JP6598333B2 - Bactericidal polymer nanofiber aggregate and dry sanitary paper using the same - Google Patents

Description

  The present invention is a hygiene in which a nanofiber made of a polymer material such as PP (polypropylene) is provided with a bactericidal coating layer such as a surfactant and this bactericidal polymer nanofiber aggregate. Regarding paper.

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

The main features of nanofibers are 1) ultra-specific surface area effect (high adsorptivity, strong adhesion, high molecular recognition), 2) nano-size effect (low pressure loss, high transparency), 3) super Examples include molecular alignment effects (high strength, high electrical conductivity, high thermal conductivity), and as a material supporting advanced technology, development in a wide range of fields is being actively carried out in various countries around the world (see Non-Patent Document 1). ).
For example, if nanofibers are used as the material of the adsorbent, the specific surface area of the adsorbent is increased and the adsorption capacity is increased, and the adsorption selectivity is increased. Therefore, using nanofibers, for example, Escherichia coli and Salmonella A technique for adsorbing a large amount of cell membrane 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 developed rapidly in the mid-70s.
Microcapsules are applied in various fields such as pharmaceuticals, agricultural chemicals, foods, paints, inks, and adhesives (see Non-Patent Document 2, Non-Patent Document 3, and Patent Document 2).

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

  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 materials and walls suitable for each technique Material is used.

  Traditionally, microcapsules containing sterilizing ingredients, analgesic ingredients, deodorant ingredients, perfume ingredients, antioxidant ingredients, skin care ingredients, etc. have been used in various fields such as sanitary paper, poultices, fragrances, deodorants, and agricultural chemicals. (See Patent Documents 3 to 5).

Among the various components, a cationic surfactant (quaternary ammonium salt) is currently used in a wide field as a disinfectant. A cationic surfactant having a positive charge has an excellent feature that its adsorption rate to a negatively charged bacterial surface is fast and a rapid bactericidal effect is observed.
As an action mechanism of the quaternary ammonium salt, it has been reported that there are two actions.
One is “physical destruction of the cell membrane”, which is an action in which the cation of the ammonium molecule binds to the anion site on the surface of the bacterium and physically destroys the cell membrane by hydrophobic interaction (see Non-Patent Document 4). ). The other is “inhibition of metabolic function of bacteria”, in which quaternary ammonium salt strongly adsorbs and reacts with bacteria to inhibit metabolic functions (growth) by inhibiting intracellular enzymes. (Non-Patent Document 5).

  Conventionally, various microencapsulation techniques including sterilizing ingredients, analgesic ingredients, deodorant ingredients, perfume ingredients, antioxidant ingredients, skin care ingredients, etc. have been studied and put to practical use, but the main techniques have already been described. Thus, a mechanical method (orifice method), a physical method (phase separation method, etc.), and a chemical method (interfacial polymerization method, etc.) can be mentioned.

  Among these microencapsulation techniques, in the orifice method, a polymer solution containing various components (core substance) is dropped from a double tube into a curable liquid to produce a microcapsule.

In the phase separation method, the core material that needs to be wrapped is dispersed in the organic solution containing the wall material, so that the periphery of the core material is wrapped and covered. At this 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.

Any of the above-described microencapsulation techniques has a problem that the process becomes complicated and mass production is difficult in industrial production.
In recent years, there has been a demand for a new functional composite material (element) using the above-described nanofiber as an alternative to such a microcapsule, but it has not yet been realized.

  On the other hand, as a sanitary paper having a sterilizing component, wet wet paper soaked with an aqueous solution such as alcohol or sodium hypochlorite has been commercially available, but in such wet sanitary paper, As the product becomes heavier, once the product provided in a sealed state is opened, the shelf life is shortened. Furthermore, since the aqueous solution is soaked in the paper, it is impossible to use ingredients that are not soluble in water. We have problems such as.

  Moreover, in the conventional wet sanitary paper, for example, about 10 times the bactericidal component solution needs to be blended with the pulp that is the raw material, and there is a problem that the cost increases, and the blending amount of the bactericidal component It was difficult to make adjustments.

2015 Patent Application Technology Trend Survey Report “Nanofiber”: Japan Patent Office “Micro-encapsulation”: Wikipedia February 2008 Research Report “Microcapsule”: Toray Research Center September 2013 “Anti-bacteria”: Hiroki Koryo 1995, Vol.23 “Chemistry of Antibacterial and Antifungal”: Hiroshi Horiguchi, Sankyo Publishing, 1982

Japanese Unexamined Patent Publication No. 2016-49527 JP-A-62-146584 JP-A-2-300301 JP 2004-324026 A JP 2006-291425 A

  The present invention has been made to solve such problems of the conventional technology, and the object of the present invention is to use a polymer-based nanofiber assembly as an alternative to a microcapsule having a complicated manufacturing process. Accordingly, an object of the present invention is to provide a bactericidal material that can be produced in large quantities by 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 that is dry, light and easy to handle, and can maintain bactericidal properties for 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 blending amount of bactericidal components without reducing the bactericidal power, and a sanitary paper using the bactericidal material.

In order to achieve the above object, the present invention has an assembly of hollow polymer nanofibers that are open at both ends, and has an inner surface portion and an outer surface of the hollow polymer nanofiber. It is a dry sterilization polymer nanofiber aggregate in which a sterilization coating layer containing a quaternary ammonium salt having at least one of a carboxyl group or a hydroxyl group is provided on the surface portion.
The present invention is a sanitary member in which the above-described bactericidal polymer nanofiber aggregate is blended with a member made of dry wood fibers.
The present invention is a sanitary paper in which the above-described disinfectant polymer nanofiber aggregate is blended with a paper made of dry wood fiber.
The present invention includes a step of performing a surface treatment of an aggregate of hollow polymer nanofibers having both ends opened, and an assembly of polymer nanofibers subjected to the surface treatment having a length of 10 μm or more and 3 mm or less. A step of pulverizing the component, 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 component of the aggregate of the pulverized polymer nanofibers And a step of providing a bactericidal coating layer to be dried and drying the bactericidal polymer nanofiber aggregate.
In the method for producing a bactericidal polymer nanofiber aggregate, the present invention is also effective in performing the surface treatment of the polymer nanofiber aggregate using a fatty acid amide and hypochlorous acid. .
The present invention uses a slurry-like material obtained by dispersing a bactericidal polymer nanofiber aggregate obtained by any of the above-described methods in pulped raw wood, and performs a predetermined papermaking process. This is a method for manufacturing sanitary paper, which includes a step of creating a sanitary paper in a dry state.

  Since the bactericidal nanofiber assembly used in the present invention is provided with a bactericidal coating layer on the surface of the polymer nanofiber, the conventional complicated microencapsulation process is not necessary, and as a result Using a facility that is easy to operate, it can be manufactured in large quantities with a simple process.

Further, in the present invention, when used, the quaternary ammonium salt, which is a bactericidal component provided in a layered manner on the surface of the nanofiber, is immediately dissolved by simply touching water to express bactericidal properties. Easy to use and very easy to use.
Moreover, since the quaternary ammonium salt has a function of adsorbing bacteria, it is possible to efficiently remove bacteria on the surface of the sterilization target.

  Furthermore, since the sanitary paper of the present invention is dry (in a dry state), it can be reduced in weight and can be kept sterilized for a long period of time because it hardly changes in the atmosphere.

  Further, in the present invention, the blending amount of the bactericidal component can be reduced as compared with the prior art without reducing the bactericidal power, and the blending amount of the bactericidal component and the selection of the type can be easily performed. it can.

(A)-(f): Schematic which shows typically the example of the component of the bactericidal polymer nanofiber aggregate | assembly which concerns on this invention. The block diagram which shows the example of the bactericidal polymer nanofiber aggregate | assembly which concerns on this invention, and the manufacturing method of sanitary paper IR spectrum showing the analysis results of PP nanofibers after surface treatment IR spectrum showing analysis results of reactants after quaternary ammonium salt synthesis Photograph showing the bactericidal PP nanofiber assembly of the example Photo showing enlarged elements of the PP nanofiber assembly

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

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

  The polymer nanofiber 1 used in the present invention is a nanofiber composed of a polymer material (a fibrous substance having a diameter of 1 nm to less than 1 μm) and has both ends opened (hereinafter referred to as “appropriately” Nanofiber ”).

  Here, as the polymer material constituting the nanofiber 1 of the present invention, it can be produced in a fiber shape and does not dissolve in water, fatty acid amide, hypochlorous acid, ethanol, isobutyltriethoxysilane, and 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), and PU (polyurethane).

  In the case of the present invention, the material of the nanofiber 1 is not particularly limited, but is made of polypropylene from the viewpoint of ease of fiber production and softness when an 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 portion 2 formed so that the inside thereof is a hollow structure, that is, along the longitudinal direction thereof.
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 preferably used.

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

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

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

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

In the present invention, the type of fatty acid amide used for degreasing the surface of the nanofiber 1 is not particularly limited, but palm fatty acid diethanolamide is preferably used.
Coconut fatty acid diethanolamide is widely used as a nonionic surfactant in shampoos, facial cleansers and the like, and is preferred because it can be easily obtained.
In addition, as long as it has a degreasing effect, another fatty acid amide, surfactant, etc. can also be used.

  On the other hand, hypochlorous acid reacts with the coconut fatty acid diethanolamide adhering to the surface of the nanofiber 1 by the degreasing treatment, and at least one of the carboxyl group or the hydroxyl group covers the surface of the nanofiber, so that the surface tension is reduced. The affinity with the quaternary ammonium salt can be improved by the effect.

  In the present invention, the material for performing this treatment is not particularly limited to hypochlorous acid, but it is a material that is used for general purposes, and from the viewpoint of easy availability, hypochlorous acid is used. It is preferable to use it.

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

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

  A predetermined amount of the nanofiber 1 after drying is dispersed in a hypochlorous acid aqueous solution (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.

The nanofiber 1 after completion of the reaction is filtered at normal pressure, dehydrated for several minutes (about 2000 rpm) with a centrifuge, and then dried at a temperature of about 60 ° C. for about 30 minutes.
Furthermore, the nanofiber 1 after the surface treatment described above is pulverized to a length of 10 μm or more and 3 mm or less using a fine pulverizer (process P2).
As a result, an assembly of nanofibers 1 made of PP is obtained.

Further, a quaternary ammonium salt synthesis step is performed (process P3).
In the present invention, the quaternary ammonium salt synthesis step P3 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, as shown in the following reaction formula (1), 4- (chloromethyl) benzyl alcohol is synthesized from benzyl alcohol, and N, N-didodecylmethylamine is synthesized into this. To synthesize 4- (chloromethyl) benzyldidodecylmethylammonium chloride, which is a quaternary ammonium salt.

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

  Further, the synthesis of 4- (chloromethyl) benzyl didodecylmethylammonium chloride is performed by first combining the synthesized 4- (chloromethyl) benzyl alcohol and N, N-didodecylmethylamine with, for example, 1: 1. It is carried out by charging the aqueous solution of sodium carbonate in a molar ratio and stirring and reacting at a temperature of about 100 ° C. and a pressure of 0.25 to 0.35 MPa for about 10 hours.

  Thereafter, ethylene glycol was added to this solution, and the mixture was reacted 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. 4- (Chloromethyl) benzyldidodecylmethylammonium chloride represented by the above reaction formula (1), which is a quaternary ammonium salt, is obtained.

  This 4- (chloromethyl) benzyl didodecylmethylammonium chloride contains a hydroxyl group and has a good affinity with the above-described polymer nanofiber 1 subjected to the surface treatment, particularly nanofiber 1 made of PP.

Then, in this example, the process of coat | covering the surface of the nanofiber 1 with the said quaternary ammonium salt is performed (process P4).
In this step, first, a predetermined amount of quaternary ammonium obtained in the synthesis step of the process P3 is dissolved in ethanol, and a solution of a predetermined amount of isobutyltriethoxysilane in ethyl acetate is dissolved in this solution. Add as.

This isobutyltriethoxysilane serves to prevent the quaternary ammonium salt from eluting into ethanol or ethyl acetate during the treatment.
Further, a predetermined amount of the nanofiber subjected to the surface treatment is added to the quaternary ammonium salt solution, and the mixture is stirred at a temperature of 70 to 80 ° C. for about 60 minutes.

  As a result, 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 quaternary ammonium on the outer surface portion 1a and the inner surface portion 1b of the nanofiber. A salt solution adheres and these surface portions are coated with a bactericidal material containing a quaternary ammonium salt.

  And after filtering this nanofiber at normal pressure and drying at a temperature of 60-70 ° C., isobutyltriethoxysilane, which is a hydrophobic material, is separated and evaporated, and ethanol and ethyl acetate are evaporated. A bactericidal polymer nanofiber aggregate 10 having a bactericidal coating layer 3 containing a quaternary ammonium salt on the surface of the nanofiber is obtained (see FIGS. 1E and 1F).

  Then, using the bactericidal polymer nanofiber aggregate 10 containing the quaternary ammonium salt described above, sanitary paper made of, for example, a sheet of paper is prepared by, for example, the following papermaking method (process P5).

In this example, first, a process of pulping various raw woods is performed, and further, the following adjustment process is performed.
In the adjustment step, various pulps are mixed and beaten using an apparatus called a refiner to disperse the particulate bactericidal polymer nanofiber aggregate 10 containing the above-described quaternary ammonium salt and predetermined. Add the chemicals.

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

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

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

In the present invention, a quaternary ammonium salt having the same group can also be used.
The sanitary 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.

  In addition to sanitary paper, the present invention can be applied to various uses such as antibacterial processed plastic products, cloth products such as lab coats, rubber products such as surgical gloves, sanitary products such as masks, leather products, paint, and synthetic wood. It is.

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

[Surface treatment of PP nanofibers]
First, hollow nanofibers (manufactured by Hiroshi Nanotechnology Co., Ltd.) made of PP having an outer diameter of 300 to 500 nm were prepared. This PP nanofiber is open at both ends.

  Then, 25 g of this PP nanofiber was dispersed in 1 L (liter) of coconut fatty acid diethanolamide solution (1 g of Coconut Dietanol Amide RSAW 6501 manufactured by Anway Co., 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, dehydrated with a centrifuge for 3 minutes (2000 rpm), and then dried at 60 ° C. for 30 minutes.
25 g of dried PP nanofibers were dispersed in 1 L of hypochlorous acid aqueous solution (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 normal pressure, and dehydrated with a centrifuge for 3 minutes (2000 rpm). After dehydration, it was dried at 60 ° C. for 30 minutes.
The PP nanofiber after the surface treatment was analyzed using an infrared spectrometer (IR). The result is shown in FIG.

  As shown in the IR spectrum of FIG. 3, the peak seen in the range of 3000-2500 and the strong single peak of 1770-1700 indicate the presence of carboxyl groups, and the broad peaks seen from around 3200 and The peak of 1420 indicates that a hydroxyl group is present, and from this, it was confirmed that the PP nanofiber of this example was surface-treated.

  Then, the above-mentioned PP nanofiber after the surface treatment was pulverized to a length of 10 μm or more and 3 mm or less using a fine pulverizer. As a result, a PP nanofiber assembly having 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 and reacted with N, N-didodecylmethylamine to give 4- (chloromethyl) benzyldidodecyl. Methyl ammonium chloride (quaternary ammonium salt) was synthesized.

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

  The quaternary ammonium salt was synthesized by introducing 4- (chloromethyl) benzyl alcohol and N, N-didodecylmethylamine into a sodium carbonate aqueous solution at a molar ratio of 1: 1, 100 ° C., 0.25 After stirring for 10 hours under a pressure of .about.0.35 MPa, ethylene glycol was further added, and the mixture was stirred for 8 hours in the presence of sodium bicarbonate at 90.degree. C. and 0.2 to 0.3 MPa. It was.

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

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

  To this quaternary ammonium salt solution, 10 kg of the above-treated PP nanofiber is added and stirred at 70 to 80 ° C. for 60 minutes, so that the inner surface portion and the outer surface portion of the PP nanofiber have a bactericidal effect. A quaternary ammonium salt solution was applied to coat these surface portions.

  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 to evaporate ethanol and ethyl acetate. A PP nanofiber assembly was obtained.

5 and 6 are photographs showing the obtained bactericidal PP nanofiber aggregates of this example, and FIG. 6 is a photograph showing enlarged constituent elements of the PP nanofiber aggregates.
As shown in FIG. 5, the bactericidal PP nanofiber assembly of this example is a solid and obtained as a collection of fine components.

  The constituent elements of this PP nanofiber aggregate are in a state where PP nanofibers are entangled like a pill, and as shown in FIG. 6, the outer diameter (about several tens of μm) of the thickness of human hair. )have.

[Creation of sanitary paper containing bactericidal PP nanofiber aggregates]
PP nanofibers containing 4- (chloromethyl) benzyldodecylmethylammonium chloride, which is the bactericidal material, are added to the pulp slurry, and the papermaking process described above is used with a BF-10 paper machine manufactured by Kawanoe Kikai Co., Ltd. 660m / min), sanitary paper was prepared. As a test sample, a plurality of sanitary papers (size: 185 mm × 180 mm) composed of a single tissue paper were prepared.

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

[Evaluation of sanitary paper containing bactericidal PP nanofiber aggregate]
A sample of the above-mentioned sanitary paper was placed in 5 mL of water, and the change with time in the concentration of the quaternary ammonium salt was measured using a quaternary ammonium salt test paper (MQuant 117,920, manufactured by Merck).

  As a result, the concentration test result 3 seconds after the sanitary paper sample was put in water was equivalent to 150 ppm.

In addition, the sanitary paper sample was subjected to a sterilization test for Escherichia coli using a biochemical incubator.
In this case, the sample was tested using one sanitary paper. The results are shown in Table 2.
The above measurements and tests were conducted by EMTEK (Shenzhen) Co., Ltd., 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 a quaternary ammonium salt to a woody pulp. A result showing a bactericidal action was obtained. And this sanitary paper can exhibit a very high sterilization effect by using, for example, three sheets in a set in use.

From the above results, the effect of the present invention could be confirmed.
The sanitary paper of the present invention can be produced in large quantities by using, for example, a best-form Yankee paper machine (BF-1000: high-speed model) manufactured by Kawanoe Machinery Co., Ltd.
If this apparatus is used, for example, sanitary paper having a paper width of 276 cm can be manufactured in a roll shape at a speed of 800 to 1000 m / min.

DESCRIPTION OF SYMBOLS 1 ... Polymer nanofiber 1a ... Outer surface part 1b ... Inner surface part 2 ... Hollow part 3 ... Bactericidal coating layer 10 ... Bactericidal polymer nanofiber aggregate

Claims (6)

It has an aggregate of hollow polymer nanofibers that are open at both ends,
Sterilization in a dry state in which a sterilizing coating 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 hollow polymer nanofiber. Polymer nanofiber assembly.   It has an aggregate of hollow polymer nanofibers that are open at both ends, and has at least one of a carboxyl group or a hydroxyl group on the inner surface portion and the outer surface portion of the hollow polymer nanofiber. A sanitary 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 with a member made of dry wood fibers.   It has an aggregate of hollow polymer nanofibers that are open at both ends, and has at least one of a carboxyl group or a hydroxyl group on the inner surface portion and the outer surface portion of the hollow polymer nanofiber. A sanitary paper in which a dry bactericidal polymer nanofiber aggregate provided with a bactericidal coating layer containing a quaternary ammonium salt is blended with a paper made of dry woody fibers. Performing a surface treatment of an aggregate of hollow polymer nanofibers having both ends opened;
Crushing the assembly of polymer nanofibers subjected to the surface treatment into components having a length of 10 μm or more and 3 mm or less;
A bactericidal coating 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 aggregate of the pulverized polymer nanofibers. And a step of drying the sterilized polymer nanofiber assembly.   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.   A slurry-like stock obtained by dispersing the bactericidal polymer nanofiber aggregate obtained by the method according to any one of claims 4 and 5 in a pulped raw material wood, A method for producing sanitary paper, comprising a step of creating a sanitary paper in a dry state through a papermaking process.