JP2008127496A - Resin composition for antibacterial/deodorant article and antibacterial/deodorant fiber and nonwoven fabric obtained therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for antibacterial/deodorant articles which comprises a biodegradable polyester and an aminopolysaccharide, an antibacterial/deodorant nanofiber and a nonwoven fabric prepared therefrom. <P>SOLUTION: The resin composition for biodegradable antibacterial/deodorant articles is prepared by mixing a biodegradable polyester with an aminopolysaccharide in respective solid states and thereafter heating and kneading the resulting mixture, by mixing a biodegradable polyester solution prepared by dissolving the biodegradable polyester in an acid amide solvent with an aminopolysaccharide solution prepared by dissolving the aminopolysaccharide in an organic acid solvent or by dissolving both the biodegradable polyester and the aminopolysaccharide in formic acid. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antibacterial / deodorant resin composition containing a biodegradable polyester and an aminopolysaccharide, and an antibacterial / deodorant fiber and a nonwoven fabric obtained therefrom.

In recent years, fiber products and resin molded products subjected to antibacterial processing have attracted attention. For example, clothing, medical supplies, daily necessities, and the like that have been given antibacterial properties are commercially available.
As an antibacterial substance used for this antibacterial processing, conventionally, an inorganic antibacterial agent having a metal ion such as copper, silver or zinc; an organic antibacterial agent such as benzalkonium chloride, an organic silicon type, or a quaternary ammonium salt; Natural polysaccharide antibacterial agents such as chitosan are known.
When an inorganic antibacterial agent is added to a synthetic resin, there is a problem that the product value is remarkably lowered due to deformation due to the influence of heat or light applied during molding. In addition, organic antibacterial agents have a problem that weather resistance and chemical resistance are poor and acute oral toxicity is high.
For this reason, attempts have been made to use natural polysaccharide antibacterial agents such as chitosan having excellent safety.

For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2-41473) discloses an antibacterial fiber in which a cotton yarn surface-treated with chitosan acetate is further treated with an isocyanate crosslinking agent, and the cotton yarn and chitosan are crosslinked with a polyurethane bond. ing. In the antibacterial fiber obtained by this method, since the fiber and chitosan which is an antibacterial agent are firmly bonded, it is possible to prevent the chitosan from falling off the fiber, and good antibacterial properties are exhibited over a long period of time.
However, in the technique of Patent Document 1, a drying step after chitosan treatment is essential, and the cotton yarn after chitosan treatment needs to be cross-linked again using a polyisocyanate compound, which makes the process complicated. There is a problem.
And when processing biodegradable fiber, such as biodegradable polyester, if the said crosslinking process is performed with respect to biodegradable fiber, there exists a possibility that the original biodegradability of fiber may not fully be exhibited.

Patent Document 2 (Japanese Patent Laid-Open No. 7-42076) discloses a coating processing agent prepared by dissolving a chitosan-containing synthetic resin prepared by salting out a synthetic resin emulsion with a chitosan acid aqueous solution in an organic solvent, and this A fiber fabric coated with a processing agent is disclosed. According to this method, a solution-like coating agent in which chitosan is uniformly dispersed is obtained, and by using this, a coating layer in which chitosan is uniformly dispersed can be formed on the fiber surface.
However, the technique of Patent Document 2 also requires a salting-out process using a chitosan acid aqueous solution, which makes the process complicated. In addition, since it is a method of coating chitosan, a drying process is required, and the chitosan is easily exposed to the fiber surface. As a result, it tends to fall off and the antibacterial property decreases over time. There is.
Moreover, when processing a biodegradable fiber, since the fiber surface is coat | covered with an acrylic resin, there exists a possibility that the original biodegradability of a fiber may not fully be exhibited.

  As described above, the method of coating the biodegradable polymer fiber with a natural antibacterial agent such as chitosan cannot be said to be suitable as an antibacterial process in terms of the complexity of the treatment process and the decrease in biodegradability. .

Recently, a technique for producing polylactic acid or chitosan nanofibers by an electrospinning method has been disclosed (Patent Document 3: International Publication No. 2004/088943, Patent Document 4: JP-A-2005-290610). reference).
For example, Patent Document 3 discloses a technique for producing a fiber structure made of a biodegradable absorbable polymer having an average fiber diameter of 0.05 to 50 μm by an electrostatic spinning method. Polylactic acid and chitosan are exemplified, and in the examples, polylactic acid nanofibers are specifically produced.
Patent Document 4 discloses a nanofiber mainly made of chitosan having a diameter of 500 nm or less and a non-woven fabric obtained therefrom produced by an electrospinning method. In this case, polylactic acid can be used as an additive. Is disclosed.

Thus, it is suggested in any of Patent Documents 3 and 4 that nanofibers can be produced using polylactic acid and chitosan in combination. However, in the Examples, nanofibers containing both of them are not manufactured, and it is not clear how to mix and spin polylactic acid and chitosan.
That is, in the technique of Patent Document 3, chitosan is not dissolved in the polylactic acid solution for spinning. Moreover, since the chitosan solution is usually an acetic acid aqueous solution as in Patent Documents 1, 2, and 4, it is not possible to prepare a solution in which both are dissolved by mixing this with a polylactic acid methylene chloride solution. Can not. Therefore, it is difficult to produce a polymer blend of polylactic acid and chitosan in the technique of Patent Document 3.
On the other hand, even in the technique of Patent Document 4, since an organic solvent solution of polylactic acid is mixed with a chitosan acid aqueous solution for spinning and a solution in which both are dissolved cannot be prepared, when preparing a blend of both, There is no method other than mixing polylactic acid in powder with an organic solvent solution of polylactic acid, but it is very difficult to prepare nano-level polylactic acid particles, which is not practical.

JP-A-2-41473 Japanese Patent Laid-Open No. 7-42076 International Publication No. 2004/088943 Pamphlet JP-A-2005-290610

  The present invention has been made in view of such circumstances, and a resin composition for an antibacterial / deodorant article containing a biodegradable polyester and an aminopolysaccharide, and an antibacterial / deodorant fiber obtained therefrom and It aims at providing a nonwoven fabric.

  As a result of intensive investigations to achieve the above object, the present inventors have conducted an organic solvent solution of a biodegradable polyester and an amino acid which are kneaded by heating a solid biodegradable polyester and a solid aminopolysaccharide. The biodegradable polyester and amino polysaccharide can be mixed with an organic acid solution of the polysaccharide, or by dissolving the biodegradable polyester and amino polysaccharide in an organic solvent such as formic acid having the solubility of both. Is found to be obtained by mixing a homogeneously mixed composition, or a composition in which a biodegradable polyester and aminopolysaccharide are uniformly dispersed in a solution, and by electrospinning the latter composition. The present invention was completed by finding that (nano) fibers and non-woven fabrics having excellent properties and biodegradability can be obtained.

That is, the present invention
1. A resin composition for an antibacterial / deodorant article, comprising 100 parts by weight of a biodegradable polyester and 0.01 to 50 parts by weight of an aminopolysaccharide;
2. 1. The resin composition for antibacterial / deodorant articles prepared by mixing the biodegradable polyester and the aminopolysaccharide in a solid state and then heating and kneading,
3. 1 or 2 resin composition for antibacterial and deodorant articles, wherein the aminopolysaccharide is uniformly dispersed in the biodegradable polyester,
4). The resin composition for an antibacterial / deodorant article according to any one of 1 to 3, comprising only the biodegradable polyester and the aminopolysaccharide,
5. Furthermore, 1 resin composition for antibacterial / deodorant articles comprising an acid amide solvent and an organic acid solvent,
6). Prepared by mixing a biodegradable polyester-containing solution obtained by dissolving the biodegradable polyester in an acid amide solvent and an aminopolysaccharide-containing solution obtained by dissolving the aminopolysaccharide in the organic acid solvent. 5. Antibacterial and deodorant resin composition for articles,
7). 1. A resin composition for antibacterial and deodorant articles, which further comprises formic acid, wherein the biodegradable polyester and the aminopolysaccharide are dissolved in formic acid,
8). The resin composition for antibacterial / deodorant articles according to any one of 5 to 7, which is uniformly transparent,
9. The resin composition for antibacterial and deodorant articles according to any one of 1 to 8, wherein the amino polysaccharide has a D-glucosamine unit or an N-acetyl-D-glucosamine unit,
10. The resin composition for antibacterial and deodorant articles according to any one of 1 to 9, wherein the biodegradable polyester is polylactic acid,
11. 1 to 10 antibacterial / deodorant fibers having an average fiber diameter of 1 nm to 10 μm formed by spinning the resin composition for antibacterial / deodorant articles,
12 Antibacterial / deodorant nonwoven fabric comprising 11 antibacterial / deodorant fibers,
13. An antibacterial / deodorant film formed by molding a resin composition for an antibacterial / deodorant article according to any one of 1 to 10;
14 A method for producing an antibacterial / deodorant nonwoven fabric characterized by spinning a resin composition comprising a biodegradable polyester and an aminopolysaccharide by an electrostatic spinning method;
15. The resin composition was prepared by mixing a biodegradable polyester-containing solution in which a biodegradable polyester was dissolved in an acid amide solvent and an aminopolysaccharide-containing solution in which the aminopolysaccharide was dissolved in an organic acid. Manufacturing method of antibacterial and deodorant nonwoven fabric,
16. The method for producing an antibacterial / deodorant nonwoven fabric according to 14, wherein the resin composition is prepared by dissolving the biodegradable polyester and the amino polysaccharide in formic acid.

According to the present invention, a composition in which a biodegradable polyester and an aminopolysaccharide are mixed at a molecular level can be easily obtained.
In addition, the antibacterial / deodorant fiber and non-woven fabric of the present invention obtained from this composition are not coated with an aminopolysaccharide, so that the aminopolysaccharide is difficult to be exposed on the surface, and this is difficult to drop off. Excellent in biodegradability and biodegradability.
Furthermore, in the present invention, the biodegradable polyester is dissolved in an organic solvent such as an acid amide solvent, the aminopolysaccharide is dissolved in an organic acid such as formic acid, and these are mixed to form a solution, or both of these are dissolved. Since it is dissolved in an organic solvent such as formic acid having a solution, the biodegradable polyester and formic acid can be easily mixed at the molecular level. In addition, by performing electrospinning using this solution, a (nano) fiber having a thinner fiber diameter can be easily and efficiently produced.

Hereinafter, the present invention will be described in more detail.
The resin composition for antibacterial and deodorant articles according to the present invention contains a biodegradable polyester and an aminopolysaccharide.
Here, as the biodegradable polyester, for example, polylactic acid aliphatic polyester, polycaprolactone aliphatic polyester, microorganism-produced aliphatic polyester, polyhydroxyalkanoate, aliphatic polyester such as polybutylene succinate, so-called What is generally called a biodegradable plastic is mentioned.

Examples of polylactic acid-based aliphatic polyesters include polymers of oxyacids such as lactic acid, malic acid, and glycolic acid, and polylactides such as copolymers thereof. Specific examples include polylactic acid, poly (α- Malic acid), polyglycolic acid, glycolic acid-lactic acid copolymer, and the like, and hydroxycarboxylic acid aliphatic polyesters represented by polylactic acid are particularly suitable.
The polycaprolactone-based aliphatic polyester can be obtained by ring-opening polymerization of ε-caprolactone and is decomposed by many bacteria while being a water-insoluble polymer, and has a general formula: — (O (CH ₂ ) ₅ CO) An aliphatic polyester represented by _n- . As a commercial item of such polycaprolactone aliphatic polyester, for example, “Tone” (trade name) sold by Nippon Unicar Co., Ltd. is available.

The microorganism-produced aliphatic polyester is a thermoplastic polymer having a melting point derived from a living body. Specific examples include polyhydroxybutyrate (PHB), poly (hydroxybutyric acid-hydroxypropionic acid) copolymer, poly (hydroxybutyric acid-hydroxyvaleric acid) copolymer, and the like.
In the present invention, in addition to biodegradable polyester, biodegradable polyurethane, polyacryl, polypropylene, non-biodegradable polyester, nylon, or the like may be mixed. Examples of the non-biodegradable polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate.

  The amino polysaccharide is not particularly limited, but an amino polysaccharide having a D-glucosamine unit or an N-acetyl-D-glucosamine unit is preferable. Specific examples include natural amino polysaccharides such as chitin and chitosan.

In the resin composition for antibacterial / deodorant articles of the present invention, the blending ratio of the biodegradable polyester and aminopolysaccharide is preferably such that the biodegradable polyester is excessive (greater than 50% by mass). 0.01-100 mass parts of amino polysaccharide is preferable with respect to 100 mass parts of biodegradable polyester, 0.01-30 mass parts is more preferable, and 0.01-5 mass parts is still more preferable.
If the aminopolysaccharide exceeds 50 parts by mass, the moldability of the composition is lowered, and the resulting molded article or the nonwoven fabric may have a hard texture and become brittle. When the aminopolysaccharide is in the range of 0.01 to 30 parts by mass, particularly 0.01 to 5 parts by mass, the antibacterial and deodorant properties are well exhibited and the resin is close to the mechanical strength of the biodegradable polyester Since the mechanical strength of the composition can be maintained, antibacterial / deodorant properties and mechanical strength can be imparted to a molded article or nonwoven fabric in a well-balanced manner.

The resin composition for antibacterial and deodorant articles of the present invention is obtained by mixing a biodegradable polyester and an aminopolysaccharide. As a method of mixing these, (1) a method in which aminopolysaccharide is kneaded and mixed in biodegradable polyester, and (2) a solution in which each of biodegradable polyester and aminopolysaccharide is dissolved in an organic solvent is prepared. There are a method of mixing these solutions, and (3) a method of dissolving and mixing in an organic solvent that dissolves both the biodegradable polyester and aminopolysaccharide.
By using these three methods, the aminopolysaccharide can be more uniformly dispersed in the biodegradable polyester. Among them, since both can be mixed at the molecular level, (2) a method of preparing a solution in which each of biodegradable polyester and aminopolysaccharide is dissolved in an organic solvent and mixing them, (3) biodegradability A method of dissolving and mixing in an organic solvent in which both polyester and aminopolysaccharide are dissolved is preferred.

In the case of the method of kneading and mixing the aminopolysaccharide into the biodegradable polyester of (1) above, for example, the biodegradable polyester and aminopolysaccharide are mixed in a solid state, and then heated and kneaded to obtain antibacterial / antibacterial properties. What is necessary is just to set it as the resin composition for odor articles.
In this case, it is preferable to use a powdered aminopolysaccharide. This powdered aminopolysaccharide can be mechanically pulverized by various types of pulverizers such as impact type, compression type, shear type, air jet type, and freeze pulverization type, and organic acids such as formic acid, acetic acid, lactic acid and citric acid. Alternatively, it can be obtained by dissolving it once in an aqueous solution of an inorganic acid such as hydrochloric acid or nitric acid, and then dispersing it in an alkaline solution such as ammonia and regenerating it, or spraying and drying it by spray drying.
The average particle size of the aminopolysaccharide is preferably 0.2 to 400 μm, more preferably 0.20 to 100 μm. The average particle diameter is a value measured by a light scattering particle size distribution measuring device.

The kneading method of the biodegradable polyester and the aminopolysaccharide is not particularly limited, and may be kneaded using a single screw kneading extruder, a twin screw kneading extruder, a batch kneader, a continuous extrusion kneader or the like.
The heating temperature is preferably from 100 to 250 ° C, more preferably from 100 to 200 ° C, considering that aminopolysaccharides are more uniformly dispersed.
The resin composition for antibacterial and deodorant articles (resin mixed pellets) obtained by kneading as described above can be used in various ways by extrusion molding, injection molding, stretched film molding, blow molding, etc., as with general thermoplastics. The molded product can be shaped.

In the case of the method of dissolving the biodegradable polyester and aminopolysaccharide of (2) and (3) in an organic solvent, the organic solvent for dissolving the biodegradable polyester includes an acid amide solvent, a chlorine solvent, Examples thereof include hydrocarbon solvents and organic solvents such as formic acid. On the other hand, examples of the organic solvent for dissolving the aminopolysaccharide include organic solvents such as an organic acid solvent that is liquid at room temperature and an acid amide solvent that dissolves a solid organic acid at room temperature.
Examples of the acid amide solvent used for the preparation of the organic solvent solution of the biodegradable polyester include N, N-dimethylformamide (hereinafter referred to as DMF) and N, N-dimethylacetamide (hereinafter referred to as DMAc). N-substituted amides may also be mentioned, and further, a compound such as N-methyl-2-pyrrolidone partially forming a ring and having a carbonyl carbon adjacent to a hetero atom may be used.
Examples of the chlorine solvent include methylene chloride and chloroform, and examples of the hydrocarbon solvent include toluene, benzene, acetone, hexane, cyclohexane, methanol, ethanol, propanol, isopropanol, and tetrahydrofuran.
Among these organic solvents, an acid amide solvent is preferable as a solvent used for preparing an organic solvent solution (biodegradable polyester-containing solution) of biodegradable polyester, and N-substituted amides such as DMF and DMAc are most suitable. . In addition, formic acid can also be suitably used.

Examples of the organic acid solvent that is liquid at room temperature used for the preparation of the aminopolysaccharide organic solvent solution include acetic acid and lactic acid in addition to formic acid that dissolves the above-described biodegradable polyester. Examples of the acid amide solvent in which a solid organic acid is dissolved at room temperature include acid amide solvents in which citric acid, malic acid, tartaric acid and the like are dissolved. The acid amide solvent is as described above.
Among these, formic acid is suitable as a solvent used for preparing an organic solvent solution of aminopolysaccharide (aminopolysaccharide-containing solution) from the viewpoint that gelation is difficult and a uniform solution can be easily prepared. In particular, when formic acid is used as a solvent for preparing a biodegradable polyester-containing solution, in addition to the method (2) above, both biodegradable polyester and aminopolysaccharide are added in small amounts in an organic solvent (formic acid). Then, it is possible to employ the method of (3) above in which dissolution and mixing are performed.

In the case of the method of dissolving and mixing both the biodegradable polyester and aminopolysaccharide of (2) above with an organic solvent, the biodegradable polyester and aminopolysaccharide are separately prepared using the above organic solvent. What is necessary is just to prepare as a solution and mix these solutions to make a liquid resin composition for antibacterial and deodorant articles.
In particular, among the above organic solvents, when an acid amide solvent is used as the solvent for the biodegradable polyester and formic acid is used as the solvent for the amino polysaccharide, a formic acid solution of the amino polysaccharide and an acid amide solvent solution of the biodegradable polyester These are the most suitable because they have good compatibility, and the mixed solution does not gel for more than 10 days at room temperature and has good storage stability as a raw material solution for electrospinning.

The biodegradable polyester-containing solution can be prepared by mixing the biodegradable polyester and an organic solvent such as an acid amide solvent by any method and heating as necessary. The temperature for heating depends on the boiling point of the solvent used, but is preferably about 25 to 150 ° C. If it is lower than 25 ° C., although it depends on the type of solvent used, it takes time to dissolve the biodegradable polyester until it becomes a homogeneous solution. This is not preferable because hydrolysis of the degradable polyester easily occurs.
In this case, the concentration of the biodegradable polyester in the solution is preferably about 2 to 50% by mass, and more preferably about 5 to 40% by mass.
The aminopolysaccharide-containing solution can be prepared by mixing the aminopolysaccharide with an organic acid solvent or an organic acid-containing acid amide solvent by any method and heating as necessary. The heating temperature is preferably not higher than the boiling point of the solvent used.
In this case, the concentration of the aminopolysaccharide in the solution is preferably about 0.1 to 20% by mass, and more preferably about 0.5 to 10% by mass.

The biodegradable polyester-containing solution prepared as described above and the aminopolysaccharide-containing solution are mixed to obtain a liquid resin composition. At this time, the aminopolysaccharide-containing solution may be added to the biodegradable polyester-containing solution, or vice versa. The obtained resin composition is obtained as a uniform transparent liquid.
Prior to molding this liquid resin composition into a solid resin composition, a solvent may be further added to the solution in order to adjust the viscosity or resin concentration of the solution in accordance with the molding method. The concentration of the biodegradable polyester and aminopolysaccharide in the solution is preferably about 2.5 to 40% by mass, more preferably about 3.5 to 30% by mass. If it is less than 2.5% by mass, the viscosity may be low, so that molding and spinning may be difficult. If it exceeds 40% by mass, the viscosity will be high, and in this case, molding and spinning may be difficult. .
In addition, since aminopolysaccharides such as chitosan are conventionally used as an acid aqueous solution, they cannot be mixed with an organic solvent solution of a resin. However, in the present invention, an organic acid solvent or an organic solvent containing an organic acid is used. Since the aminopolysaccharide solution is prepared, it can be easily mixed with the organic solvent solution of the biodegradable polyester.

The obtained liquid resin composition is formed into a thin film by a casting method, an extrusion method, a spray method, a roll coating method, a dipping method, etc., and then the solvent is vacuum dried or immersed in water. The film can be formed by wet-coagulating and gelling the resin solution and then drying.
Moreover, this resin composition can be made into a (nano) fiber by spinning by an electrostatic spinning method, a spunbond method, a melt blow method, a flash spinning method, or the like. Among these spinning methods, an electrostatic spinning method with little influence of heat is preferable.

The electrostatic spinning method is a method in which a charged resin composition is twisted in an electric field, and the resin composition is ruptured by the repulsive force of the charge to form an extremely fine fibrous material made of the resin composition. is there.
The basic structure of an apparatus for performing electrostatic spinning is composed of one electrode that serves as a nozzle for discharging the resin composition and is applied to the resin composition at a high voltage, and the other electrode that faces the electrode. The resin composition discharged or shaken from one electrode becomes an extremely fine fibrous material made of the resin composition in an electric field between two opposing electrodes, and is deposited on the surface of the other electrode.
Specifically, the biodegradable polyester-containing solution and the aminopolysaccharide-containing solution are mixed, pressed from the die, and a high voltage of about several thousand to 50,000 volts is applied to the mixed solution (resin composition), and the mixed solution (Nano) fiber fibers and nonwoven fabrics are obtained by bending and expansion of the high-speed jet and subsequent jet.

In the present invention, since an acid component is included in the resin composition, charges are easily accumulated when a voltage is applied to the composition (solution), and the resin composition can be more finely divided when sprayed in the electric field. it can. By increasing the acid concentration in the resin composition, the fiber diameter of the obtained (nano) fiber can be reduced. The acid component in the resin composition is preferably 0.1 to 90% by mass, more preferably 0.5 to 85% by mass, and still more preferably 0.5 to 75% by mass. If it is less than 0.1% by mass, the fineness of the fiber diameter is not affected, and if it exceeds 90% by mass, there is a possibility that spinning cannot be stably performed.
By spinning the resin composition of the present invention by electrostatic spinning, the average fiber diameter was relatively uniform in the range of 1 nm to 10 μm including the nanofiber region, preferably in the range of 1 to 1000 nm which is the nanofiber region. Can be adjusted to the diameter.

  As mentioned above, although the method of shape | molding the liquid resin composition of this invention in a film, (nano) fiber, and a nonwoven fabric was described, a molded article is not restricted to these. For example, a liquid resin composition is formed into droplets and vacuum-dried solvent, or is immersed in water to wet-solidify and gel, and then dried into pellets. Similarly, various molded products can be formed using molding methods such as extrusion molding, injection molding, stretched film molding, and blow molding.

  In addition, in the various antibacterial / deodorant article resin compositions described above, as other additives, an antistatic agent, a foaming agent, a heat stabilizer, a light stabilizer, as long as the effects of the present invention are exhibited. In addition, a weather resistance stabilizer, a heat and humidity resistance stabilizer, a lubricant, a release agent, an inorganic filler, a pigment dispersant, a pigment, a dye, and the like can be appropriately added.

  Various molded articles such as (nano) fibers, non-woven fabrics, and films obtained from the resin composition for antibacterial and deodorant articles of the present invention include, for example, wiping sheets, masks, filters, filter media, hazardous substance removal products, gloves , Wiper, wiper, mat, car seat, ceiling material, wallpaper, diapers, hospital gowns, clothes for medical staff, sheets, packaging materials, interlining, seedling pots, seedling mats, civil engineering construction materials, etc. .

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. The evaluation items in the following examples and comparative examples were carried out by the following methods.

[1] Average fiber diameter 20 fibers were selected at random from the photograph obtained by photographing the sample surface with a scanning electron microscope (“S-4800I” manufactured by Hitachi High-Technologies Corporation) at a magnification of 5000 times. The diameter was measured. The average value (n = 20) of all fiber diameters was determined and used as the average fiber diameter.
[2] Thickness of Nonwoven Fabric Using a digital thickness gauge ("SMD-565" manufactured by Teclock Co., Ltd.), the thickness was measured by randomly selecting five locations with a measuring force of 1.5N. The average value (n = 5) of all thicknesses was determined and used as the thickness of the nonwoven fabric.
[3] Fabric weight of nonwoven fabric The mass of the sample was measured and converted per square meter.
[4] Antibacterial performance measurement test (bacteria count measurement method)
The following bacterial count measurement method described in the processing effect evaluation test manual for antibacterial and deodorant processed products formulated by the Textile Products Sanitation Processing Council was adopted.
Staphylococcus aureus was used as a test cell, and this was cultured and adjusted in advance in a normal bouillon medium to 106 to 107 cells / ml to obtain a test cell suspension. 0.2 ml of this suspension is uniformly inoculated into 0.4 g of a sterilized screw-capped vial, statically cultured at 36-38 ° C. for 18 hours, and then sterilized buffered saline is placed in the container. Add 20 ml, shake vigorously 25-30 times by hand with an amplitude of 30 cm, disperse the test bacteria in the solution, make an appropriate dilution series with sterilized buffered saline, and dilute each stage 1 ml was placed in two petri dishes, and about 15 ml of standard agar medium was further added. After culturing this at 36 to 38 ° C. for 24 to 48 hours, the number of growing colonies was counted, and the number of viable bacteria in the sample was calculated according to the dilution rate. And the determination of the effect determined the test establishment, when the proliferation value exceeded 1.5. Moreover, bacteriostatic activity value S and bactericidal activity value L were calculated | required by the following formula.
Bacteriostatic activity value S = BC
Bactericidal activity value L = A-C
A: Average value of common logarithm of the number of viable bacteria of three specimens immediately after contact of the test cloth on the standard cloth B: Average value of common logarithm of the number of viable bacteria of the three specimens after 18 hours culture of the standard cloth C: Antibacterial processing Average value of common logarithm of the number of viable bacteria of 3 specimens after 18 hours of culturing [5] Biodegradation performance measurement test Samples after 3 months and 5 months after being buried in field soil (5 cm x 5 cm) The disassembly status was determined with the naked eye.
[6] Spinnability The discharge state when the liquid resin composition was electrostatically spun under the conditions of a discharge tip inner hole diameter of 0.4 mm, an applied voltage of 25 KV, room temperature, and atmospheric pressure was visually observed and evaluated according to the following criteria. .
○: Stable discharge is possible Δ: Discharge is possible while being interrupted X: Discharge is impossible [7] Texture The obtained nonwoven fabric was grasped by hand, and the tactile sensation at that time was judged. Sensory evaluation was performed according to the following criteria.
◎: More flexible ○: Flexible △: Normal ×: Hard

[1] Production of film [Example 1]
In a biaxial extruder, 100 parts by mass of polylactic acid resin (LACEA H400, manufactured by Mitsui Chemicals, Inc.) and 2.5 parts by mass of chitosan powder (produced by Kimika Co., Ltd., average particle diameter of about 1 to 5 μm) A resin composition for an antibacterial / deodorant article was produced by kneading and mixing at 0 ° C., and this resin composition was then extruded in a sheet form from a T die die at a temperature of 210 ° C. while being measured with a gear pump. Then, it cooled to 20 degreeC and obtained the 100-micrometer-thick antimicrobial film.

[Example 2]
A polylactic acid-containing solution was prepared by mixing 100 parts by mass of a polylactic acid resin (LACEA H280, manufactured by Mitsui Chemicals) and 300 parts by mass of dimethylacetamide and dissolving polylactic acid at 60 ° C. On the other hand, 2.5 parts by mass of chitosan (manufactured by Kimika Co., Ltd., deacetylated 75 to 85%) and 164 parts by mass of formic acid were mixed at room temperature, and chitosan was dissolved to prepare a chitosan-containing solution. This was added to the previously prepared polylactic acid-containing solution and mixed at room temperature to prepare a uniform transparent liquid antibacterial / deodorant resin composition.
The obtained resin composition was cast on a glass plate with a knife coater and dried with a vacuum dryer at 60 ° C. for 10 hours to obtain an antibacterial film having a thickness of 100 μm.

[2] Fabrication of nonwoven fabric [Example 3]
100 parts by mass of polylactic acid resin (LACEA H280, manufactured by Mitsui Chemicals) and 570 parts by mass of dimethylformamide were mixed, and polylactic acid was dissolved at 60 ° C. to prepare a polylactic acid-containing solution. On the other hand, 0.1 parts by mass of chitosan (manufactured by Kimika Co., Ltd., deacetylated 75 to 85%) and 6.6 parts by mass of formic acid were mixed at room temperature to dissolve chitosan to prepare a chitosan-containing solution. This was added to the previously prepared polylactic acid-containing solution and mixed at room temperature to prepare a uniform transparent liquid antibacterial / deodorant resin composition.
This resin composition (spinning solution) is put into a syringe, the inner diameter of the discharge tip is 0.4 mm, the applied voltage is 25 KV (at room temperature, atmospheric pressure), and the distance from the inner diameter of the discharge tip to the fibrous material collecting electrode is 15 cm. Electrospinning was performed to obtain an antibacterial nonwoven fabric. The obtained nonwoven fabric had an average fiber diameter of 1 μm, fibers having a fiber diameter of 10 μm or more were not observed, and the fibers constituting the nonwoven fabric contained nanofiber regions. The nonwoven fabric had a thickness of 150 μm and a basis weight of 30 g / m ² . The electron micrograph of the obtained antibacterial nonwoven fabric is shown in FIG.

[Example 4]
A uniform transparent liquid antibacterial / deodorant resin composition was prepared in the same manner as in Example 3 except that 0.5 parts by mass of chitosan and 33 parts by mass of formic acid were used. This resin composition was electrospun in the same manner as in Example 3 to obtain an antibacterial nonwoven fabric.
The obtained nonwoven fabric had an average fiber diameter of 0.5 μm, fibers having a fiber diameter of 1 μm or more were not observed, and the fibers constituting the nonwoven fabric were nanofiber regions. The nonwoven fabric had a thickness of 100 μm and a basis weight of 10 g / m ² . An electron micrograph of the obtained antibacterial nonwoven fabric is shown in FIG.

[Example 5]
A uniform transparent liquid antibacterial / deodorant resin composition was prepared in the same manner as in Example 3 except that 1 part by weight of chitosan and 66 parts by weight of formic acid were used. This resin composition was electrospun in the same manner as in Example 3 to obtain an antibacterial nonwoven fabric.
The obtained nonwoven fabric had an average fiber diameter of 0.3 μm, fibers having a fiber diameter of 0.5 μm or more were not observed, and the fibers constituting the nonwoven fabric were nanofiber regions. The nonwoven fabric had a thickness of 50 μm and a basis weight of 6 g / m ² . An electron micrograph of the obtained antibacterial nonwoven fabric is shown in FIG.

[Example 6]
A uniform transparent liquid antibacterial / deodorant resin composition was prepared in the same manner as in Example 3 except that 2.5 parts by mass of chitosan and 164 parts by mass of formic acid were used. This resin composition was electrospun in the same manner as in Example 3 to obtain an antibacterial nonwoven fabric.
When the obtained nonwoven fabric was observed with an electron microscope, it was almost the same as in FIG. 3, the average fiber diameter was 0.3 μm, fibers having a fiber diameter of 0.5 μm or more were not observed, and the fibers constituting the nonwoven fabric were nanofibers. It was an area. The nonwoven fabric had a thickness of 50 μm and a basis weight of 5.5 g / m ² .

[Example 7]
A uniform transparent liquid antibacterial / deodorant resin composition was prepared in the same manner as in Example 3 except that 5 parts by mass of chitosan and 330 parts by mass of formic acid were used. This resin composition was electrospun in the same manner as in Example 3 to obtain an antibacterial nonwoven fabric.
The obtained nonwoven fabric had an average fiber diameter of 0.3 μm, fibers having a fiber diameter of 0.5 μm or more were not observed, and the fibers constituting the nonwoven fabric were nanofiber regions. The nonwoven fabric had a thickness of 35 μm and a basis weight of 2.5 g / m ² . The electron micrograph of the obtained antibacterial nonwoven fabric is shown in FIG.

[Example 8]
A uniform transparent liquid antibacterial / deodorant resin composition was prepared in the same manner as in Example 3 except that 30 parts by mass of chitosan and 1980 parts by mass of formic acid were used. This resin composition was electrospun in the same manner as in Example 3 to obtain an antibacterial nonwoven fabric.
The obtained nonwoven fabric had an average fiber diameter of 0.3 μm, fibers having a fiber diameter of 0.5 μm or more were not observed, and the fibers constituting the nonwoven fabric were nanofiber regions. The nonwoven fabric had a thickness of 35 μm and a basis weight of 2.5 g / m ² . The electron micrograph of the obtained antibacterial nonwoven fabric is shown in FIG.

[Example 9]
A uniform transparent liquid antibacterial / deodorant resin composition was prepared in the same manner as in Example 3 except that 0.5 parts by mass of chitosan, 33 parts by mass of formic acid, and dimethylformamide were replaced with dimethylacetamide. did. This resin composition was electrospun in the same manner as in Example 3 to obtain an antibacterial nonwoven fabric.
The obtained nonwoven fabric had an average fiber diameter of 0.4 μm, fibers having a fiber diameter of 0.8 μm or more were not observed, and the fibers constituting the nonwoven fabric were nanofiber regions. The nonwoven fabric had a thickness of 100 μm and a basis weight of 10 g / m ² . An electron micrograph of the obtained antibacterial nonwoven fabric is shown in FIG.

[Example 10]
A uniform transparent liquid antibacterial / deodorant resin composition as in Example 3 except that 0.5 parts by mass of chitosan, 33 parts by mass of formic acid, and 900 parts by mass of dimethylformamide were replaced with chloroform. Was prepared. This resin composition was electrospun in the same manner as in Example 3 to obtain an antibacterial nonwoven fabric.
The obtained nonwoven fabric had an average fiber diameter of 2 μm, fibers having a fiber diameter of 10 μm or more were not observed, and the fibers constituting the nonwoven fabric contained nanofiber regions. The nonwoven fabric had a thickness of 200 μm and a basis weight of 35 g / m ² . The electron micrograph of the obtained antibacterial nonwoven fabric is shown in FIG.

[Example 11]
A uniform transparent liquid antibacterial / deodorant resin composition as in Example 3, except that 0.5 parts by mass of chitosan, 33 parts by mass of formic acid, and 900 parts by mass of dimethylformamide were replaced with methylene chloride. Was prepared. This resin composition was electrospun in the same manner as in Example 3 to obtain an antibacterial nonwoven fabric.
The obtained nonwoven fabric had an average fiber diameter of 2 μm, fibers having a fiber diameter of 10 μm or more were not observed, and the fibers constituting the nonwoven fabric contained nanofiber regions. The nonwoven fabric had a thickness of 200 μm and a basis weight of 35 g / m ² . An electron micrograph of the obtained antibacterial nonwoven fabric is shown in FIG.

[Example 12]
100 parts by mass of polylactic acid resin (LACEA H280, manufactured by Mitsui Chemicals, Inc.) and 0.5 parts by mass of chitosan (manufactured by Kimika Co., Ltd., 75 to 85% deacetylated) are heated to 60 ° C. under 600 parts. In addition to part by mass of formic acid, polylactic acid and chitosan were dissolved to prepare a uniform transparent liquid antibacterial / deodorant resin composition. This resin composition was electrospun in the same manner as in Example 3 to obtain an antibacterial nonwoven fabric.
The obtained nonwoven fabric had an average fiber diameter of 0.4 μm, fibers having a fiber diameter of 0.8 μm or more were not observed, and the fibers constituting the nonwoven fabric were nanofiber regions. The nonwoven fabric had a thickness of 100 μm and a basis weight of 10 g / m ² . An electron micrograph of the obtained antibacterial nonwoven fabric is shown in FIG.

[Comparative Example 1]
100 parts by mass of polylactic acid resin (LACEA H280, manufactured by Mitsui Chemicals) and 300 parts by mass of dimethylacetamide were mixed, and polylactic acid was dissolved at 60 ° C. to prepare a polylactic acid solution.
The obtained polylactic acid solution was cast on a glass plate with a knife coater and dried with a vacuum dryer at 60 ° C. for 10 hours to obtain a film having a thickness of 100 μm.

[Comparative Example 2]
100 parts of chitosan (manufactured by Kimika Co., Ltd., deacetylated 75 to 85%), 200 parts of formic acid and 19700 parts of distilled water were mixed and stirred at room temperature for 10 hours or more to dissolve chitosan.
A commercially available polylactic acid nonwoven fabric (manufactured by Terramac Unitika) was immersed in the obtained 0.5 mass% chitosan acid aqueous solution and dried at room temperature. After drying, heat treatment was performed at 70 ° C. for 30 minutes to obtain an antibacterial nonwoven fabric. The dry adhesion amount of chitosan determined from the weight difference before and after the coating treatment was about 1.5% by mass.

[Comparative Example 3]
A coating treatment was performed in the same manner as in Comparative Example 2 except that a commercially available polypropylene nonwoven fabric (Stratec, manufactured by Idemitsu Tech Co., Ltd., average fiber type 4 μm) was used to obtain an antibacterial nonwoven fabric. The dry adhesion amount of chitosan determined from the weight difference before and after the coating treatment was about 1.5% by mass.

[Comparative Example 4]
A uniform transparent liquid antibacterial / deodorant resin composition was prepared in the same manner as in Example 3 except that chitosan was 55 parts by mass and formic acid was 3630 parts by mass. This resin composition was electrospun in the same manner as in Example 3 to obtain an antibacterial nonwoven fabric.
The obtained nonwoven fabric had an average fiber diameter of 0.2 μm, fibers having a fiber diameter of 0.5 μm or more were not observed, and the fibers constituting the nonwoven fabric were nanofiber regions. The nonwoven fabric had a thickness of 35 μm and a basis weight of 1.5 g / m ² .

  Table 1 shows the results of the above-described antibacterial performance measurement test for the films and nonwoven fabrics obtained in Examples 1 to 12 and Comparative Examples 1 to 4.

  Next, Table 2 shows the results of the biodegradation performance measurement test described above for the films and nonwoven fabrics obtained in Examples 1-12 and Comparative Examples 1-4.

  Moreover, the above-mentioned feeling was evaluated about the nonwoven fabric obtained in the said Examples 3-12 and Comparative Examples 2-4, and the above-mentioned spinnability was evaluated about the nonwoven fabric obtained in the said Examples 3-12 and Comparative Example 4, respectively. Is shown in Table 3.

As shown in Table 1, the antibacterial film and the nonwoven fabric of the present invention obtained in Examples 1 to 12 were obtained by coating chitosan on a film made of only polylactic acid of Comparative Examples 1 to 3 and a commercially available polylactic acid nonwoven fabric. It can be seen that the antibacterial performance is far superior.
As Table 2 shows, it turns out that the antibacterial film and nonwoven fabric of this invention obtained in Examples 1-12 show favorable biodegradability. It can be seen that the antibacterial nonwoven fabrics of Examples 3 to 12 are particularly superior in biodegradability compared to the commercially available polylactic acid nonwoven fabric of Comparative Example 2 coated with chitosan.
As shown in Table 3, the nonwoven fabrics of the present invention obtained in Examples 3 to 12 have a texture equivalent to or higher than that of the comparative nonwoven fabric, and chitosan is particularly 0.5% by mass with respect to polylactic acid. In the following, it can be seen that when an acid amide solvent is used as the solvent of the polylactic acid solution, the solution is remarkably excellent. In addition, when an acid amide solvent was used as the solvent for the polylactic acid solution, the spinnability in the electrospinning method was good.

It is a figure which shows the electron micrograph of the antibacterial nonwoven fabric obtained in Example 3. It is a figure which shows the electron micrograph of the antibacterial nonwoven fabric obtained in Example 4. It is a figure which shows the electron micrograph of the antimicrobial nonwoven fabric obtained in Example 5. FIG. It is a figure which shows the electron micrograph of the antimicrobial nonwoven fabric obtained in Example 7. FIG. It is a figure which shows the electron micrograph of the antibacterial nonwoven fabric obtained in Example 8. It is a figure which shows the electron micrograph of the antibacterial nonwoven fabric obtained in Example 9. It is a figure which shows the electron micrograph of the antimicrobial nonwoven fabric obtained in Example 10. FIG. It is a figure which shows the electron micrograph of the antibacterial nonwoven fabric obtained in Example 11. It is a figure which shows the electron micrograph of the antibacterial nonwoven fabric obtained in Example 12.

Claims (16)

  A resin composition for antibacterial and deodorant articles, comprising 100 parts by mass of biodegradable polyester and 0.01 to 50 parts by mass of amino polysaccharide.   The resin composition for an antibacterial / deodorant article according to claim 1, wherein the biodegradable polyester and the aminopolysaccharide are mixed in a solid state and then heated and kneaded.   The resin composition for antibacterial and deodorant articles according to claim 1 or 2, wherein the aminopolysaccharide is uniformly dispersed in the biodegradable polyester.   The resin composition for antibacterial / deodorant articles according to any one of claims 1 to 3, comprising only the biodegradable polyester and the aminopolysaccharide.   The resin composition for antibacterial and deodorant articles according to claim 1, further comprising an acid amide solvent and an organic acid solvent.   Prepared by mixing a biodegradable polyester-containing solution obtained by dissolving the biodegradable polyester in an acid amide solvent and an aminopolysaccharide-containing solution obtained by dissolving the aminopolysaccharide in the organic acid solvent. The resin composition for antibacterial and deodorant articles according to claim 5.   The resin composition for antibacterial and deodorant articles according to claim 1, further comprising formic acid, wherein the biodegradable polyester and the aminopolysaccharide are dissolved in formic acid.   The resin composition for antibacterial and deodorant articles according to any one of claims 5 to 7, which is uniformly transparent.   The resin composition for antibacterial / deodorant articles according to any one of claims 1 to 8, wherein the aminopolysaccharide has a D-glucosamine unit or an N-acetyl-D-glucosamine unit.   The said biodegradable polyester is polylactic acid, The resin composition for antibacterial and deodorizing articles | goods of any one of Claims 1-9.   An antibacterial / deodorant fiber having an average fiber diameter of 1 nm to 10 μm formed by spinning the resin composition for antibacterial / deodorant articles according to claim 1.   An antibacterial / deodorant nonwoven fabric comprising the antibacterial / deodorant fiber according to claim 11.   The antibacterial and deodorant film formed by shape | molding the resin composition for antibacterial and deodorant articles of any one of Claims 1-10.   A method for producing an antibacterial and deodorant nonwoven fabric, comprising spinning a resin composition containing a biodegradable polyester and an aminopolysaccharide by an electrostatic spinning method.   The resin composition is prepared by mixing a biodegradable polyester-containing solution in which a biodegradable polyester is dissolved in an acid amide solvent and an aminopolysaccharide-containing solution in which the aminopolysaccharide is dissolved in an organic acid. Item 15. A method for producing an antibacterial / deodorant nonwoven fabric according to Item 14.   The method for producing an antibacterial / deodorant nonwoven fabric according to claim 14, wherein the resin composition is prepared by dissolving the biodegradable polyester and the amino polysaccharide in formic acid.