JP2013174029A - Tissue paper and tissue paper product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide tissue paper having a chemical solution applied thereon, which exhibits mildew resistance when being stored and bactericidal effect when being used.SOLUTION: The tissue paper is obtained by making the tissue paper having the chemical solution applied thereon carry powdery porous materials which adsorb at least either one of a salt of alkali metal chlorite and a salt of alkaline-earth metal chlorite thereon.

Description

  The present invention relates to tissue paper and tissue paper products.

There are two types of tissue paper: a chemical solution application type in which a chemical solution is applied to impart flexibility and smoothness, and a general-purpose product or general-purpose type to which no chemical solution or the like is applied.
Chemical-coated tissue paper is superior in softness and smoothness compared to general-purpose type paper, but moisture in the air tends to be absorbed by the base material and chemical components during storage in high temperature and high humidity environments such as summer in Japan. There was a possibility that mold and bacteria may be generated as chemical nutrients as nutrients.
In particular, tissue paper stores a bundle of multiple folded tissue papers in a storage box, and the tissue papers are sequentially taken from the outlet provided on one side of the storage box (also called a carton box or tissue carton). As a tissue paper product that is pulled out and used one by one, it is common to put multiple items on the market. (The form in which the next sheet is continuously pulled out from the outlet when a sheet is taken out is called a pop-up type. ).
The tissue paper combined with such product forms and commercial forms is often unused and stored for a long period of time, and it is required to continuously prevent the generation of mold and bacteria over a long period of time.

Special table 2008-544953 Special table 2004-513961 JP 2002-370974 A

  Therefore, a main problem of the present invention is to provide a chemical-coated tissue paper that has antifungal and antibacterial properties and also exhibits a bactericidal effect when used.

  The present invention that has solved the above problems is as follows.

[Invention of Claim 1]
A tissue paper is coated with a powdered porous material on which a chemical solution is applied and at least one of an alkali metal chlorite and an alkaline earth metal chlorite is adsorbed. Tissue paper.

[Invention of Claim 2]
The tissue paper according to claim 1, wherein the tissue paper is coated with an oil-based chemical solution containing a powdered porous material in which at least one of an alkali metal chlorite and an alkaline earth metal chlorite is adsorbed. .

[Invention of Claim 3]
The tissue paper according to claim 1 or 2, wherein the tissue paper is two-ply or three-ply, and a powdery porous material is supported on an inner surface of the laminated layer.

[Invention of Claim 4]
A tissue paper product, wherein a plurality of the tissue papers according to any one of claims 1 to 3 are folded and stacked in a pop-up manner and stored in a storage box having an outlet on an upper surface.

(Function and effect)
Chlorine dioxide is a substance that has excellent fungicidal and fungicidal effects and is said to have little effect on the human body. Although this chlorine dioxide has a boiling point as low as 11 ° C., it can be handled as a liquid, but even if it is applied to tissue paper as it is, it will volatilize immediately and the tissue paper has the desired fungicidal and bactericidal effects. It cannot be.

  Here, chlorine dioxide can be generated by a reaction between an alkali metal chlorite and an alkaline earth metal chlorite (hereinafter also referred to as an alkali metal chlorite) and an acid.

  Therefore, in the present invention, a powder-coated porous material on which at least one of an alkali metal chlorite and an alkaline earth metal chlorite is adsorbed is supported on a tissue-coated tissue paper. Chlorine dioxide is generated by utilizing the fact that the water absorbed by various factors becomes acidic when the paper is absorbed during storage or use.

  That is, when chemical-coated tissue paper is stored in a humid environment, moisture is taken into the tissue paper due to the moisture absorption effect of the base paper and the chemical. At that time, the tissue paper exhibits weak acidity due to elution of components contained in the chemical solution. Therefore, if the tissue paper is preliminarily supported with alkali metal chlorite, the alkali metal chlorite reacts when the tissue paper absorbs moisture in a humid environment where mold and bacteria are likely to occur. Chlorine dioxide is generated.

  In particular, in the present invention, by using a powdery porous material adsorbed with an alkali metal chlorite, etc., coupled with a very small amount of water in the air due to moisture absorption of the base paper or chemical solution, Chlorine dioxide is generated continuously over a long period of time without an abrupt reaction of alkali metal chlorate or the like, and the fungicidal and bactericidal properties are maintained over a long period of time.

  In addition, for example, when biting the nose, a large amount of water in the nasal fluid is absorbed by the tissue paper, so that the contact with the powdered porous material adsorbed with the alkali metal chlorite is improved. In addition, chlorine dioxide is generated and has a bactericidal effect during use.

  Of course, in order to ensure the generation of chlorine dioxide, acidic substances that elute and dissolve in water in advance in tissue paper so that moisture woven into tissue paper, such as moisture due to moisture absorption, moisture such as runny nose, is acidic May be supported.

  As a secondary effect, chlorine dioxide is known to inactivate allergens such as Japanese cedar pollen in addition to bactericidal and antifungal effects. Also, when wiping other than the skin, it also has an effect of inactivating pollen adhered to the wiping place.

  Here, there are various types of chemicals used for chemical-coated tissue paper, but water-based chemicals mainly composed of water and polyol (usually also called “aqueous chemicals” or “aqueous lotion chemicals”), mainly water-insoluble. It is roughly divided into oil-based chemicals that contain wax and the like and are semi-solid at room temperature.

  Aqueous chemicals are excellent in affinity with the pulp fibers constituting the sheet when applied to the sheet, impregnate in the thickness direction of the sheet (also referred to as the Z direction), and act to modify the entire sheet. The system chemicals mainly act to coat the surface, and in particular improve the smoothness of the surface. And, regarding the problem of mold and bacteria generation related to the above-mentioned chemical-type tissue paper, when using an aqueous chemical solution, by including a water-soluble antibacterial agent in the aqueous chemical solution, the anti-mold effect is expressed on the entire paper In the case of an oil-based chemical solution, it is difficult to contain an antifungal agent and an antibacterial agent in the entire paper layer.

  In the present invention, whether it is an oil-based chemical solution or an aqueous-based chemical solution, as long as it supports a powdery porous material that adsorbs at least one of an alkali metal chlorite salt and an alkaline earth metal chlorite salt. Although it is possible to achieve the effects of the present invention, it is particularly useful when using a chemical solution that is difficult to contain a water-soluble antibacterial agent even in the paper layer, such as an oil-based chemical solution.

  Rather, in the present invention, in the case of an oil-based chemical solution, it can be applied in a state in which a powdery porous material is previously contained, and it is easy to carry the powdery porous material. In addition, the oil-based chemical solution acts to coat the base paper as described above, but the base paper itself absorbs moisture. Therefore, even if a powdery porous material is included in the oil-based chemical solution, tissue paper is absorbed by moisture absorption. Contact with moisture taken in can be ensured. Rather, it is desirable that the contact with a small amount of moisture is gradually performed continuously over a long period of time. Of course, the water does not become acidic.

  In addition, when chemical tissue-giving tissue paper absorbs moisture or absorbs moisture, there are various reasons why the moisture becomes acidic. When the chemical solution is applied to the antioxidant and tissue paper contained for the purpose, the chemical solution should be changed from neutral to weakly acidic to acidic using a pH adjuster so as not to corrode the production equipment. It is done.

  In other words, the tissue paper after drying is neutral, but the applied chemical solution usually contains substances that dissolve and dissolve in water and become acidic to weakly acidic. Is taken into tissue paper, the substance dissolves and elutes in the water and becomes acidic to weakly acidic. In addition, when a cationic surfactant is contained as a soft component in the chemical solution, it also exhibits acidity to weak acidity due to this. Furthermore, it can be one of the factors that the chemical solution components are partially oxidized when the chemical solution is exposed to the atmosphere.

  On the other hand, in the present invention, it is preferable that the tissue paper has two or three plies and a porous powder material is supported on the inner surface of the laminate. Tissue paper is used in such a manner that it directly touches the skin, such as when blowing a nose. Some consumers dislike that the disinfectant or the like does not touch the skin directly, so it is preferable to carry it on the inner surface of the laminate.

  In the tissue paper according to the present invention, a bundle of a plurality of tissue papers is stored in a storage box, and the tissue paper is removed from an outlet provided on one surface of the storage box (also referred to as a carton box or tissue carton). The tissue paper is stored in the storage box, as in the tissue paper products that are pulled out one by one (the pop-up type is the type in which the next sheet is pulled out from the outlet when it is removed) Therefore, it is particularly effective for a tissue paper product to be stored.

  According to the present invention as described above, there are provided chemical-coated tissue paper that has antifungal properties at the time of storage and exhibits a bactericidal effect when used, and tissue paper products in which this is stored in a storage box.

It is sectional drawing of the two-ply tissue paper based on this invention. It is sectional drawing of the 3-ply tissue paper based on this invention. It is a figure for demonstrating generation | occurrence | production of the chlorine dioxide in the tissue paper which concerns on this invention.

  Hereinafter, tissue paper and tissue paper products according to the present invention will be described in detail with reference to the drawings.

  In the present invention, a tissue paper is coated with a powdery porous material coated with a chemical solution and adsorbing at least one of an alkali metal chlorite and an alkaline earth metal chlorite. is there.

Although the basis weight and paper thickness of the tissue paper of the present invention are not particularly limited, a preferred example is a basis weight according to JIS P 8124 of 10 to ²⁰ g / m ² per ply, a paper thickness (a dial thickness gauge: Peacock manufactured by Ozaki Seisakusho). (Measured by) is 100 to 200 μm. When the basis weight and the paper thickness are out of the above ranges, it is not preferable in terms of strength and softness as tissue paper.

  The tissue paper base paper is a crepe paper obtained by making a papermaking raw material in which a known chemical agent such as a dry paper strength agent or a wet strength paper strength agent is added to a pulp slurry in a papermaking facility having a Yanki dryer.

  The pulp raw material in the tissue paper base paper of the present invention is preferably composed of NBKP (conifer kraft pulp) and LBKP (hardwood kraft pulp). Although used paper pulp may be blended as appropriate, it is desirable that it is composed only of NBKP and LBKP of virgin pulp because it is desirable in terms of the texture of the resulting tissue paper. In this case, the blending ratio (JIS P 8120) is preferably NBKP: LBKP = 20: 80 to 80:20, and particularly preferably NBKP: LBKP = 30: 70 to 60:40.

  On the other hand, sodium chlorite and potassium chlorite can be illustrated as specific examples of the alkali metal chlorite according to the tissue paper of the present invention. Specific examples of the alkaline earth metal chlorite include calcium chlorite and magnesium chlorite. In particular, sodium chlorite is desirable in terms of handleability and cost.

Further, in the present invention, alkali metal chlorite is adsorbed on a powdery porous material and supported on tissue paper base, but as the powdery porous material, adsorptivity of alkali metal chlorite and the like, The specific surface area is preferably about 500 to 1,500 m ² / g from the point of contact with moisture and handling, and the average particle size (laser diffraction / scattering method (microtrack method)) is 5 to 30 μm. Things are desirable.

  Specific examples of the powdery porous material include zeolite, mesoporous silica, porous silicate and the like. Particularly preferred is mesoporous silica from the viewpoint of handleability and cost.

  Examples of a method for adsorbing and fixing alkali metal chlorite to these powdery porous materials include, for example, powdered porous metal in a 1 to 25% by weight solution of alkaline earth metal chlorite. A method of fixing the alkali metal chlorite to the powdered porous material by immersing the material and adsorbing the alkali metal chlorite in the pores and then drying under reduced pressure. Can be mentioned.

  On the other hand, the chemical | medical solution apply | coated to the tissue paper base paper in this invention means what improves the softness | flexibility and surface smoothness of a tissue paper base paper. As described above, this type of chemical used for tissue paper is roughly classified into an aqueous chemical and an oil based chemical, but the present invention may be any. However, as will be described later, the effect of the chemical solution, the point that the powdered porous material adsorbed with alkali metal chlorite and the like is easy to carry on the tissue paper base, the manufacture is easy, and the antifungal and sterilizing effect is sustained It is desirable to use oil-based chemicals from the viewpoint of properties.

  As the oil-based chemical solution which is a preferable chemical solution, a tissue paper solution can be used. Oil-based chemicals are mainly waxes and fats and oils, and are generally liquid or semi-solid (cream) at room temperature and pressure. Examples of the fats and oils include white petrolatum, liquid paraffin, coconut oil, palm oil, and saturated fatty acids such as palmitic acid.

  The application amount of the oil-based chemical solution is preferably 10 to 30 wt% of the tissue paper base paper. If the amount is less than 10 wt%, the surface smoothness may not be sufficiently improved by the oil-based chemical, and if it exceeds 30 wt%, stickiness may be felt.

  On the other hand, the thing for tissue paper can be used for an aqueous | water-based chemical | medical solution. The aqueous chemical solution generally contains about 70 to 90 wt% of a polyol such as glycerin or propylene glycol and about 10 to 20 wt% of water.

  If an aqueous chemical solution is used, the application amount of the aqueous chemical solution is preferably 15 to 35 wt% of the tissue paper base paper. If it is less than 15 wt%, the improvement in flexibility may not be sufficient, and if it exceeds 35 wt%, stickiness will be felt, which is not desirable.

  Here, to support the powdery porous material on the tissue paper base, if an oil-based chemical solution is used, the powdered porous material is previously mixed in the oil-based chemical solution and then applied to the tissue paper base paper. And can be supported. It is possible to mix a powdery porous material in advance in an oil-based chemical solution because the oil-based chemical solution has a low water content and water does not exist as a solvent or solute. This is because the contact and reactivity with the porous material are poor. The specific water content in the oil-based chemical solution may be appropriately designed in consideration of the applicability and handling properties of the oil-based chemical solution, but from the viewpoint of mixing the powdery porous material in advance. The water content in the oil-based chemical solution should be low. Specifically, it is desirable that the water content is less than 1 wt%.

  On the other hand, water-based chemicals are superior to oil-based chemicals in terms of ease of cleaning of equipment after coating processing, etc., but the main component is a mixed solution of polyol and water, usually by adjusting the pH. Since the aqueous solution is weakly acidic to acidic as a whole, when the powdered porous material is mixed, the reaction is completed at that moment and chlorine dioxide is immediately generated. Therefore, when using an aqueous chemical solution, after applying the aqueous chemical solution to tissue paper and drying it, the powdered porous material is supported using an adhesive such as a binder. In this respect, the aqueous chemical solution requires more labor for loading than the oil-based chemical solution.

  Of course, even when an oil-based chemical solution is used, the powdery porous material may be supported on the tissue paper base by a binder separately from the oil-based chemical solution.

  When using an aqueous chemical solution, it is necessary to select a water-insoluble one that does not react with an alkali metal chlorite as a binder. An example of such a binder is silicone oil. However, the mechanism of the flexibility improvement effect of the aqueous chemical solution is that the chemical solution is modified by the penetration of the chemical solution in the Z direction (in the paper layer) of the paper. However, the water-insoluble binder seems to coat the surface. Therefore, there is a tendency to reduce the flexibility improvement effect by the aqueous chemical solution.

  As described above, in the present invention, to support the powdered porous material on the tissue paper, in the case of an oily chemical solution, the powdered porous material is mixed and applied in the chemical solution at the same time as the chemical solution application. The effect of improving the smoothness of the oil-based chemical solution can be sufficiently expressed, whereas in the case of the water-based chemical solution, it is necessary to carry a powdered porous material with a binder separately from the chemical solution application, and the binder May reduce the flexibility improvement effect of aqueous chemicals. Therefore, in the present invention, an oil-based chemical solution is more suitable than an aqueous chemical solution from the viewpoint of ease of loading on tissue paper base paper and improvement in function by the chemical solution.

  In addition, it is desirable to contain 0.1-2.0 wt% of cationic surfactants as a soft component in the chemical solution regardless of oil-based chemical solution or aqueous chemical solution. When the cationic surfactant is contained in the above range, the moisture taken into the tissue paper at the time of moisture absorption and nose biting is preferably made weakly acidic to acidic.

  Regardless of whether it is an oil-based chemical solution or an aqueous-based chemical solution, this type of chemical solution usually contains a solution that dissolves and elutes in water to make the water an acidic solution. In order to control the generation of chlorine dioxide, and to control the generation of chlorine dioxide, substances such as pH adjusters such as lactic acid, ascorbic acid, hyaluronic acid, gluconic acid salt are intentionally supported on tissue paper, This may dissolve and dissolve in the absorbed moisture to make the moisture weakly acidic to acidic, and react with sodium chlorite adsorbed on the powdered porous material.

  On the other hand, the bactericidal effect of chlorine dioxide and the inactivation of cedar pollen allergen are most effective at 600 to 3,000 ppm. Moreover, about 10-30 wt% of adsorption | suction rates, such as an alkali metal chlorite, with respect to a powdery porous material, can be ensured. Therefore, the amount of powdery porous material supported on tissue paper is based on the chlorine dioxide concentration, adsorption rate, etc., and the loading method, the expected storage time (season), and the atmosphere (temperature / humidity) of the storage location. ) Etc. In addition, when it is assumed that it is stored in any season and place in Japan, it is adsorbed with alkali metal chlorite, etc. The mixing ratio of the powdery porous material to the oil-based chemical is 0.2 to 1.0 wt%.

  On the other hand, the specific position for supporting the powdery porous material can be the front and back surfaces of the tissue paper, and as shown in FIGS. 1 and 2, 2-ply or 3 which is a preferred form of the tissue paper. In the case of adopting a ply mode, it can be a laminated inner surface (in the figure, each ply is indicated by a symbol P). In addition, a lamination | stacking inner surface means the surface where each ply P and P are facing each other. 1 and 2 both show an example in which an oil-based chemical solution 10 is used.

  When the inner surface is laminated as described above, the powdered porous materials 20, 20... Do not directly touch the skin when used such as when blowing a nose with tissue paper T. Among those who use tissue paper T, many people dislike that chemicals such as bactericides and fungicides directly touch the skin, so if the powdery porous material 20 is positioned on the inner surface of the laminate, Such appeal to consumers can be secured.

  In the case of the oil-based chemical solution 10, since the effect of the chemical solution is exhibited by coating the surface of the tissue paper base paper 1, as shown in FIG. 1 and FIG. The oil-based chemical solution 10 needs to be applied to the surface. Therefore, it becomes difficult for moisture in the air to be absorbed by the tissue paper 1 through the outer surface to which the oil-based chemical solution 10 is applied (laminated outer surface: the surface indicated by the symbol A in FIGS. 1 and 2).

  For this reason, as shown in FIG. 1 and FIG. 2, in the form in which the oil-based chemical solution 10 is used and the powdered porous materials 20, 20. As a result, a reaction such as an alkali salt of chlorite adsorbed on the powdered porous material 20, 20... Occurs in the process. As it progresses, the fungicidal and bactericidal effects are manifested over an extremely long period of time.

  On the other hand, when a large amount of water is absorbed, such as when the nose is bitten as shown in FIG. 3, a large amount of water (nasal mucus) L and powder even on the surface to which the oil-based chemical is applied. Since the porous porous materials 20, 20 ... are in contact with each other, the reaction often occurs and chlorine dioxide is generated, effectively inactivating allergens such as viruses and pollen adhering to the runny nose or hands and face. .

  In the case of aqueous chemicals, chlorine dioxide can be generated at the time of use, but aqueous chemicals do not have the function of inhibiting moisture absorption in the air against tissue paper, but rather actively absorb moisture in the air. Since it acts so as to maintain softness, the antifungal effect inevitably tends to be shorter than that of oil-based chemicals.

  On the other hand, in the tissue paper according to the present invention, a bundle of a plurality of tissue papers is stored in a rectangular parallelepiped storage box and provided on the upper surface of the storage box (also referred to as a carton box or tissue carton). A tissue paper product that is used by sequentially pulling out tissue paper one by one from the take-out port (a type in which when the sheet is taken out, the next sheet is drawn out from the take-out port continuously is called a pop-up type).

  Such tissue paper products can be manufactured with known manufacturing equipment for this type of product. For example, a rotary interfolder or a multi-stand interfolder can be used for manufacturing a bundle.

The tissue paper of the present invention was tested for suitable conditions such as mold resistance.
The test was performed according to the general industrial product test method of JIS Z 2911 (mold resistance test). As test fungi, Aspergillus niger, Penicillium citrinum, Rhizopus oryzae, Cladosporium cladosporioides, Chaetomium globosum were used.

The test procedure was to inoculate the test mold on a potato dextrose agar medium and incubate at 25 ° C. for 10 days. Then, a spore solution was prepared using an inorganic salt solution to 10 ⁶ CFU / ml. Thereafter, the surface of the tissue paper according to each example was spray-inoculated with a test spore solution, cultured at 28 ± 2 ° C. and RH 95-99% or more for 28 days, and then the growth of the mold was observed.

  The evaluation of the test (antifungal performance in the table) is as follows: “0: no hyphal growth is observed, 1: the area where hyphal growth is recognized does not exceed 1/3 of the total area, 2: hyphal growth. Is larger than 1/3 of the total area. It was said.

Details of the results and the physical properties and composition of each example are shown in Table 1 below. In addition, Examples 1-5 are chemical | medical solution application type tissue paper manufactured by apply | coating the oil-type chemical | medical solution containing the mesoporous silica which adsorb | sucked sodium chlorite. Immobilization of sodium chlorite on mesoporous silica was performed by immersing mesoporous silica in a sodium chlorite solution and drying under reduced pressure (the same applies to Reference Examples).
In Reference Examples 1 and 2, the amount of mesoporous silica used was small.
In Reference Examples 3 to 5, the mesoporous silica adsorbed with sodium chlorite was mixed in the aqueous chemical solution in accordance with the manufacturing method of the chemical-coated tissue paper using the normal aqueous chemical solution. This is a manufactured chemical-coated tissue paper.

  First, it was confirmed that Examples 1 to 5 of the present invention exhibited extremely good antifungal properties, and the effects of the present invention were confirmed.

  Further, when Examples 1 to 5 and Reference Examples 1 and 2 are compared, since the difference in effect is seen depending on the amount of mesoporous silica used, the antifungal effect of the present invention is the mesoporous silica adsorbed with sodium chlorite. It can be confirmed that it is caused. In addition, also as content of the powdery porous material of the reference examples 1 and 2, an effect may be expressed by the storage form and storage form of tissue paper.

  On the other hand, even if a powdery porous material is contained in the aqueous chemical solutions of Reference Examples 3 to 5, sufficient effects cannot be obtained. This is probably because the chlorine dioxide generation reaction has progressed during the manufacturing process when using aqueous chemicals. Therefore, if it is contained in a chemical solution, it is necessary to use an oil-based chemical solution. When using an aqueous chemical solution, it is necessary to separately apply the chemical solution.

  DESCRIPTION OF SYMBOLS 1 ... Tissue paper base paper, 10 ... Chemical solution (oil type chemical solution), 20 ... Powdery porous material, P ... Ply, T ... Tissue paper, G ... Chlorine dioxide, L ... Water (nasal nose).

Claims (4)

  A tissue paper is coated with a powdered porous material on which a chemical solution is applied and at least one of an alkali metal chlorite and an alkaline earth metal chlorite is adsorbed. Tissue paper.   The tissue paper according to claim 1, wherein the tissue paper is coated with an oil-based chemical solution containing a powdered porous material in which at least one of an alkali metal chlorite and an alkaline earth metal chlorite is adsorbed. .   The tissue paper according to claim 1 or 2, wherein the tissue paper is two-ply or three-ply, and a powdery porous material is supported on an inner surface of the laminated layer.   A tissue paper product, wherein a plurality of the tissue papers according to any one of claims 1 to 3 are folded and stacked in a pop-up manner and stored in a storage box having an outlet on an upper surface.

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