Patent Description:
Collagen mainly exists in the connective tissue of mammals and is the main component of ligaments. It is also the major component of extracellular matrix. Moreover, in addition to being non-toxic to humans, collagen has biodegradable, biocompatible, and low antigenic properties and has excellent effects of stanching bleeding, promoting angiogenesis, promoting wound healing, and preventing wound scar formation. Therefore, collagen has a high value in the fields of medical care and beauty care.

Collagen can be prepared into different types (for example, fibers, plates, sponges, granules, etc.) by cross-linking to making it easy to process with other molecules. However, at present, artificial fibers and/or plastic products containing collagen are mostly obtained by coating or immersing of collagen solutions, and the artificial fibers and/or plastic products containing collagen obtained therefrom have problems with the collagen being easily worn out or lost. Moreover, at present, medical textiles on the market are mainly cotton, polypropylene (PP) and other materials, and there are no biomedical material or medical application textiles developed for bio-functional designs.

Therefore, there is a need for a collagen-containing artificial fiber and/or plastic product in which the collagen will not fall off.

Examples of fibers made from compositions containing a modified polyolefin and collagen are provided in <CIT> and in the article by <NPL>.

The article by <NPL>, describes polylactic/collagen fibers and non-woven mats, wherein the fibers are obtained by spinning a solution containing collagen type I and polylactic.

<CIT> discloses a composition, which can be used for making woven and non-woven fabrics or spun bonded fibers, comprising at least one biodegradable aliphatic-aromatic copolyester obtainable starting from mixtures comprising at least one diol, at least one polyfunctional aromatic acid and at least two aliphatic dicarboxylic acids, and at least one polymer of natural origin, which can be collagen.

<CIT> discloses fibers obtained by dissolving and decomposing animal fibers, which can be collagen fibers collected from animal leather in an acid solution; adding nylon to the resulting solution with stirring to completely mix and dissolve the nylon therewith; thereafter reducing the solubility of the protein and nylon mixture in the solution thus prepared to precipitate a high molecular bonded product of protein and nylon molecules; and subjecting the high molecular bonded product thus dried to melt spinning.

<CIT> discloses a copolyester material with peptide formed by the polymerization of ethylene glycol, collagen, and terephthalic acid, which can be used to spun into fibers for weaving, making clothes, bedding, curtains, sheets and carpets.

<CIT> discloses a composition to make fibers by melt spinning, and textiles, containing collagen and a modified polyethylene terephthalate, which has a lower melting point to avoid decomposition of the collagen.

The article by <NPL>, describes fibers obtained by electrospinning a solution containing PET and collagen type I.

The present invention discloses a collagen containing non-woven fabric, which is made from at least one plastic masterbatch by a meltblowing technique, wherein the at least one plastic masterbatch comprises a collagen containing-plastic masterbatch of which the composition comprises:.

In an embodiment of the present invention the non-woven fabric is made from at least one plastic masterbatch, which further comprises a collagen-free plastic masterbatch, wherein composition of the collagen-free plastic masterbatch comprises another thermoplastic polymer. In a particular aspect of this embodiment, the weight ratio of the collagen containing-plastic masterbatch to the collagen-free plastic mastermatch is <NUM>:<NUM>-<NUM> and in a further aspect of this embodiment, the thermoplastic polymer and the other thermoplastic polymer are the same.

A further embodiment of the present invention discloses a medical appliance, comprising the collagen containing non-woven fabric. In a particular aspect of this embodiment, the medical appliance comprises a hemostatic gauze or a dressing.

A detailed description is given with reference to the accompanying drawings.

In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, that one or more aspects of the present disclosure may be practiced without these specific details.

The present invention provides a collagen containing non-woven fabric, which is made from at least one plastic masterbatch by a meltblowing technique. In the collagen containing-plastic masterbatch mentioned above, the collagen content is about <NUM>-<NUM> wt%, such as <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%. A composition of the foregoing collagen containing-plastic masterbatch comprises a thermoplastic polymer and a collagen, wherein the collagen is uniformly distributed in the thermoplastic polymer. By making the collagen in the plastic masterbatch be uniformly distributed in the thermoplastic polymer, the collagen in the plastic product formed by the plastic masterbatch may not be easily damaged due to cleaning or other external forces.

Examples of the thermoplastic polymer can be nylon, polyethylene terephthalate (PET), polypropylene (PP), acrylic acid or spandex. Examples nylon may comprise nylon <NUM>, but they are not limited thereto. Nylon <NUM> is linear polycaprolactam. Nylon <NUM> has high mechanical strength, high temperature resistance (HDT=<NUM>), corrosion resistance (well chemical resistance), high lubricity, low surface friction and high tensile strength and impact strength. According to the present invention, the thermoplastic polymer in the collagen containing-plastic masterbatch mentioned above is polyethylene terephthalate.

Moreover, the type of the collagen in the collagen containing-plastic masterbatch of the present disclosure also has no specific limitation. In one embodiment, the foregoing collagen may have heat resistance to about <NUM>-<NUM>. Furthermore, in one embodiment, the foregoing collagen may comprise type I collagen.

The foregoing collagen containing-plastic masterbatch of the present invention is formed by a melt polymerization method.

According to the present invention, the foregoing melt polymerization method used for forming the collagen containing-plastic masterbatch comprises the following steps:.

First, a melting procedure is performed on at least one monomer raw material constituting the thermoplastic polymer to obtain a melted monomer raw material.

The temperature of the melting procedure may depend on the monomer raw material which is adopted. The temperature of the melting procedure may be about <NUM>-<NUM>. As an example not according to the present invention, when the foregoing monomer raw material is a monomer raw material of nylon, the temperature of the melting procedure may be about <NUM>-<NUM>: for example the monomer raw material of nylon can be nylon <NUM>, i.e. caprolactam, and the temperature of the melting procedure may be about <NUM>-<NUM>, such as about <NUM>. According to the present invention, the monomer raw material is a monomer raw material of polyethylene terephthalate, and it may comprise pure terephthalic acid (PTA) and ethylene glycol (EG), and the temperature of the melting procedure may be about <NUM>-<NUM>, such as about <NUM>.

There is no specific limitation for time required for the melting procedure, as long as the monomer raw material can be melted. The time required for the melting procedure may be about <NUM>-<NUM> hours, such as about <NUM>-<NUM> hours, but it is not limited thereto.

Next, a heating and mixing procedure is performed on the foregoing melted monomer raw material and collagen to form a mixture. The weight ratio of the collagen to the at least one monomer raw material is about <NUM>:<NUM>-<NUM>, such as <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>. In one embodiment, the weight ratio of the collagen to the at least one monomer raw material may be about <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM> or <NUM>:<NUM>.

Furthermore, similarly, the temperature of the foregoing heating and mixing procedure may depend on the monomer raw material which is adopted. The temperature of the foregoing heating and mixing procedure is about <NUM>-<NUM>. As an example not according to the present invention, when foregoing monomer raw material is a monomer raw material of nylon, the temperature of heating and mixing procedure may be about <NUM>-<NUM>: for example the monomer raw material of nylon can be nylon <NUM>, i.e. caprolactam, and the temperature of the heating and mixing procedure may be about <NUM>-<NUM>, such as about <NUM>. According to the present invention, the foregoing monomer raw material is a monomer raw material of polyethylene terephthalate, and it may comprise pure terephthalic acid and ethylene glycol, and the temperature of the heating and mixing procedure may be about <NUM>-<NUM>, such as about <NUM>.

In addition, there is not specific limitation for the heating and mixing procedure, as long as the melted monomer raw material and the collagen can be uniformly mixed. The time required for the heating and mixing procedure may be about <NUM>-<NUM> hours, such as about <NUM>-<NUM> hours, but it is not limited thereto.

After that, according to the present invention, a polymerization reaction is performed on a mixture of the melted monomer raw material and the collagen to form the foregoing thermoplastic polymer and to make sure that the collagen is uniformly distributed in the thermoplastic polymer to form a collagen-containing polymer. Similarly, the temperature of the foregoing polymerization reaction may depend on the monomer raw material which is adopted.

In one embodiment, the temperature of the polymerization reaction mentioned above is about <NUM>-<NUM>. As an example not according to the present invention, when the foregoing monomer raw material is a monomer raw material of nylon, and the temperature of the polymerization reaction may be about <NUM>-<NUM>: for example the monomer raw material of nylon can be nylon <NUM>, i.e. caprolactam, and the temperature of the polymerization reaction may be about <NUM>-<NUM>, such as about <NUM>. According to the present invention, the foregoing monomer raw material is a monomer raw material of polyethylene terephthalate, and it may comprise pure terephthalic acid and ethylene glycol, and the temperature of the polymerization reaction may be about <NUM>-<NUM>, such about <NUM>.

Similarly, the time required for the polymerization may depend on the monomer raw material which is adopted. The time required for the polymerization may be about <NUM>-<NUM> hours, such as about <NUM> hours, about <NUM> hours, but it is not limited thereto.

After that, according to the present invention, a granulation procedure is performed on the obtained collagen-containing polymer to form the collagen containing-plastic masterbatch of the present disclosure. The granulation procedure mentioned above may use any procedure that can divide the obtained polymer into granular finished products and have no specific limitation, for example, a granulation procedure well known in the art can be used. The granulation procedure may be a procedure in which the obtained collagen-containing polymer is cut into granules by a slicer. The granulation procedure may be a procedure in which the obtained collagen-containing polymer is sent to an extruding and mixing granulator and mixed and extruded to form pellets. The particle size of the obtained collagen containing-plastic masterbatch depends on the requirements and has no specific limitation. The particle size of the collagen containing-plastic masterbatch may be about <NUM>-<NUM>.

In addition, the foregoing melt polymerization method used for forming the collagen containing-plastic masterbatch may further comprise a step of adding water, a polymerization regulator and an external lubricant or adding at least one catalyst to the foregoing melted monomer raw material between performing the foregoing melting procedure and performing the foregoing heating and mixing procedure. The weight ratio of water to the monomer raw material may be about <NUM>:<NUM>-<NUM>, such as <NUM>:<NUM>-<NUM>. The weight ratio of water to the monomer raw material may be about <NUM>:<NUM>, but it is not limited thereto. The weight ratio of the polymerization regulator to the monomer raw material may be about <NUM>:<NUM>-<NUM>, such as <NUM>:<NUM>-<NUM>. The weight ratio of the polymerization regulator to monomer raw material may be about <NUM>:<NUM>, but it is not limited thereto. The weight ratio of the external lubricant to the monomer raw material may be about <NUM>:<NUM>-<NUM>, such as <NUM>:<NUM>-<NUM>. The weight ratio of the external lubricant to the monomer raw material may be about <NUM>:<NUM>, but it is not limited thereto. The weight ratio of the catalyst to the monomer raw material may be about <NUM>:<NUM>-<NUM>, such as <NUM>:<NUM>-<NUM>. The weight ratio of the catalyst to the monomer raw material may be about <NUM>:<NUM>-<NUM>.

The polymerization regulator mentioned above may comprise, but is not limited to, acids, such as acetic acid, adipic acid, or dodecyl mercaptan, etc. Moreover, the external lubricant mentioned above may comprise fatty acid amide, oleamide or stearic acid, etc., but it is not limited thereto. Examples of the at least one catalyst mentioned above may comprise, but are not limited to, antimony trioxide (Sb<NUM>O<NUM>), titanium butoxide (Ti(Obu)<NUM>), antimony acetate (Sb(AC)<NUM>), ethylene glycol antimony (Sb<NUM>(EG)<NUM>) and any combination thereof.

Furthermore, the foregoing melt polymerization method used for forming the collagen containing-plastic masterbatch may further comprise performing an extraction procedure on the obtained collagen containing-plastic masterbatch after the granulation procedure, and performing a drying procedure on the collagen containing-plastic masterbatch after the extraction procedure.

The foregoing extraction procedure is used to remove oligomers, remaining monomers, and/or other impurities in the masterbatch to avoid the oligomers, remaining monomers, etc. in the masterbatch from being oxidized to produce bubbles during the subsequent manufacture of desired plastic products and affecting the quality of the product. The extraction procedure may be performed by adding the obtained collagen containing-plastic masterbatch into hot water, and the temperature of the hot water may be about <NUM>-<NUM>, but it is not limited thereto. Moreover, since the masterbatch after the extraction procedure will have a higher moisture content, for example, equal to or more than <NUM>%, a drying procedure is performed after the extraction procedure to avoid the masterbatch from subsequent thermal oxidation. The foregoing drying procedure may be performed by drying the collagen containing-plastic masterbatch after the extraction process in a vacuum environment at a temperature of about <NUM>-<NUM>, such as <NUM>.

In addition, the foregoing melt polymerization method used for forming the collagen containing-plastic masterbatch may further comprise the step of adding water, a polymerization regulator and an external lubricant or adding at least one catalyst to the foregoing melted monomer raw material mentioned above between performing the foregoing melting procedure and performing the foregoing heating and mixing procedure, and further comprise the extraction procedure mentioned above and the drying procedure mentioned above after the granulation procedure.

As an example not according to the present invention, in any melt polymerization method used for forming the collagen containing-plastic masterbatch of the present disclosure mentioned above, the at least one monomer raw material constituting the thermoplastic polymer is caprolactam, and the collagen is type I collagen. Moreover, the weight ratio of the type I collagen to the caprolactam may be about <NUM>:<NUM>-<NUM>, such as about <NUM>:<NUM>, <NUM>:<NUM>, <NUM>: <NUM>, <NUM>:<NUM>, but it is not limited thereto.

Accoding to a specific embodiment of the present invention, in any melt polymerization method used for forming the collagen containing-plastic masterbatch mentioned above, the at least one monomer raw material constituting the thermoplastic polymer comprises pure terephthalic acid and ethylene glycol, and the collagen is type I collagen. Moreover, in this specific embodiment, the weight ratio of the pure terephthalic acid to the ethylene glycol may be about <NUM>:<NUM>-<NUM>, such as about <NUM>:<NUM>, but it is not limited thereto. Furthermore, in this specific embodiment, the weight ratio of the type I collagen to the at least one monomer raw material is about <NUM>:<NUM>-<NUM>, such as about <NUM>:<NUM>, <NUM>:<NUM> or <NUM>:<NUM>.

Based on the foregoing, the present invention discloses a collagen containing non-woven fabric, which is made from at least one plastic masterbatch by a meltblowing technique, wherein the at least one plastic masterbatch, wherein the least one plastic masterbatch is as disclosed adove.

Furthermore, herein is also disclosed a collagen containing-fiber. The foregoing collagen containing-fiber may be made from at least one plastic masterbatch by a melt spinning technique, and the at least one plastic masterbatch comprises any collagen containing-plastic masterbatch mentioned above, but it is not limited thereto. The collagen content of the collagen containing-fiber may be about <NUM>-<NUM> wt%, such as <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, but it is not limited thereto.

The "melt spinning technique" described herein may be any melt spinning technique known in the art, for example, after the masterbatch (or polymer) is melted, it is drawn through a spinneret to make it in the form of line, and then is cooled and cured, but the melt spinning technique is not limited thereto. The temperature of the melting mentioned above has no specific limitation, and may depend on the material of the masterbatch, for example, the foregoing temperature of melting may be about <NUM>-<NUM>. The foregoing temperature of melting may be about <NUM>.

The at least one plastic masterbatch mentioned above may be any collagen containing-plastic masterbatch of the present disclosure mentioned above. In an example the thermoplastic polymer of the collagen containing-plastic masterbatch mentioned above is nylon <NUM>. In this specific embodiment, the collagen content of the collagen containing fiber may be about <NUM>-<NUM> wt%, such as <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, but it is not limited thereto.

The at least one plastic masterbatch mentioned above may further comprise a collagen-free-plastic masterbatch, and the composition of this collagen-free-plastic masterbatch comprise another thermoplastic polymer. Examples of this another thermoplastic polymer may comprise, but is not limited to nylon, polyethylene terephthalate, polypropylene, acrylic acid and spandex. In the at least one plastic masterbatch mentioned above, the weight ratio of the collagen containing-plastic masterbatch to the collagen-free-plastic masterbatch may be <NUM>:<NUM>-<NUM>, but it is not limited thereto. In the collagen containing-fiber, the collagen content may be about <NUM>-<NUM> wt%, such as <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, but it is not limited thereto.

The at least one plastic masterbatch mentioned above may further comprise collagen-free-plastic masterbatch, the thermoplastic polymer of the collagen containing-plastic masterbatch and the other thermoplastic polymer of the collagen-free-plastic masterbatch may be the same or different. The thermoplastic polymer of the collagen containing-plastic masterbatch and the other thermoplastic polymer of the collagen-free-plastic masterbatch can be the same. In an example the thermoplastic polymer of the collagen containing-plastic masterbatch and the other thermoplastic polymer of the collagen-free-plastic masterbatch are both nylon, and a monomer raw material constituting the nylon is caprolactam. In the specific example mentioned above, in the collagen containing-fiber, the collagen content may be about <NUM>-<NUM> wt%, such as <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, but it is not limited thereto.

Moreover, herein it is disclosed a textile, which is made from any foregoing collagen containing-fiber of the present disclosure.

The present invention provides a collagen containing non-woven fabric. The foregoing collagen containing non-woven fabric is made from at least one plastic masterbatch by a meltblowing technique, and the at least one plastic masterbatch mentioned above comprises a collagen containing-plastic masterbatch of which the composition comprises:.

The collagen content of the collagen containing non-woven fabric may be about <NUM>-<NUM> wt%, such as <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, but it is not limited thereto.

The "meltblowing technique" described herein may be any meltblowing technique known in the art, for example, the masterbatch (or polymer) is melted and ejected from a spinneret to make it in the form of net, and then is cooled and cured. The temperature of the melting mentioned above has no specific limitation, and may depend on the material of the masterbatch, for example, the foregoing temperature of melting may be about <NUM>-<NUM>. The foregoing temperature of melting may be about <NUM>.

According to the present invention, the thermoplastic polymer of the collagen containing-plastic masterbatch mentioned above is polyethylene terephthalate and the collagen content of the collagen containing non-woven fabric is about <NUM>-<NUM> wt%, such as <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%.

In one embodiment of the present invention, the at least one plastic masterbatch mentioned above may further comprise a collagen-free-plastic masterbatch, and the composition of this collagen-free-plastic masterbatch comprise another thermoplastic polymer. Examples of this another thermoplastic polymer may comprise, but is not limited to, nylon, polyethylene terephthalate, polypropylene, acrylic acid and spandex. In the at least one plastic masterbatch mentioned above, the weight ratio of the collagen containing-plastic masterbatch of the present disclosure to the collagen-free-plastic masterbatch may be <NUM>:<NUM>-<NUM>, but it is not limited thereto. Moreover, in this embodiment, in the collagen containing non-woven fabric, the collagen content may be about <NUM>-<NUM> wt%, such as <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, but it is not limited thereto.

In addition, in the embodiment in which the at least one plastic masterbatch mentioned above may further comprise collagen-free-plastic masterbatch, the thermoplastic polymer of the collagen containing-plastic masterbatch and the other thermoplastic polymer of the collagen-free-plastic masterbatch may be the same or different. In one embodiment, the thermoplastic polymer of the collagen containing-plastic masterbatch and the other thermoplastic polymer of the collagen-free-plastic masterbatch are the same. In one specific embodiment, the thermoplastic polymer of the collagen containing-plastic masterbatch and the other thermoplastic polymer of the collagen-free-plastic masterbatch are both polyethylene terephthalate, and a monomer raw material constituting the polyethylene terephthalate may comprise pure terephthalic acid and ethylene glycol. In the specific embodiment mentioned above, in the collagen containing non-woven fabric, the collagen content may be about <NUM>-<NUM> wt%, such as <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, but it is not limited thereto.

Furthermore, not according to the present invention, it is also disclosed a collagen containing plastic product which is made from at least one plastic masterbatch by a compression molding, calendering, extrusion molding or injection molding technique, and the least one plastic masterbatch described therein is the at least one plastic masterbatch adopted by the collagen containing-fiber or non-woven fabric of the present disclosure mentioned above.

In addition, herein it is also disclosed a medical appliance, commodity or clothing. In a particular embodiment according to the present invention, a medical appliance, comprising the collagen containing non-woven fabric of the present invention is disclosed.

The medical appliance according to the present invention, has the effect of stanching bleeding and/or promoting wound healing because it contains collagen. Examples of the medical appliance mentioned above may comprise, but are not limited to medical gauze (such as hemostatic gauze), various dressings, band-aid (such as the gauze part of the band-aid), surgical suture. In a particular aspect of the present invention the medical appliance comprises a hemostatic gauze or a dressing. Moreover, examples of the commodity may comprise a non-woven facial mask, a sanitary pad, a diaper, but they are not limited thereto. Examples of clothing may comprise underwear, corset, girdle, silk stockings, but they are not limited thereto. The haemostatic gauze formed with the collagen fiber or non-woven fabric has excellent hemostatic effect.

Although collagen has biodegradable, biocompatible, and low antigenic properties and has excellent effects of stanching bleeding, promoting angiogenesis, promoting wound healing, and preventing wound scar formation, if only collagen dressings are used as general wounds dressings, there will be a problem of excessive cost. In the present invention, collagen and polyethylene terephthalate, are polymerized to form, for example, collagen-polyethylene terephthalate gauze which can adsorb blood and tissue fluid. Moreover, because polyethylene terephthalate, have properties of smooth surfaces and small pores, they are not susceptible to bacterial growth. Therefore, gauze of the present invention can achieve hemostatic effect, and will not cause sticking to the wound. At the same time, it can reduce production costs, and also increase the value of collagen and plastics in medical appliance field and clinical application.

<FIG> shows a flow process of a melt polymerization (granulation) <NUM>. Preparation of collagen-containing nylon <NUM> masterbatch of this example can be referred to <FIG> and interpreted as follows:.

<FIG> shows a flow process for performing melt spinning with a single screw spinning machine <NUM>. Preparation of yarn of collagen containing nylon <NUM> of this example can be referred to <FIG> and interpreted as follows:.

The <NUM> wt% collagen-containing yarn obtained above was woven into silk stockings to obtain silk stockings containing <NUM> wt% collagen (Denier: <NUM>; Spun of yarn: <NUM>).

The <NUM> wt% collagen-containing yarn obtained above was dyed and then woven into socks to obtain dyed socks containing <NUM> wt% of collagen (Denier: <NUM>; Spun of yarn: <NUM>) (referring to <FIG>).

The silk stockings were water-washed with an operator wearing a plastic glove to perform the usual hand wash. The silk stockings were immersed in <NUM> of pure water (ddH<NUM>O) to wash by hand, and then the silk stocking samples were squeezed to dry. For different silk stocking samples, the above steps were repeated for different times to obtain silk stocking samples with different number of times for washing (<NUM> time, <NUM> time, <NUM> times, <NUM> tomes, <NUM> times, and <NUM> times). After that, the silk stocking samples were vacuum dried at <NUM>.

<NUM> of the dried silk stocking sample mentioned above was placed in a test tube and <NUM> of sulfuric acid (H<NUM>SO<NUM>; <NUM>) was added therein. After that, the opening of the tube was sealed and the tube was heated at <NUM> for <NUM> hours. After heating, the test tube was placed at room temperature for cooling. Then, <NUM> of sodium hydroxide (NaOH; <NUM>) was added to the tube and mixed evenly with the contents in the tube. Next, <NUM>µl of liquid was taken from the tube to a new tube. The new tube was vacuum dried at <NUM> for <NUM> hours. Then, <NUM> of <NUM>% alcohol was added to this test tube and mixed evenly with the contents in this tube. <NUM>µl of liquid was taken from this tube to another new tube and vacuum dried for <NUM> hours. After that, the dry distillated sample was added to <NUM> of citric acid phosphate buffer (pH=<NUM>) (<NUM> times dilution) to obtain a treated sample to be tested.

Since there is currently no standard method for quantifying collagen contained in yarn, in the present disclosure, a method for determining the content of the collagen in the yarn by determining the hydroxyproline (Hyp) content is developed.

Hydroxyproline is the major component of collagen, and thus the collagen content in the sample can be represented by the content of hydroxyproline.

Hydroxyproline standard sample solutions at concentrations of <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and <NUM>µg/ml were prepared. Different concentrations of hydroxyproline standard sample solution and test sample were respectively taken <NUM>µl and added into different wells of a <NUM>-well plate. After that, <NUM>µl/well of chloramine T was added to the <NUM>-well plate and reacted at room temperature for <NUM> minutes. Then, <NUM>µl/well of Ehrlich's reagent (dimethylaminobenzaldhyde, DAMB) was further added to the <NUM>-well plate and reacted at <NUM> for <NUM> minutes. Finally, the absorbance at <NUM> (OD<NUM>) of different concentrations of hydroxyproline standard sample solutions and the sample to be tested was determined by an ELISA reader.

According to the absorbance values at <NUM> (OD<NUM>) corresponding to different concentrations of hydroxyproline, a standard curve of hydroxyproline concentration versus absorbance value of was plotted (referring to <FIG>). Moreover, based on the standard curve, the determined absorbance at <NUM> (OD<NUM>) of the sample to be tested was converted into the hydroxyproline content of the sample to be tested to further determine the collagen content of the sample to be tested.

The residual collagen contents of the silk stocking samples that have been washed a different number of times (<NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and <NUM> times) were measured by the above method to evaluate the water washing resistance of the silk stocking containing collagen. The results are shown in Table <NUM> and <FIG>.

Tables <NUM> and <FIG> clearly show that after being water-washed <NUM> times, the silk stocking woven with the <NUM> wt% collagen-containing yarn of the present disclosure could still retain up to <NUM> wt% or more of collagen. Moreover, even after <NUM> washes with water, silk stocking woven with the <NUM> wt% collagen-containing yarn of the present disclosure could still maintain <NUM> wt% of the collagen.

Accordingly, it is known that a product woven with the <NUM> wt% collagen-containing yarn of the present disclosure has extremely excellent water washing resistance.

The water washing method for the dyed sock samples was the same as the washing method described in "<NUM>. Water washing for silk stocking sample" of "A. Method" of "Reference Example <NUM>-<NUM>-<NUM>: Test of water washing resistance of silk stockings".

The method for acid hydrolysis treatment for dyed sock sample samples was the same as the treat method described in "<NUM>. Acid hydrolysis treatment for silk stocking sample" of "A. Method" of "Reference Example <NUM>-<NUM>-<NUM>: Test of water washing resistance of silk stockings".

The quantifying method for collagen contained in the yarn of dyed sock sample can be referred to the quantifying method recited in "<NUM>. Quantification of collagen contained in the yarn of silk stocking sample" of "A. Method" of "Reference Example <NUM>-<NUM>-<NUM>: Test of water washing resistance of silk stockings".

The residual collagen contents of the dyed sock samples that have been washed a different number of times (<NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and <NUM> times) were measured by the above method to evaluate the water washing resistance of the dyed sock containing collagen. The results are shown in Table <NUM> and <FIG>.

Tables <NUM> and <FIG> clearly show that after being water-washed <NUM> times, the dyed sock woven with the <NUM> wt% collagen-containing yarn of the present disclosure could still retain up to <NUM> wt% or more of collagen.

Accordingly, it is known that a product woven with the <NUM> wt% collagen-containing yarn of the present disclosure has excellent water washing resistance.

<FIG> shows a flow process of a melt polymerization (granulation) <NUM>'. Preparation of collagen-containing polyethylene terephthalate masterbatch of this example can be referred to <FIG> and interpreted as follows:.

<FIG> shows a flow process of meltblowing for forming non-woven fabric <NUM>. Preparation of polyethylene terephthalate non-woven fabric containing collagen of this example can be referred to <FIG> and interpreted as follows:.

<FIG> shows the photographs of polyethylene terephthalate masterbatches obtained in the above process respectively containing <NUM> wt%, <NUM> wt%, and <NUM> wt% collagen ((A) <NUM> wt% collagen; (B) <NUM> wt% collagen; (C) <NUM> wt% collagen).

<NUM> of polyethylene terephthalate masterbatches containing <NUM> wt%, <NUM> wt% or <NUM> wt% collagen were placed in a test tube and <NUM> of sulfuric acid (H<NUM>SO<NUM>; <NUM>) was added therein. After that, the opening of the tube was sealed and the tube was heated at <NUM> for <NUM> hours. After heating, the test tube was placed at room temperature for cooling. Then, <NUM> of sodium hydroxide (NaOH; <NUM>) was added to the tube and mixed evenly with the contents in the tube. Next, <NUM>µl of liquid was taken from the tube to a new tube. The new tube was vacuum dried at <NUM> for <NUM> hours. Then, <NUM> of <NUM>% alcohol was added to this test tube and mixed evenly with the contents in this tube. <NUM>µl of liquid was taken from this tube to another new tube and vacuum dried for <NUM> hours. After that, the dry distillated sample was added to <NUM> of citric acid phosphate buffer (pH=<NUM>) (<NUM> times dilution) to obtain a treated sample to be tested.

Samples to be tested were respectively taken <NUM>µl and added into different wells of a <NUM>-well plate. After that, <NUM>µl/well of chloramine T was added to the <NUM>-well plate and reacted at room temperature for <NUM> minutes. Then, <NUM>µl/well of Ehrlich's reagent (dimethylaminobenzaldhyde, DAMB) was further added to the <NUM>-well plate and reacted at <NUM> for <NUM> minutes. Finally, the absorbance at <NUM> (OD<NUM>) of different concentrations of hydroxyproline standard sample solutions and the sample to be tested was determined by an ELISA reader.

Based on the standard curve shown in <FIG>, the determined absorbance at <NUM> (OD<NUM>) of the sample to be tested was converted into the hydroxyproline content of the sample to be tested to further determine the collagen content of the sample to be tested.

The actual collagen contents of the above-obtained polyethylene terephthalate masterbatches containing <NUM> wt%, <NUM> wt%, and <NUM> wt% collagen were determined by the foregoing method. The results are shown in <FIG> and Table <NUM>.

Table <NUM> and <FIG> clearly show that masterbatches containing the three collagen contents produced by the process of the present disclosure have actual collagen contents similar to the theoretical collagen contents thereof. In the polyethylene terephthalate masterbatch containing <NUM> wt% and <NUM> wt% collagen, the actual collagen contents were even higher than the theoretical collagen contents. Therefore, it is known that the process of the present disclosure is a stable process that is able to effectively produce plastic masterbatches with a predetermined collagen content.

Six Sprague-Dawley female rats used in the experiment were purchased from BioLASCO Taiwan Co. , and body weights of the rats were between <NUM> and <NUM>. The rats were divided into two groups which were one control group and one experimental group while there were <NUM> rats in each group. The collagen-polyethylene terephthalate gauze obtained by the above process was used as the testing gauze in the experimental group while commercial collagen-free polyethylene terephthalate nonwoven fabric (China Surgical Dressings Center Co. , Ltd, medicinal gauze-sterilized non-woven mat (material: polyethylene terephthalate, Rayon)) was used as the testing gauze in the control group. All experiments were performed by the same person.

Hemostatic efficacy evaluation for the collagen-polyethylene terephthalate gauze of the present disclosure and common PET gauze was performed by the foregoing method. The results are shown in Table <NUM> and <FIG> ((A) Experimental group: collagen-polyethylene terephthalate gauze; (B) Control group: medicinal gauze).

<FIG> shows bleeding condition of the rat at 30th second in each group. According to <FIG>, it is known that in the experimental group, at the 30th second, a blood clot was produced at the site of arterial trauma in the rat, and coagulation occurred. In contrast, in the control group, at the 30th second, no blood clot was produced at the site of arterial trauma in the rat.

The bleeding stanching time of rats in the experimental group and the control group shown in Table <NUM> were statistically analyzed with student's t-test, and the p value was <NUM>, and thus it was confirmed that statistically significant differences between the experimental group and the control group. Specifically, compared to the commercially medicinal gauze, the collagen-polyethylene terephthalate gauze of the present disclosure can stanch bleeding in a shorter time.

In addition, in the literature, <NPL>. , an object with a bleeding stanching time of less than <NUM> seconds is defined as that it has a hemostatic effect. Since a bleeding stanching time for the collagen-polyethylene terephthalate gauze of the present disclosure is <NUM>±<NUM> seconds, it is determined that the collagen-polyethylene terephthalate gauze of the present disclosure has a hemostatic effect.

Accordingly, the above mentioned tests have confirmed that the collagen-polyethylene terephthalate gauze of the present disclosure has an excellent hemostatic effect and can be used for medical hemostasis.

Claim 1:
A collagen containing non-woven fabric, which is made from at least one plastic masterbatch by a meltblowing technique, wherein the at least one plastic masterbatch comprises a collagen containing-plastic masterbatch of which the composition comprises:
a thermoplastic polymer, wherein the thermoplastic polymer is polyethylene terephthalate; and
a collagen, wherein the collagen is uniformly distributed in the thermoplastic polymer,
wherein in the collagen containing-plastic masterbatch, a content of the collagen is about <NUM>-<NUM> wt%, and
wherein the collagen containing-plastic masterbatch is formed by a melt polymerization method, wherein the melt polymerization method comprises:
(a) performing a melting procedure on at least one monomer raw material constituting the thermoplastic polymer to obtain a melted monomer raw material;
(b) performing a heating and mixing procedure on the melted monomer raw material and the collagen to form a mixture;
(c) performing a polymerization reaction on the mixture to form the thermoplastic polymer and make sure that the collagen is uniformly distributed in the thermoplastic polymer to form a collagen-containing polymer; and
(d) granulating the collagen-containing polymer to form the collagen containing-plastic masterbatch.