JPH07242772A - Chitosan-polymer composite, its production, and composition containing it - Google Patents

Abstract

PURPOSE:To improve the durability of a chitosan deriv. without detriment to the antibacterial properties inherent in chitosan to thereby enable a suitable antibacterial treatment of fiber, etc. CONSTITUTION:A chitosan-polymer composite powder is obtd. by dissolving a decomposition product of chitosan in an aq. medium, adding an emulsifier and a polymn. initiator to the resulting soln., adding an alpha, beta-ethylenically unsatd. monomer to the soln. dropwise to polymerize it, and drying the resulting emulsion. The composite powder is mixed with a fine hot-melt resin powder, scattered on a fiber, and heated to adhere to the surface of the fiber.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a chitosan-polymer composite compound and its production in which a chitosan degradation product having antibacterial properties derived from chitosan is complexed with a polymer compound to improve durability. The present invention relates to a method and a composition which can be suitably used as an antibacterial processing agent for fibers and the like using the method.

[0002]

2. Description of the Related Art It has been conventionally known that polymeric chitosan exhibits antibacterial properties by forming a quaternary salt by forming a salt with an organic acid such as acetic acid. In addition, Japanese Patent Laid-Open No. 2-4
Japanese Patent No. 1473 discloses that a chitosan degradation product obtained by cleaving the main chain of a high molecular weight chitosan to reduce its molecular weight and then using it as a salt also exhibits antibacterial properties. Also, according to the recent researches by the present inventors,
It has been elucidated that the salt of this chitosan degradation product exhibits antibacterial properties even in the neutral and alkaline regions. Chitosan derivatives such as high molecular weight chitosan salts having antibacterial properties, chitosan decomposition products, and chitosan decomposition products in which salts have been eliminated by neutralization are attached to fibers to obtain antibacterial fibers. It is highly expected that However, since these chitosan derivatives are water-soluble, there is a problem that the antibacterial effect of the fibers is easily impaired by washing or the like when they are directly attached to the fibers, resulting in poor practicability.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to improve the durability of a chitosan derivative without impairing the antibacterial property derived from chitosan and to improve its practicality.

[0004]

This problem can be solved by physically compositing a chitosan degradation product and a polymer compound.

[0005]

The chitosan-polymer composite used in the present invention is a physical composite of a decomposed product of chitosan and a polymer compound. Here, to physically combine,
It means that the chitosan degradation product and the high molecular compound can be integrated with each other without forming a chemical bond. And preferably in the form of particles, the chitosan decomposition product may be distributed in the particles of the polymer compound in the particle form, may be on the surface of the polymer compound, further the polymer compound It may be in a finely dispersed state. For example, it may be in the form of a microcapsule or the like. The complex thus obtained has antibacterial properties derived from the chitosan degradation product because there is no chemical bond between the chitosan degradation product and the polymer compound. In addition, the decomposed product of chitosan has a sustained release property because it is complexed with a polymer compound, and has improved durability against external action by water or the like. Therefore, an antibacterial product having durability and capable of exhibiting antibacterial properties for a long period of time can be obtained by subjecting a substrate such as a fiber to antibacterial treatment using a chitosan-polymer composite. Furthermore, the antibacterial effect time can be arbitrarily controlled by localizing the chitosan degradation product in the particles during the complexing.

The reason why chitosan is used as a decomposed product is as follows. Acetic acid aqueous solution of polymer chitosan,
When a particulate compound is formed by complexing with a polymer compound in a dispersion medium, the polymer chitosan itself functions as an aggregating agent because it is a polymer electrolyte. As a result, the dispersion system for preparing the composite is destroyed, and it is difficult to efficiently obtain the composite. further,
If the pH of the dispersion system is adjusted to neutral or alkaline in order to obtain the complex, there is a problem that the antibacterial property derived from chitosan disappears due to the elimination of the salified salt of the salt (Journal of the Fiber Society of Japan, Vol. Issue Issued on April 10, 1991
Textile Society of Japan). For the above reasons, the decomposed product of chitosan is preferably used.

The present invention will be described in detail below. In the present invention, the decomposed product of chitosan is a polymer chitosan, which is decomposed using enzymes such as cellulase, chitosanase and chitinase, hydrogen peroxide and hydrochloric acid to obtain a decomposed product of chitosan,
Then, the salt obtained by neutralizing this chitosan decomposition product salt with a basic compound (ammonia water, aqueous sodium hydroxide solution, etc.) is collectively referred to.

The chitosan degradation product can be obtained, for example, as follows. First, preferably, a solution is prepared by dissolving 2% by weight of powdery polymer chitosan in 1% by weight of acetic acid aqueous solution, and 5% by weight to 50% by weight of cellulase which is an enzyme for a chitosan substrate is added. Next, by heating and stirring treatment under a temperature condition of preferably 40 to 50 ° C., the high molecular weight chitosan is reduced in molecular weight to obtain a chitosan decomposition product salt. At this time, if the treatment time is preferably 24 to 48 hours, the average molecular weight of chitosan can be reduced to approximately 280,000 to 1,100. Furthermore, the decomposition reaction is stopped by preferably performing heat treatment at 100 ° C. for 30 minutes. After cooling, the solution is adjusted to about pH 7 with an aqueous sodium hydroxide solution to obtain a chitosan decomposition product.

The chitosan-polymer composite material of the present invention can be obtained by compositing the above chitosan decomposition product with a polymer compound by various compositing methods. As the polymer compound, a polymer compound of acrylic resin type, polyester resin type, urethane resin type, amino resin type, polysaccharide type, inorganic type or the like can be used.

The production of chitosan-polymer composite is (1)
It can be carried out by a method of obtaining an emulsion chitosan-polymer composite by an emulsion polymerization method or (2) a method of obtaining a powdered chitosan-polymer composite by a spray drying method. And as a monomer which comprises a high molecular compound, (alpha), (beta) -ethylenically unsaturated monomer is used suitably.

First to produce chitosan-polymer composite
An emulsion polymerization method will be described as the above method.
Specifically, in the presence of a decomposed product of chitosan, water, and optionally an emulsifier, α, β-ethylenically unsaturated monomers are dropped into a reaction vessel, and an emulsion polymerization method is performed in the presence of a polymerization initiator. By polymerizing with, an aqueous emulsion of the complexed compound can be obtained. This emulsion polymerization is 0
It is carried out at a temperature of -100 ° C, preferably 30-90 ° C. Here, as the water, ion-exchanged water is preferably used.
Further, the α, β-ethylenically unsaturated monomers to be dropped may be in an emulsified state, and the dropping can be performed separately or continuously. The amount of chitosan degradation products used is
0.0 with respect to the total amount of α, β-ethylenically unsaturated monomers
A range of 1-5% by weight is preferred. If it exceeds 5% by weight, the dispersed state in the reaction system becomes unstable, which is not preferable. 0.0
If it is less than 1% by weight, the antibacterial effect is small and satisfactory performance is not exhibited. The ratio of the total amount of α, β-ethylenically unsaturated monomers to water is set so that the final solid content is in the range of 1 to 60% by weight of water, preferably 15 to 55% by weight. The composition of the α, β-ethylenically unsaturated monomers has a glass transition point of -1 of the emulsion particles obtained.
It is preferably set to be in the range of 0 ° C to 50 ° C.

[0012] In carrying out such emulsion polymerization, a seed polymerization method in which emulsion particles are present in the aqueous phase in advance to carry out the polymerization is used to grow or control the particle size and to decompose the chitosan degradation product in the particles. It is also possible to localize it arbitrarily. Specifically, in the presence of a pre-emulsion containing a decomposed product of chitosan, α, β-ethylenically unsaturated monomers (which may contain a decomposed product of chitosan, if necessary) are additionally polymerized. As a result, on the pre-emulsion surface containing the chitosan degradation product synthesized above,
The α, β-ethylenically unsaturated monomers can be deposited and polymerized. To obtain a chitosan-polymer composite by this method, the pre-emulsion is 0.1% on a solids basis.
It is sufficient to polymerize 50 to 99.9 parts by weight of α, β-ethylenically unsaturated monomers under the condition that -50 parts by weight are present.

Specific examples of the above α, β-ethylenically unsaturated monomer include the following compounds. (Meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and other carboxyl group-containing monomers, maleic anhydride, itaconic anhydride and other polyvalent carboxylic acid anhydride group-containing unsaturated monomers such as α, β-ethylenically unsaturated carboxylic acids; hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and the like, , Hydroxyl group-containing monomers represented by unsaturated group-containing polyhydroxyalkyl esters such as di-hydroxyalkyl esters of polyvalent carboxylic acids such as maleic acid; (meth) acrylamide, N, N-dimethyl ( (Meth) acrylamide, N-alkoxymethylated (meth)
Carboxamide group-containing monomers represented by acrylamide, diacetone acrylamide, etc .; represented by p-styrenesulfonamide, N-methyl-p-styrenesulfonamide, N, N-dimethyl-p-styrenesulfonamide, etc. Sulfonamide group-containing monomers; N, N
-Tertiary amino group-containing monomers represented by N, N-dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate; (meth)
Cyano group-containing monomers represented by acrylonitrile;
Monomers having a sulfonic acid group such as 2-acrylamido-2-methylpropanesulfonic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth ) (Meth) acrylic acid alkyl esters having a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms such as acrylate; styrene, α-methylstyrene, p-tert-butyl-styrene, p-methylstyrene, etc. Aromatic compounds such as styrene or its derivatives; vinyl acetate, vinyl benzoate, "Veova (trade name)" (vinyl ester,
(Made by Shell Co.) and the like; vinyl chloride, vinylidene chloride, vinyl fluoride, ethylene, propylene,
Olefin such as butadiene; Epoxy group-containing monomers such as glycidyl (meth) acrylate; Isocyanate group-containing monomers such as isocyanate ethyl (meth) acrylate and (blocked) isocyanate group-containing units such as blocked products thereof Body; having two or more polymerizable unsaturated groups in the molecule such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, divinylbenzene and diallyl phthalate. Monomers; vinyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane,
Examples of the hydrolyzable silyl group-containing monomers such as γ- (meth) acryloyloxypropylmethyldimethoxysilane and γ- (meth) acryloyloxypropyltriethoxysilane. One kind or two or more kinds are appropriately selected and used according to the required performance to be used.

Examples of the emulsifier include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, as well as reactive emulsifiers and substances having surface activity such as acrylic oligomers. Among these, nonionic and anionic emulsifiers are included. However, it is preferably used because the amount of aggregates generated during the polymerization is small and a stable emulsion can be obtained.
As the nonionic emulsifier, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ether, polyoxyethylene higher fatty acid ester, ethylene oxide-propylene oxide block copolymer and the like are typical, and as the anionic emulsifier, Alkylbenzene sulfonic acid alkali metal salts, alkyl sulfate alkali metal salts, polyoxyethylene alkylphenol sulfate alkali metal salts, and the like. Further, a water-soluble oligomer composed of a polycarboxylic acid or a sulfonate can be used in place of or in combination with the above-mentioned anionic emulsifier. Further, a water-soluble polymer substance such as polyvinyl alcohol or hydroxyethyl cellulose can be used as a protective colloid. The amount of these emulsifiers used is preferably about 0.1 to 10% by weight based on the total amount of monomers.

The polymerization initiator is not particularly limited as long as it is one generally used in emulsion polymerization,
Specific examples include water-soluble inorganic peroxides such as hydrogen peroxide; persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate; organic peroxides such as cumene hydroperoxide and benzoyl peroxide.
There are azo-based initiators such as azobisisobutyronitrile and azobiscyanovaleric acid, which may be used alone or in combination. The amount used is preferably 0.1 to 2% by weight based on the total amount of monomers. It is also possible to use these polymerization initiators in combination with a metal ion and a reducing agent to perform polymerization by a known redox polymerization method in which polymerization is performed at a low temperature.

The thus obtained aqueous dispersion of the complexed compound can be used as it is, but by removing the aqueous medium from this system and pulverizing it, powdery chitosan- A polymer composite can be obtained. Here, the removal method of the aqueous medium is as follows:
Spray drying at a temperature of 00 to 250 ° C. (spray drying method), tray drying at a temperature of 50 to 70 ° C., fluidized bed drying, or the like can be used, but it causes denaturation of the chitosan-polymer composite by heat. The spray dry method is preferred because it is difficult. The obtained powder particles are generally agglomerates (secondary particles) of primary particles (fine particles having a particle size in an emulsion state), which are, if necessary, dispersants, emulsifiers, protective colloids, etc. Can be added and redispersed in water.

Second Method for Producing Chitosan-Polymer Complex
The spray dry method will be described as a method. In this method, a chitosan degradation product is mixed with a polymer of an α, β-ethylenically unsaturated monomer in an aqueous medium, and then the aqueous medium is removed from the system to obtain a powdered chitosan-polymer. This is a method of obtaining a composite. Specifically, first, emulsion polymerization is carried out using the above-mentioned monomers in an aqueous medium to prepare an emulsion-like polymer dispersion liquid containing no chitosan decomposition product in advance. Next, after mixing this dispersion and the chitosan decomposition product, the aqueous medium is removed by a spray drying method. In such a method, the mixture of the polymer dispersion and the chitosan decomposition product undergoes a drying process by spray drying, whereby the chitosan decomposition product is immobilized on the polymer by heat, and the chitosan decomposition product and A complex with the molecular compound is formed. At this time, the amount of the decomposed product of chitosan mixed with the polymer is preferably in the range of 0.01 to 5% by weight based on the solid content of the polymer.

In addition to the above-mentioned methods, various methods generally used for producing microcapsules can be used as the method for producing a chitosan-polymer composite. For example, as a chemical preparation method, an interfacial polymerization method, in
-Situ polymerization method, coacervation method, in-liquid drying method, or a physical preparation method such as a hybridization method can be used.

The chitosan-polymer composite thus obtained is used in the case of subjecting a substrate such as a fiber to an antibacterial treatment, and the powder, emulsion, or film containing this and an organic binder is used. It is preferable to use a composition having a shape. Here, examples of the organic binder used include room temperature drying, forced drying, baking drying, and the like.
Alternatively, the film is formed by curing,
As long as it is usually used for fiber processing and coating, it can be used without any particular problems. Specific examples thereof include aqueous emulsion type resins; solvent type acrylic lacquer type resins, urethane resins, isocyanate curing type resins, non-aqueous dispersion type resins, acrylic-melamine resins, polyester-melamine resins, alkyd resins, alkyd-type resins.
Examples thereof include melamine resin; or these aqueous resins; acrylic resin, polyester resin, polyamide resin, polyolefin resin powder resin, and the like. These organic binders are appropriately selected and used depending on the form of the chitosan-polymer composite such as emulsion or powder, and are thermoplastic or thermosetting acrylic or urethane aqueous emulsion type resins. Alternatively, acrylic-based, polyester-based, polyamide-based, polyolefin-based powder resins and the like are preferably used from the viewpoint of workability.

In addition to the organic binder, the composition may also contain various additives as shown below. For example, heavy calcium carbonate, precipitated barium sulfate, mica, titanium oxide, inorganic pigments or fillers such as kaolin, ultrafine particle silica, zinc white, carbon black; phthalocyanine-based, azo-based, quinacridone-based, etc. Pigments such as organic pigments or dispersion pigments thereof; Chisso Sizer CS-12 (product of Chisso Corporation),
Film-forming aids or plasticizers such as butyl carbitol acetate, butyl cellosolve, and dibutyl phthalate; various anionic and nonionic surfactants; pyrophosphoric acid,
Dispersing agents such as salts of tripolyphosphoric acid, polycarboxylic acids, salts of naphthalene sulfonic acid; antifoaming agents such as silicone-based or acrylic-based oligomers; and other preservatives, etc. It is determined as appropriate. Other than these, any additives commonly used for fiber treatment or coatings can be used without any particular problems.

The composition thus obtained can be applied to various base materials to give an antibacterial product having an antibacterial effect for a long period of time. In particular, it is effective when used as an antibacterial processing agent having fibers as a base material. When the composition of the present invention is used as an antibacterial agent for fibers, the composition is made into a powder form, a method of attaching and processing the composition to the fiber by heat fusion, the composition is made into an emulsion form, and the composition is coated on the fiber. After applying by spraying or impregnation, if necessary, a method of curing by drying at room temperature or forced drying, a composition in the form of a film, and laminating this with a fiber, etc. Can be given. Furthermore, preferably, a monomer containing a functional group such as a hydroxyl group, a carboxyl group or a sulfhydryl group in the fiber used as a material, or a functional group reactive with a functional group in an organic binder is α, β-ethylene. It is preferable to use it during the polymerization of the polymerizable unsaturated monomer. Specific examples of such functional group-containing monomers include methylol group-containing monomers such as N-methylolated (meth) acrylamide, epoxy group-containing monomers such as glycidyl (meth) acrylate, and isocyanate. Examples thereof include isocyanate group-containing monomers such as ethyl (meth) acrylate and (blocked) isocyanate group-containing monomers such as blocked products thereof. By introducing these functional group-containing monomers into the chitosan-polymer composite, the composite and the fiber surface or the organic binder partially react, or the affinity is improved, and the composite or composition It is possible to improve the adhesion to the fiber material.

[0022]

EXAMPLES Examples of the present invention will be shown below. In the examples, “part” represents “part by weight”. Reference Example 1 A chitosan degradation product was prepared. First, 2% by weight of powdery polymer chitosan (manufactured by Katakura Chikkarin Co., Ltd., having a deacetylation degree of 82%) was dissolved in a 1 wt% acetic acid aqueous solution to prepare a polymer chitosan acetic acid solution. Next, 0.5 wt% of cellulase enzyme was added to the polymer chitosan in the solution, and the enzyme treatment was carried out at 40 ° C. for 2 to 3 hours. Then, heat treatment at 100 ° C. was performed to stop the enzyme reaction. FIG. 1 shows the relationship between the enzyme treatment time and the viscosity of the aqueous solution of polymer chitosan in acetic acid. The viscosity of the solution by enzyme treatment of 3 hours from 4,000C _p 100
It fell to C _p . Moreover, the average molecular weight of the polymer chitosan calculated from this viscosity was 5 by the enzyme treatment for 3 hours.
It dropped from 0,000 to 38,000. Further, using a 2% by weight aqueous solution of sodium hydroxide, p
H-substantially neutralized, and a chitosan decomposition product from which acetic acid was eliminated was prepared. In this way, a chitosan decomposition product aqueous solution (A-1) of about 2% by weight was obtained.

Example 1 A chitosan-polymer composite was prepared by an emulsion polymerization method. In the emulsion polymerization, the seed polymerization method described above was used. An aqueous solution (A-1) 25 of the decomposed product of chitosan obtained in Reference Example 1 was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube.
Parts, deionized water 106.5 parts, and emulsifier 0.6 parts (polyoxyethylene nonylphenyl ether (HLB
13) 0.2 part and a mixture of 0.4 part of sodium dodecylbenzene sulfonate) are added and heated to 75 ° C.,
The chitosan degradation product was dissolved. Then, a mixture of 19 parts of methyl methacrylate (MMA) and 1 part of ethylene glycol dimethacrylate (EDMA) and a mixture of 0.06 part of potassium persulfate and 1.2 parts of ion-exchanged water were separately charged in the reaction vessel for 1 hour. Was added dropwise. After the dropping was completed, the temperature was maintained for 1 hour. Then, in a solution prepared by dissolving 0.2 parts of sodium dodecylbenzenesulfonate in 20 parts of ion-exchanged water, 73 parts of styrene (St), 4 parts of divinylbenzene (DVB), 1 part of acrylic acid (AA), N-methylol 2 parts of modified acrylamide was added and mixed to emulsify. The obtained mixture and 0.24 parts of potassium persulfate dissolved in 4.8 parts of ion-exchanged water were added dropwise to the above reaction vessel separately for 2 hours. After the dropping was completed, the temperature was maintained for 3 hours. After the reaction is completed, the temperature is cooled to room temperature, and then 200
The mixture was filtered through a mesh screen to prepare an aqueous dispersion of chitosan-polymer composite (B-1). The obtained aqueous dispersion (B-1) had a nonvolatile content (NV) of 40% and a pH of
4.8, a white emulsion having an average particle size of 0.25 μm according to Coulter Counter Model N-4,
It contained 0.5% by weight of chitosan degradation product per emulsion solids.

(Example 2) A powdered composite was prepared from the aqueous dispersion of the composite obtained by the emulsion polymerization method. The chitosan-polymer compound aqueous dispersion (B-1) obtained in Example 1 was dried with a mobile minor type spray dryer (manufactured by Nilo Atomizer, Denmark) and powdered to give a powdered chitosan-polymer. A composite was prepared. At this time, the operating conditions of the spray dryer are: inlet temperature 200 ° C., exhaust heat temperature 70 ° C., atomizer rotation speed 25000 rpm / min, (B-1) supply rate 50.
It was set to 0 g / hr. The obtained composite has a water content of 0.7.
%, An aggregate of primary particles having an average secondary particle diameter of 15 μm and containing 0.5% by weight of a chitosan decomposition product per solid content. Hereinafter, this is described as (B-2).

Reference Example 2 A polymer of α, β-ethylenically unsaturated monomer mixed with a decomposition product of chitosan was prepared when a chitosan-polymer composite was prepared by a spray drying method. Polymerization was carried out in the same manner as in Example 1 except that ion-exchanged water was used instead of the chitosan decomposition product of Example 1, to prepare a fine particle polymer containing no chitosan acetate. The obtained emulsion (A-2) was NV. The white emulsion was 40.0%, pH 4.8, and had an average particle size of 0.23 μm according to Coulter Counter Model N-4.

Examples 3 to 5 Chitosan-polymer composites were prepared by the spray drying method. White emulsion (A-2) of a polymer of α, β-ethylenically unsaturated monomer containing no chitosan decomposition product obtained in Reference Example 2 above.
And the chitosan degradation product (A-1) obtained in Reference Example 1 above
Were mixed in three different formulations shown in Table 1 below, and powdered under the same spray dryer operating conditions as in Example 2. Table 1 also shows the water content, the average particle diameter (secondary particle diameter), and the content of the decomposed product of chitosan immobilized on the surface of the fine particles of the obtained powdered composite. still,
The composite compounds obtained in Examples 3 to 5 are described below as (B-3), (B-4) and (B-5), respectively.

[0027]

[Table 1]

(Application Example 1) A powdered chitosan-polymer composite was used, mixed with an organic binder and subjected to heat fusion processing. First, the powdered composite (B-3) obtained in Example 3 and the fine particle heat fusion resin (Finedec,
It was well mixed with Dainippon Ink and Chemicals, Inc. at a weight ratio of 1: 2. Then, this powder mixture was evenly spread over the cotton knitted fabric using a spatula. Furthermore, a cotton knitted fabric on which the powder mixture was sprinkled was wrapped in a sandwich with a Teflon film, and this was heat-treated using a dry heat tester. The thermal treatment at this time was 150 ° C. for 3 minutes.
The amount of the powder mixture fixed was about 0.5 g per 1 g of the base cloth. The amount of the chitosan degradation product attached to the obtained cotton knitted fabric was 0.37 mg per 1 g of the raw cloth. (Application Examples 2 and 3) Further, using the composites (B-4) and (B-5) obtained in Examples 4 and 5, respectively,
A cotton knit fabric was processed in the same manner as in Application Example 1. The amounts of the chitosan degradation products attached to the obtained cotton knitted fabric were 0.67 mg and 1.1 mg, respectively, per 1 g of the raw cloth.

(Test Examples 1 to 3) Antibacterial tests were conducted on the cotton knitted fabrics having different contents of the three types of decomposed products of chitosan obtained in Application Examples 1 to 3. Antibacterial test is a gram-positive bacterium Staphylococcus epidermidis
Was used by a combined method of the usual shake flask method and flat plate pour method. First, 20 ml of a 1/300 mol phosphate buffer having a pH of 7.2 containing a predetermined culture broth was placed in an Erlenmeyer flask, and 1 g of the processed dough was further placed. The test solution was shaken at 10 ° C. 80 times per minute and cultured for a certain period of time. After the start of the culture, a predetermined amount of the test solution was sampled from the Erlenmeyer flask every predetermined time, and the test solution was collected at a pH of 1 / 7.2.
Diluted with 15 molar phosphate buffer. 1 ml of this diluent
Was collected in a Petri dish, and the mixture was poured into a standard agar medium, and then placed in a Flanker at 35 ° C. and cultured for 48 hours. After culturing, the number of colonies generated in the Petri dish was measured, and the number of viable bacteria present in 1 ml of the test solution in the Erlenmeyer flask was determined from the value. The results are shown in the graph of FIG. In the graph of FIG. 2, the horizontal axis represents the culture time in the Erlenmeyer flask, and the vertical axis represents the number of viable bacteria present in 1 ml of the test solution in the Erlenmeyer flask.
The broken line in the graph indicates the result of a control test in which only the culture solution was cultured under the same conditions without using the cloth.

(Comparative Test Example 1) A cotton knitted fabric was prepared in the same manner as in Application Example 1 except that the particulate heat-fusion resin not mixed with the compound (B-3) was used. An antibacterial test was conducted in the same manner as 1. The result is shown in Figure 2.
Is shown in the graph. (Comparative Test Example 2) An unprocessed cotton knitted fabric base cloth was prepared, and an antibacterial test was conducted in the same manner as in Test Example 1 above. The results are shown in the graph of FIG.

From the results in the graph of FIG. 2, the antibacterial performance of the cotton knitted fabric was more excellent as the content of the decomposed product of chitosan in the processed fabric was larger.

[0032]

As described above, the chitosan of the present invention
The polymer composite is a physical composite of a decomposed product of chitosan and a polymer compound. Therefore, the durability of the decomposed product of chitosan can be improved without impairing the antibacterial property. Therefore, using this, it is possible to suitably perform antibacterial processing on the fiber or the like. In addition, the sustained release property of the decomposed product of chitosan can be improved, and the antibacterial retention time can be extended.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the treatment time of an aqueous polymer chitosan acetic acid solution with an enzyme and the viscosity.

FIG. 2 is a graph showing the results of an antibacterial test when the chitosan-polymer composite material of the present invention was processed into a fabric.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Onozaki 1 of 13-1 Imamiya, Utsunomiya City, Tochigi Prefecture (72) Inventor Shinichi Kuwamura 1-4-2-206 (72) Invention, Mammanaka, Hiroryo-cho, Kitakatsuki-gun, Nara Prefecture Fumio Yoshino 3-5-504 Oi Chihara, Izumiotsu City, Osaka Prefecture

Claims (4)

[Claims] 1. A chitosan-polymer composite obtained by physically composing a decomposed product of chitosan and a polymer compound. 2. A method for producing a chitosan-polymer composite, which comprises polymerizing an α, β-ethylenically unsaturated monomer in the presence of a decomposed product of chitosan in an aqueous medium. 3. A chitosan decomposition product, α,
A method for producing a chitosan-polymer composite, which comprises mixing a polymer compound obtained by polymerizing a β-ethylenically unsaturated monomer, and then removing the aqueous medium to form a powder. 4. A composition containing the chitosan-polymer composite according to claim 1 and an organic binder.