotes bacteria number of un-processed sample after being incubated for 18˜24 hours.
Mc denotes bacteria number of processed sample after being incubated for 18˜24 hours.
Calculating formula:
The growing activity value of the bacteria (BGA) is calculated by following formula such that BGA>1.5 means valid of the experiment.
Evaluating criterion:
According to criterion from the Japan Association of Fiber Evaluating Technology for new function (JAFET), the anti-bacteria function is that:
The testing sample has bacteriostatic effect if its bacteriostatic value BSN>2.2.
The testing sample has bactericidal effect if its bactericidal value BKN>0.
And, the numerical (1.3 E+4) denotes 13,000 with analog below.
Each testing result in anti-bacteria capability for each respective sample of cellulose nonwoven is listed in TABLES 4 and 5, wherein chitosan is contained therein while the anti-bacteria capability includes bacteriostatic capability and bactericidal capability.
Evaluating inference:
From TABLES 4 and 5, the sample cellulose nonwoven containing the modified chitosan of the present invention has excellent anti-bacteria capability both in bacteriostatic and bactericidal effects for both of bacteria of Methicillin Resistant Staphyloccous Aureus (MRSA) (ATCC 6538P) and Klebsiella Pheumoniae (ATCC 4352).
The experiment for assaying deodorizing effect is on the testing basis in absorption of the ammonia odor.
Testing method is that first fill the ammonia gas of specific concentration into the air-tight bottle; next put the nonwoven with modified chitosan of specific quantity into the same bottle aforesaid for 15 minutes absorption; then measure the gas concentration in the nonwoven with chitosan before and after putting into the bottle by gas chromatograph (GC).
The ratio of the deodorizing property for ammonia absorption rate (Aa) is calculated by following formula.
Where,
Each testing result in deodorizing capability for each respective sample of cellulose nonwoven is listed in TABLE 6.
Testing method is to launder each sample under condition in 70° C. hot water with 5 g/L laundry detergent for 45 minutes. The experimental result for testing the anti-mildew, anti-bacteria and deodorizing capabilities for each sample by foregoing laundering method for 10 times is shown in the TABLES 7, 8 and 9 below.
From manifestation by experimental data and assess results for anti-mildew and anti-bacteria capability of the cellulose nonwoven fabric with chitosan in the above TABLES 3 through 5, the nonwoven fabric of natural cellulose produced by the method of the present invention really has anti-mildew and anti-bacteria capability if mixing percentage of nano-miniaturized chitosan contain therein is over 0.5 wt %. Besides, all these exemplary embodiments prove that the nonwoven fabric of natural cellulose with nano-miniaturized chitosan produced by the method of the present invention really has anti-mildew and anti-bacteria capability.
From manifestation by experimental data and assess results for deodorizing capability of the cellulose nonwoven fabric with chitosan in the above TABLE 6, the nonwoven fabric of natural cellulose produced by the method of the present invention really has deodorizing capability via illustrative rate of ammonia absorption being over 50% if mixing percentage of nano-miniaturized chitosan contain therein is over 0.5 wt %.
From manifestation by experimental data and assess results for anti-mildew, anti-bacteria and deodorizing capability of the cellulose nonwoven fabric with chitosan under condition of 10 times laundering in 70° C. hot water with 5 g/L detergent for 45 minutes in the above TABLES 7 through 9, the nonwoven fabric of natural cellulose produced by the method of the present invention can still keep about 90% of anti-mildew, anti-bacteria and deodorizing capability as that before laundering for mixing percentage of nano-miniaturized chitosan contain therein is over 0.5 wt %. Therefore, all foregoing exemplary embodiments demonstrate that the nonwoven fabric of natural cellulose with nano-miniaturized chitosan produced by the method of the present invention really has long-term effects in anti-mildew, anti-bacteria and deodorizing capability, which much far exceeds that of the conventional nonwoven fabrics sold in the market as they are only coated or added with anti-bacterias.
In conclusion, the nonwoven fabric of natural cellulose, which is produced by the method of the present invention, indeed has the effects in anti-mildew, anti-bacteria and deodorizing capability. Thereby, it is not only conducive to promote the product application field and decrease the infection probability for human beings, agricultural and fishery livestock as well as by microorganism but also well for reducing the odor creating. Thus, it is really good for adoption in mass production in agricultural and fishery business.
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