JP2019112756A - Bactericidal polymer nanofiber assembly and dry hygiene paper using the same - Google Patents

Abstract

Disclosed is a germicidal material that can be mass-produced in a simple process using equipment that is easy to operate by using a polymer nanofiber aggregate as an alternative to a microcapsule having a complicated manufacturing process. Provide sanitary paper using The germicidal polymer nanofiber aggregate of the present invention has a dry aggregate in which hollow polymer nanofibers (1) having open ends are assembled. A bactericidal coating layer 3 containing a quaternary ammonium salt having at least one of a carboxyl group and a hydroxyl group is provided on an inner surface portion and an outer surface portion of the hollow polymer nanofiber 1. The sanitary paper of the present invention is a paper in which the above-described germicidal polymer nanofiber aggregate is mixed with paper made of dry wood fiber. [Selection diagram] Fig. 1

Description

  The present invention is a hygienic product wherein an assembly obtained by providing a bactericidal coating layer such as a surfactant to a nanofiber made of a polymer material such as PP (polypropylene) and the bactericidal polymer nanofiber assembly are blended. Related to paper.

  In recent years, nanofibers attracting attention are not only used alone based on their own physical properties, but in the field of composite materials, they are used in a wide range of fields such as general-purpose products, filter materials, electronic parts, automotive parts and medical / biomaterials. It has been put into practical use, and applied development is being considered in each company and national project.

The main features of nanofibers are: 1) super specific surface area effect (high adsorptivity, strong adhesion, high molecular recognition) 2) nano size effect (low pressure loss, high transparency) 3) super As a material to support the advanced technology, development in a wide range of fields is actively carried out in various fields around the world, including the molecular alignment effect (high strength, high electrical conductivity, high thermal conductivity) etc. (see Non-Patent Document 1) ).
For example, when nanofibers are used as the material of the adsorbent, the specific surface area of the adsorbent is expanded to increase the adsorption capacity and the adsorption selectivity is enhanced. A technique for adsorbing a large amount of cell membranes has also been developed (see Patent Document 1).

On the other hand, microcapsule production technology began with the commercialization of non-carbon copying paper in the 1950s, and achieved rapid development in the mid 70's.
Microcapsules are applied in a wide range of fields such as pharmaceuticals, agricultural chemicals, foods, paints, inks, adhesives and the like (see Non-Patent Document 2, Non-Patent Document 3, Patent Document 2).

  The main effects of microencapsulation are the stabilization of the form of fixing the core material such as liquid, the isolation effect to prevent the reaction and mixing between the surrounding material and the core material, the storage effect of the core material, shielding of toxicity and odor The effect, the effect which suppresses the discharge | release of a core material, etc. are mentioned, It is used by the above-mentioned various use.

  Encapsulation techniques are roughly divided into three methods: mechanical methods (orifice method), physical methods (phase separation method etc.), and chemical methods (interfacial polymerization method etc.), core material suitable for each technique, wall Wood is used.

  Conventionally, microcapsules containing a bactericidal component, an analgesic component, a deodorizing component, a perfume component, an antioxidant component, a skin care component, etc. are used in various fields such as hygiene paper, wet cloth, fragrance, deodorant, agrochemicals (See Patent Documents 3 to 5 and the like).

Among the various components mentioned above, cationic surfactants (quaternary ammonium salts) are currently used in a broad field as a bactericidal agent. The positively charged cationic surfactant has an excellent feature that the rate of adsorption to the negatively charged bacterial surface is fast, and the development of a rapid bactericidal effect is observed.
Two actions have been reported as the action mechanism of quaternary ammonium salts.
One is "physical destruction of the cell membrane", which is the action that the cation of the ammonium molecule binds to the anion site of the bacterial surface and physically destroys the cell membrane by hydrophobic interaction (see Non-patent Document 4). ). The other is "bacterial metabolic function inhibition", which quaternary ammonium salt strongly adsorbs to bacteria and inhibits intracellular enzymes to inhibit / inhibit metabolic function (growth). (Non-Patent Document 5).

  Conventionally, various techniques for microencapsulation including a bactericidal component, an analgesic component, a deodorizing component, a perfume component, an antioxidant component, a skin care component and the like have been variously studied and put to practical use, but the main techniques have already been described. Examples include mechanical methods (orifice method), physical methods (phase separation method, etc.), and chemical methods (interface polymerization method, etc.).

  Among the techniques of microencapsulation, in the orifice method, a polymer solution containing various components (core substances) is dropped from a double pipe into a curing liquid to produce microcapsules.

In the phase separation method, the core material that needs to be wrapped is dispersed in the organic solution containing the wall material to wrap and cover the core material, but at that time the pH value, concentration, temperature, etc. of the solution It is necessary to adjust the conditions and gradually deposit the wall material on the capsule core surface.
In the interfacial polymerization method, microcapsules are produced by causing a polymerization reaction at the interface between a hydrophobic organic solvent containing a core substance and water.

The above-described microencapsulation technique has a problem that the process becomes complicated and the mass production is difficult in industrial production with any technique.
In recent years, a new functional composite material (element) using the above-described nanofiber as a substitute for such a microcapsule has been required, but has not been realized yet.

  On the other hand, conventionally, as a hygienic paper having a sterilizing component, wet wet paper impregnated with an aqueous solution such as alcohol or sodium hypochlorite is commercially available. With such wet hygienic paper, While the weight of the product is heavy, once the product provided in a sealed state is opened, the shelf life is shortened, and furthermore, since the aqueous solution is impregnated in the paper, it is impossible to use a component that is not soluble in water And other issues.

  Further, in the conventional wet type sanitary paper, for example, it is necessary to blend the bactericidal component solution by about 10 times with respect to the raw material pulp, and there is a problem that the cost becomes high. It was difficult to make adjustments.

FY 2015 Patent Application Technical Trend Survey Report "Nanofiber": Patent Office "Micro-encapsulation": Wikipedia, February 2008 Survey report "Microcapsule": Toray Research Center September 2013 "Antibacterial / Antifungal": Hiroki Korei 1995, Vol. "Antibacterial and Antifungal Chemistry": Hiroshi Horiguchi, Sankyo Publishing 1982

JP, 2016-49527, A Japanese Patent Application Laid-Open No. 62-146584 Japanese Patent Application Laid-Open No. 2-300301 JP, 2004-324026, A JP, 2006-291425, A

  The present invention has been made to solve the problems of the prior art, and the object of the present invention is to use a polymer-based nanofiber assembly as a substitute for microcapsules having a complicated manufacturing process. It is an object of the present invention to provide a bactericidal material that can be mass-produced in a simple process using equipment that is easy to operate, and a sanitary paper using the same.

  Another object of the present invention is to provide a bactericidal material which is dry, light and easy to handle, and can maintain its bactericidal property over a long period of time, and a sanitary paper using the same.

  Another object of the present invention is to provide a bactericidal material capable of reducing and adjusting the amount of bactericidal component without reducing bactericidal activity and a sanitary paper using the same.

The present invention made to achieve the above object comprises an aggregate of hollow polymeric nanofibers open at both ends, wherein the inner surface portion and the outer surface of the hollow polymeric nanofibers It is a bactericidal polymeric nanofiber aggregate in a dry state provided with a bactericidal coating layer containing a quaternary ammonium salt having at least one of a carboxyl group or a hydroxyl group on the surface portion.
The present invention is a hygienic member in which the above-mentioned germicidal polymer nanofiber aggregate is blended in a member comprising dry wood fibers.
The present invention is a hygienic paper in which the above-mentioned germicidal polymer nanofiber aggregate is blended in paper made of dry wood fibers.
In the present invention, the step of surface-treating an aggregate of hollow polymer-based nanofibers opened at both ends, and the aggregate of polymer-based nanofibers subjected to the surface treatment are 10 μm to 3 mm in length. Crushing into components, and a quaternary ammonium salt having at least one of a carboxyl group or a hydroxyl group on the inner surface portion and the outer surface portion of the components of the assembly of the pulverized polymer nanofibers. Providing a bactericidal coating layer to be contained and drying it, and a method of producing a bactericidal polymer nanofiber assembly.
According to the present invention, it is also effective to perform the surface treatment of the aggregate of the polymer nanofibers with a fatty acid amide and hypochlorous acid in the method for producing the above-mentioned germicidal polymer nanofiber aggregate. .
The present invention uses a slurry-like stock obtained by dispersing the bactericidal polymer nanofiber aggregate obtained by any of the above-described methods in pulped raw material wood, using a predetermined papermaking process. It is a manufacturing method of the sanitary paper which has the process of making the sanitary paper of a dry state through.

  Since the bactericidal nanofiber assembly used in the present invention is provided with a bactericidal coating layer on the surface of the polymeric nanofiber, there is no need for the conventional complicated microencapsulation process, and as a result Using a facility that is easy to operate, it can be mass-produced in a simple process.

Moreover, in the present invention, when used, the quaternary ammonium salt, which is a bactericidal component provided in a layer on the surface of the nanofibers, dissolves immediately upon contact with water, and the bactericidal property is expressed. Easy to use and very easy to use.
Moreover, since the quaternary ammonium salt has a function of adsorbing bacteria, bacteria on the surface of the object to be sterilized can be efficiently removed.

  Furthermore, the sanitary paper of the present invention can be reduced in weight because it is dry (in a dry state), and can be maintained in the atmosphere over a long period of time because it is difficult to deteriorate.

  Further, in the present invention, the compounding amount of the bactericidal component can be reduced compared to the prior art without reducing the bactericidal activity, and the adjustment of the compounding amount of the bactericidal component and the selection of the type can be easily performed. it can.

(A) to (f): A schematic view schematically showing an example of components of the bactericidal polymer nanofiber assembly according to the present invention A block diagram showing an example of a method of producing a bactericidal polymer nanofiber assembly and a sanitary paper according to the present invention IR spectrum showing analytical results of PP nanofibers after surface treatment IR spectrum showing analysis results of reaction products after synthesis of quaternary ammonium salt Photograph showing the bactericidal PP nanofiber assembly of the example Photograph showing elements of the same PP nanofiber assembly in an enlarged manner

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.
Fig.1 (a)-(f) is schematic which shows typically the example of the component of the sterilizable polymeric nanofiber assembly which concerns on this invention.

Here, FIG. 1 (a) and FIG. 1 (c) are front views showing the appearance of the polymeric nanofiber used in the present invention, and FIG. 1 (b) is a side view of the same polymeric nanofiber. 1 (d) is a cross-sectional view taken along line AA of FIG. 1 (c).
Moreover, FIG.1 (e) is a front view of the same polymeric nanofiber provided with the germicidal coating layer, FIG.1 (f) is a BB sectional view taken on the line of FIG.1 (e).
On the other hand, FIG. 2 is a block diagram showing an example of the method for producing the bactericidal polymer nanofiber aggregate and the sanitary paper according to the present invention.

  The polymer-based nanofiber 1 used in the present invention is a nanofiber (a fibrous substance having a diameter of 1 nm to less than 1 μm) composed of a polymer material, which is open at both ends (hereinafter referred to as “ It is called a nanofiber.).

  Here, the polymer material constituting the nanofiber 1 of the present invention can be produced in the form of fibers and does not dissolve in water, fatty acid amide, hypochlorous acid, ethanol, isobutyltriethoxysilane, ethyl acetate It is preferable to use one.

  Examples of such a polymer material include those made of a thermoplastic resin such as PP (polypropylene), PET (polyethylene terephthalate), PE (polyethylene), PU (polyurethane) and the like.

  In the case of the present invention, the material of the nanofiber 1 is not particularly limited, but it is made of polypropylene in terms of easiness of production of the fiber and softness when the aggregate is formed. Can be suitably used.

As shown in FIGS. 1 (a) to 1 (d), the nanofiber 1 used in the present invention has a hollow structure inside, that is, a hollow portion 2 formed along the longitudinal direction.
In this case, as the nanofiber 1 of the present invention, a fiber having an inner diameter of about 1/2 of the outer diameter can be suitably used.

  Specifically, hollow nanofibers having an outer diameter of 200 to 1000 nm and an inner diameter of 100 to 500 nm are preferable, and more preferably, the outer diameter is 300 to 500 nm and the inner diameter is 150 to 250 nm.

  As shown in FIG. 1 (e) (f), the bactericidal polymer nanofiber assembly 10 of the present invention is a quaternary ammonium in the surface portion of the fiber (the outer surface portion 1a and the inner surface portion 1b) A bactericidal coating layer 3 containing a bactericidal material consisting of a salt is provided.

Hereinafter, examples of the method for producing the bactericidal polymer nanofiber assembly and the sanitary paper according to the present invention will be described with reference to FIGS. 1 (a) to (f) and FIG.
As shown in FIG. 2, in this example, first, a surface treatment step of the nanofibers 1 is performed (process P1).

In the present invention, for example, fatty acid amide and hypochlorous acid can be used as materials for surface treatment of the nanofibers 1.
Here, the fatty acid amide is used to degrease the surface portions of the nanofibers 1 (the outer surface portion 1a and the inner surface portion 1b: see FIGS. 1 (a) to (d)).

In the case of the present invention, the type of fatty acid amide used for degreasing the surface of the nanofibers 1 is not particularly limited, but it is preferable to use coconut fatty acid diethanolamide.
Coconut fatty acid diethanolamide is widely used as a nonionic surfactant in shampoos, face wash and the like, and is preferred because it can be easily obtained.
Other fatty acid amides, surfactants and the like can also be used as long as they have a degreasing effect.

  On the other hand, hypochlorous acid reacts with coconut fatty acid diethanolamide adhering to the surface of the nanofiber 1 by the above-mentioned degreasing treatment, and at least one of the carboxyl group or the hydroxyl group covers the surface of the nanofiber, thereby the surface tension thereof. By the effect, the affinity to the quaternary ammonium salt can be improved.

  In the present invention, the material to be subjected to this treatment is not particularly limited to hypochlorous acid, but it is a material used for general purpose and hypochlorous acid is preferred from the viewpoint of easy availability. It is preferred to use.

  When the surface treatment of the nanofibers 1 is performed using the above fatty acid amide and hypochlorous acid, for example, the following treatment is performed.

First, a predetermined amount of nanofibers 1 is dispersed in an aqueous solution of fatty acid amide, and boiled, for example, at a temperature of about 100 ° C. for 30 to 40 minutes.
After the boiling step, the nanofibers 1 are washed with water, dehydrated for, eg, several minutes (about 2000 rpm) using a centrifugal separator, and then dried at a temperature of about 60 ° C. for about 30 minutes.

  A predetermined amount of dried nanofibers 1 is dispersed in an aqueous solution of hypochlorous acid (concentration 8 g / L), and stirred at a temperature of about 30 ° C. for about 1 hour while maintaining the pH at 5 to 5.5. Hypochlorous acid is reacted with the fatty acid amide adhering to the surface of 1.

Then, after completion of the reaction, the nanofiber 1 is filtered under normal pressure, dehydrated for several minutes (about 2000 rpm) in a centrifuge, and then dried at a temperature of about 60 ° C. for about 30 minutes.
Furthermore, the nanofibers 1 after the surface treatment described above are crushed using a pulverizer to a length of 10 μm or more and 3 mm or less (Process P2).
Thereby, an assembly of nanofibers 1 composed of PP is obtained.

Furthermore, a synthesis step of quaternary ammonium salt is carried out (process P3).
In the case of the present invention, the synthesis step P3 of the quaternary ammonium salt may be performed before the nanofiber crushing step P2 or may be performed in parallel with the nanofiber crushing step P2.

  In the synthesis step P3 of the quaternary ammonium salt of this example, 4- (chloromethyl) benzyl alcohol is synthesized from benzyl alcohol as shown in the following reaction formula (1), and N, N-didodecylmethylamine is added thereto. Are reacted to synthesize 4- (chloromethyl) benzyldidodecylmethylammonium chloride, which is a quaternary ammonium salt.

  In this example, 4- (chloromethyl) benzyl alcohol is synthesized from benzyl alcohol by adding formaldehyde to the benzene ring by, for example, Friedel-Crafts reaction and then bubbling hydrogen chloride (about 45 ° C., 8 hours Degree) do.

  Also, in the synthesis of 4- (chloromethyl) benzyldidodecylmethylammonium chloride, first, 4- (chloromethyl) benzyl alcohol synthesized above and N, N-didodecylmethylamine are, for example, 1: 1. It carries out by carrying out stirring reaction for about 10 hours at a temperature of about 100 ° C. and under a pressure of 0.25 to 0.35 MPa by charging into an aqueous solution of sodium carbonate in molar ratio.

  Thereafter, ethylene glycol is added to this solution, and reaction is carried out by stirring for about 8 hours at a temperature of about 90 ° C. and a pressure of 0.2 to 0.3 MPa in the presence of sodium hydrogen carbonate and reacting 4- (chloromethyl) benzyldidodecylmethylammonium chloride shown in the above reaction formula (1) which is a quaternary ammonium salt is obtained.

  The 4- (chloromethyl) benzyl didodecylmethyl ammonium chloride contains a hydroxyl group, and has a good affinity to the surface-treated polymer-based nanofiber 1, particularly a nanofiber 1 composed of PP.

Thereafter, in the present example, the surface of the nanofiber 1 is coated with the quaternary ammonium salt (process P4).
In this step, first, a predetermined amount of quaternary ammonium obtained by the synthesis step of the process P3 is dissolved in ethanol, and a solution obtained by dissolving a predetermined amount of isobutyltriethoxysilane in ethyl acetate in this solution is a hydrophobic material. Add as.

The isobutyltriethoxysilane plays a role of preventing the quaternary ammonium salt from eluting into ethanol or ethyl acetate during the treatment.
Further, a predetermined amount of the surface-treated nanofibers is added to the quaternary ammonium salt solution, and stirred at a temperature of 70 to 80 ° C. for about 60 minutes.

  Thereby, the hydroxyl group of the quaternary ammonium salt reacts with the carboxyl group present on the surface of the nanofiber after the surface treatment, and the above-mentioned quaternary ammonium is applied to the outer surface portion 1a and the inner surface portion 1b of the nanofibers. The salt solution is deposited and these surface parts are coated with the bactericidal material containing quaternary ammonium salt.

  Then, the nanofibers are filtered at normal pressure and then dried at a temperature of 60 to 70 ° C. to separate and evaporate the isobutyl triethoxysilane which is a hydrophobic material, and at the same time, ethanol and ethyl acetate are evaporated. A bactericidal polymer nanofiber aggregate 10 is provided, which is provided with a bactericidal coating layer 3 containing a quaternary ammonium salt on the surface of the nanofibers (see FIG. 1 (e) (f)).

  Thereafter, using the bactericidal polymer nanofiber aggregate 10 compounded with the above-mentioned quaternary ammonium salt, hygienic paper made of, for example, a sheet of paper is prepared, for example, by the following paper making method (process P5).

In this example, first, a step of pulping various kinds of raw material wood is performed, and further, the following adjustment step is performed.
In the preparation step, various pulps are mixed, beaten using an apparatus called refiner, and the particulate germicidal polymer nanofiber aggregate 10 containing the above-mentioned quaternary ammonium salt is dispersed, and also predetermined. Add the following chemicals.

The pulp that has undergone this adjustment step is called slurry in the form of slurry.
Furthermore, the hygienic paper of the present invention can be obtained by passing through a known papermaking process, a coating process, and a finishing / processing process.

The present invention can be modified in various ways.
For example, in the above embodiment, the bactericidal component is used as a component of the bactericidal coating layer of the polymer nanofiber, but other analgesic component, deodorizing component, perfume component, antioxidant component, skin care component, etc. are used It can also be used for uses other than sanitary paper.

  In the above embodiment, the reaction product of 4- (chloromethyl) benzyl alcohol and N, N-didodecylmethylamine was used as the quaternary ammonium salt, but at least one of a carboxyl group or a hydroxyl group is used as the quaternary ammonium salt. It is contained, and the affinity with the surface-treated PP nanofibers is good.

In the present invention, quaternary ammonium salts having similar groups to this can also be used.
The hygienic paper of the present invention is not particularly limited, but can be applied to thin paper products such as disposable paper towels and tissue paper.

  The present invention is applicable to various applications such as antibacterially processed plastic products, cloth products such as white coats, rubber products such as surgical gloves, hygiene products such as masks, leather products, paints, synthetic wood, etc. It is.

The following examples illustrate the invention but are not intended to limit it.
Moreover, unless otherwise indicated,% described below shows weight%.

[Surface treatment of PP nanofibers]
First, hollow nanofibers (manufactured by Hirotaka Nanotechnology Co., Ltd.) made of PP with an outer diameter of 300 to 500 nm were prepared. The PP nanofibers are open at both ends.

  Then, 25 g of this PP nanofiber was dispersed in a 1 L (liter) coconut fatty acid diethanolamide solution (1 g of an Anway Coconut Diethanol Amide RSAW 6501 added to 1 L of water) and boiled at 100 ° C. for 30 to 40 minutes .

After boiling, the PP nanofibers were washed with water, dewatered in a centrifuge for 3 minutes (2000 rpm), and then dried at 60 ° C. for 30 minutes.
Twenty-five grams of the dried PP nanofibers were dispersed in a 1 L aqueous solution of hypochlorous acid (concentration 8 g / L), and stirred at 30 ° C. for 1 hour while maintaining the pH at 5 to 5.5.

After completion of the reaction, the PP nanofibers were filtered at atmospheric pressure and dehydrated in a centrifuge for 3 minutes (2000 rpm). After dehydration, it was dried at 60 ° C. for 30 minutes.
An analysis of the surface treated PP nanofibers was performed using an infrared spectrometer (IR). The results are shown in FIG.

  As shown in the IR spectrum of FIG. 3, a peak observed in the range of 3000-2500 and a strong single peak of 1770-1700 indicate the presence of a carboxyl group, and a broad peak observed from around 3200 and The peak at 1420 indicates the presence of a hydroxyl group, from which it was confirmed that the PP nanofibers of this example were surface-treated.

  Then, the PP nanofibers after the surface treatment described above were crushed to a length of 10 μm or more and 3 mm or less using a pulverizer. As a result, an assembly of PP nanofibers of a predetermined length was obtained.

[Synthesis of quaternary ammonium salt]
As shown in the above reaction formula (1), 4- (chloromethyl) benzyl alcohol is synthesized from benzyl alcohol, which is reacted with N, N-didodecylmethylamine to give 4- (chloromethyl) benzyl didodecyl. Methyl ammonium chloride (quaternary ammonium salt) was synthesized.

  Here, the synthesis of 4- (chloromethyl) benzyl alcohol from benzyl alcohol was carried out by adding formaldehyde to a benzene ring by Friedel-Crafts reaction, and then by bubbling hydrogen chloride (45 ° C., 8 hours).

  In addition, synthesis of quaternary ammonium salt is carried out by adding 4- (chloromethyl) benzyl alcohol and N, N-didodecylmethylamine in a molar ratio of 1: 1 to an aqueous solution of sodium carbonate at 100 ° C., 0.25. After stirring and reacting for 10 hours under a pressure of -0.35MPa, ethylene glycol is further added, and stirring is performed for 8 hours under conditions of 90 ° C and 0.2 to 0.3MPa in the presence of sodium hydrogen carbonate. The

After the above synthesis, the reaction product was analyzed using an infrared spectrometer (IR) to confirm formation of a quaternary ammonium salt. The results are shown in FIG.
As shown in the IR spectrum of FIG. 4, in the resulting synthesized product, a single peak was observed at 817, confirming that a benzene ring was bonded at the para position.

[Preparation of bactericidal PP nanofiber assembly]
1 kg of the synthesized quaternary ammonium salt is dissolved in 30 kg of ethanol, and a solution of 1 kg of a hydrophobic material (isobutyl triethoxysilane, manufactured by Dow Corning, trade name: OFS-6403) in 30 kg of ethyl acetate is dissolved in this solution. added.

  10 kg of the surface-treated PP nanofibers are added to this quaternary ammonium salt solution and stirred at 70-80 ° C. for 60 minutes to have a bactericidal effect on the inner surface portion and the outer surface portion of the PP nanofibers A quaternary ammonium salt solution was deposited to cover these surface areas.

  Then, the PP nanofibers are filtered at normal pressure and then dried at 60 to 70 ° C. to separate and evaporate the isobutyltriethoxysilane which is a hydrophobic material, and evaporate ethanol and ethyl acetate, thereby sterilizing PP nanofiber assembly was obtained.

FIGS. 5 and 6 are photographs showing the obtained bactericidal PP nanofiber assembly of the present example, and FIG. 6 is a photograph showing the components of the PP nanofiber assembly in an enlarged manner.
As shown in FIG. 5, the bactericidal PP nanofiber assembly of the present example is obtained as a collection of solid and fine components.

  Constituent elements of this PP nanofiber assembly are in a state in which PP nanofibers are entangled like hairballs, and as shown in FIG. 6, the outer diameter of human hair (about several tens of μm) )have.

[Preparation of hygienic paper blended with bactericidal PP nanofiber assembly]
PP nanofibers containing 4- (chloromethyl) benzyldodecylmethylammonium chloride as the bactericidal material are added to the pulp slurry, and using the BF-10 paper machine made by Kawanoe S Co., Ltd. according to the paper making process described above Hygiene paper was produced at 660 m / min). A plurality of sanitary papers (size: 185 mm × 180 mm) composed of a sheet of tissue paper were prepared as test samples.

  As a result, the total weight of one sheet of paper is 0.5328 g, and as shown in Table 1, it contains 0.1% of PP nanofibers, and 0.1% of the quaternary ammonium salt contained in one sheet. A sample of hygienic paper was obtained.

[Evaluation of hygienic paper blended with bactericidal PP nanofiber assembly]
A sample of the above-mentioned one sheet of sanitary paper was placed in 5 mL of water, and the time course of concentration of quaternary ammonium salt was measured using quaternary ammonium salt test paper (Merck, MQuant 117920).

  As a result, the density test result 3 seconds after putting the sample of the sanitary paper into water was equivalent to 150 ppm.

Moreover, the sterilization test of E. coli was performed on the sample of the sanitary paper in a biochemical incubator.
In this case, the sample was tested using a sheet of sanitary paper. The results are shown in Table 2.
The above measurements and tests are performed by EMTEK (Shenzhen) Co., Ltd., which is a third party analysis organization.

  As shown in Table 2 below, one sample of the sanitary paper of the present invention is sufficient by adding a very small amount (0.1%) of quaternary ammonium salt to woody pulp. The result showing the bactericidal action was obtained. And this sanitary paper can exhibit a very high sterilizing effect by, for example, using 3 sheets in piles and using it in 1 set.

From the above results, the effects of the present invention could be confirmed.
The sanitary paper of the present invention can be mass-produced, for example, by using a Best Former Yankee paper machine (BF-1000: high speed model) manufactured by Kawanoe Sozo Co., Ltd.
Using this apparatus, for example, sanitary paper having a width of 276 cm can be manufactured in a roll at a speed of 800 to 1000 m / min.

DESCRIPTION OF SYMBOLS 1 ...... Polymer-type nanofiber 1a ... outer surface part 1b ... inner surface part 2 ...... hollow part 3 ... bactericidal coating layer 10 ... bactericidal polymer nanofiber assembly

Claims (6)

An aggregate of hollow polymer nanofibers having open ends,
The sterilization in the dry state is provided with a bactericidal coating layer containing a quaternary ammonium salt having at least one of a carboxyl group or a hydroxyl group on the inner surface part and the outer surface part of the hollow polymeric nanofibers. Polymeric Nanofiber Assemblies.   It has an aggregate in which hollow polymeric nanofibers open at both ends are assembled, and at least one of a carboxyl group or a hydroxyl group is provided on the inner surface and the outer surface of the hollow polymeric nanofiber. A hygienic member in which a bactericidal polymer nanofiber aggregate in a dry state provided with a bactericidal coating layer containing a quaternary ammonium salt is blended in a member comprising dry wood fibers.   It has an aggregate in which hollow polymeric nanofibers open at both ends are assembled, and at least one of a carboxyl group or a hydroxyl group is provided on the inner surface and the outer surface of the hollow polymeric nanofiber. Sanitary paper in which a bactericidal polymer nanofiber aggregate in a dry state provided with a bactericidal coating layer containing a quaternary ammonium salt is blended in a paper comprising dry wood fibers. Performing a surface treatment of the assembly of hollow polymeric nanofibers open at both ends;
Grinding the aggregate of the polymer-based nanofibers subjected to the surface treatment into components having a length of 10 μm or more and 3 mm or less;
A bactericidal coated layer containing a quaternary ammonium salt having at least one of a carboxyl group or a hydroxyl group is provided on the inner surface portion and the outer surface portion of the component of the assembly of the pulverized polymer nanofibers. And drying it.   The method for producing a bactericidal polymer nanofiber aggregate according to claim 4, wherein the surface treatment of the polymer nanofiber aggregate is performed using a fatty acid amide and hypochlorous acid.   6. A slurry-like stock obtained by dispersing the bactericidal polymer nanofiber aggregate obtained by the method according to any one of claims 4 or 5 in pulped raw material wood, using a predetermined stock A method of producing sanitary paper, comprising the steps of: producing hygienic paper in a dry state through a papermaking process.