JP4836597B2 - Deodorant antibacterial fiber products - Google Patents

Description

  The present invention relates to a deodorant antibacterial fiber product. The present invention also relates to an absorbent article provided with the deodorant antibacterial fiber product.

  Various sheet-like materials utilizing the adsorption performance of activated carbon have been conventionally known. For example, Patent Document 1 describes an activated carbon-containing pulp sheet that can be applied to various deodorizing uses containing activated carbon fine particles. However, this sheet has no antibacterial action. In addition, there is a drawback that activated carbon is easily dropped.

  Various zeolites are known as substances having an antibacterial action in addition to a deodorizing action. One method for supporting zeolite on a sheet is to knead it into the resin used. However, the efficiency is poor because only a part of the zeolite is exposed on the surface. On the other hand, when adhering to the surface of the sheet, zeolite has poor adhesion to fiber materials such as pulp, so it is difficult to carry a large amount on a sheet made of fiber materials such as wet papermaking paper. Moreover, even if it mix | blends abundantly, an efficient deodorant antibacterial effect cannot be expressed. In other words, the deodorizing and antibacterial effect cannot be effectively exhibited even with a small amount.

JP-A-9-173429

  Accordingly, an object of the present invention is to provide a deodorant and antibacterial fiber product that can eliminate the drawbacks of the above-described prior art, and an absorbent article having a deodorizing and antibacterial action.

  The present invention achieves the above object by providing a deodorized antibacterial fiber product including a cancrinite-like mineral containing a metal having antibacterial properties, a clay mineral, softwood bleached kraft pulp and hardwood bleached kraft pulp.

  The present invention also provides an absorbent article in which the deodorized antibacterial fiber product in the form of a sheet is disposed between the top sheet and the absorbent body, between the absorbent body, or between the absorbent body and the back sheet. It is to provide.

  The deodorant antibacterial fiber product of the present invention has sufficiently high deodorant ability and antibacterial ability due to the interaction between a cancrinite-like mineral containing a metal having antibacterial properties and a clay mineral. Therefore, the absorbent article provided with the deodorant antibacterial fiber product of the present invention can effectively prevent the generation of malodor and bacteria caused by excrement. Moreover, the paper strength of the deodorant antibacterial fiber product of the present invention is adjusted by using the cancrinite-like mineral and the viscosity mineral in combination with softwood bleached kraft pulp and hardwood bleached kraft pulp, and the product is soft. can do.

  Hereinafter, the present invention will be described based on preferred embodiments thereof. The deodorant antibacterial fiber product of the present invention is one in which a deodorant antibacterial agent is attached to a fiber material. The deodorizing antibacterial agent includes a cancrinite-like mineral containing a metal having antibacterial properties (hereinafter referred to as a metal-substituted cancrinite-like mineral) and a clay mineral. The metal-substituted cancrinite-like mineral is obtained by replacing the metal element in the cancrinite-like mineral with a metal element having antibacterial properties. The fiber material includes softwood bleached kraft pulp (hereinafter also referred to as NBKP) and hardwood bleached kraft pulp (hereinafter also referred to as LBKP).

  A cancrinite-like mineral has a structure similar to an aluminosilicate compound. In the present invention, the cancrinite-like mineral is JCPDS (Joint Committee on Powder Diffraction Standards) No. 20-379, 20-743, 25-776, 25-1499, 25-1500, 30-1170, 31-1272, 34-176, 35-479, 35-653, 38-513, 38-514, 38- One having at least one X-ray diffraction pattern selected from the group consisting of 515 and 45-1373. In the X-ray diffraction pattern, one having a main peak at d = 0.365 ± 0.015 nm is preferable.

  Metal-substituted cancrinite-like minerals have a broad deodorant spectrum and various malodors, such as alkaline odors such as ammonia, amines and pyridine, acidic odors such as lower fatty acids and mercaptans, and other neutral odors such as esters, ketones and aldehydes. It has been found by the present inventors that the present invention has a good deodorizing action against malodors consisting of It has also been found to exhibit a high antibacterial action. In other words, it has been found that the metal-substituted cancrinite-like mineral exhibits a high deodorizing and antibacterial action even when the amount used is small. In addition, the metal-substituted cancrinite-like mineral particles have a tetrapod-like shape, a confetti-like shape, or a sea-urchin-like shape, and it has also been found that the adhesion to fiber materials such as pulp is extremely good due to the shape. .

  However, when a metal-substituted cancrinite-like mineral is attached to a fiber material, particularly when a metal-substituted cancrinite-like mineral is attached to a fiber material by internal addition in a wet process, the metal-substituted cancrinite-like mineral has an inherent property. It became clear by examination of the present inventors that odor antibacterial action will fall. Although this reason is not clear, it is thought to be due to the influence of various additives (for example, wet paper strength agent) added when the metal-substituted cancrinite-like mineral is adhered to the fiber material. In order to prevent the deodorization and antibacterial action of the metal-substituted cancrinite-like minerals from being lowered, the present inventors have made various studies. It has been found that even when adhered to a fiber material, the deodorizing and antibacterial action can be prevented from decreasing, and the present invention has been completed.

  As a result, the deodorant antibacterial fiber product of the present invention can attach a large amount of metal-substituted cancrinite-like mineral, and the fiber product exhibits extremely high deodorant ability and antibacterial ability. Of course, even if the adhesion amount is small, the textile product exhibits sufficiently high deodorizing ability and antibacterial ability.

  The amount of the clay mineral in the deodorant antibacterial fiber product of the present invention is 1 to 30% by weight, particularly 1 to 10% by weight, based on the type of the clay mineral. It is preferable from the viewpoint of preventing the deodorization and antibacterial action of the knight-like mineral from being lowered. As the clay mineral, for example, zeolite, sepiolite, bentonite or the like which is a silicate other than the cancrinite-like mineral can be used. In particular, it is preferable to use zeolite from the viewpoint that the effect of preventing the deodorization and antibacterial action of the metal-substituted cancrinite-like mineral from decreasing is high. Various types of zeolite are known, but it is particularly preferable to use a ZSM-5 type.

  The amount of clay mineral used is also related to the amount of metal-substituted cancrinite-like mineral. Specifically, the amount of the clay mineral is 100 to 800% by weight, particularly 200 to 600% by weight, based on the amount of the metal-substituted cancrinite-like mineral. It is preferable from the viewpoint of preventing the decrease in the thickness.

  On the other hand, the adhesion amount of the metal-substituted cancrinite-like mineral to the fiber material in the deodorant antibacterial fiber product of the present invention can be adjusted in a wide range depending on the specific use of the fiber product. For example, it can be 0.01 to 20% by weight, particularly 0.2 to 10% by weight, based on the fiber material.

  The fiber material in the deodorant antibacterial fiber product of the present invention contains NBKP and LBKP. By using a combination of the two, an appropriate paper strength can be imparted to the textile and softness can be imparted. When only NBKP is used without using LBKP, the deodorized antibacterial fiber product tends to be hardened. For example, when the product is manufactured by incorporating the fiber product into a processing machine, trouble may occur. On the contrary, when only LBKP is used without using NBKP, the strength of the deodorant antibacterial fiber product tends to decrease, and there is a possibility that troubles such as running out of paper may occur in the processing machine. From these viewpoints, the weight ratio of NBKP / LBKP is preferably 95/5 to 50/50, and more preferably 95/5 to 60/40.

  In the case of producing the deodorized antibacterial fiber product of the present invention by wet papermaking, the beating state of the blended pulp of NBKP and LBKP is controlled from the viewpoint of successful papermaking, and the Canadian standard freeness (JIS) of the blended pulp is controlled. P8121, hereinafter also referred to as CSF) is preferably 400 to 600 ml, particularly 450 to 600 ml.

  The fiber material in the deodorant antibacterial fiber product of the present invention may be composed only of NBKP and LBKP, or may contain rayon in addition to these. A small amount of heat-fusible fibers made of a thermoplastic resin can be used in combination.

  Furthermore, it is preferable to add a wet paper strength agent to the deodorant antibacterial fiber product of the present invention. Thereby, high wet strength can be imparted to the textile. Increasing the wet strength of the textile product is advantageous from the viewpoint that, when the textile product is used as a constituent material of an absorbent article such as a disposable diaper, it is difficult to break even if the textile product gets wet with urine or the like. is there. In addition, an increase in wet strength means an increase in strength in a dry state. Accordingly, troubles are less likely to occur when a product is manufactured by incorporating the deodorant antibacterial fiber product of the present invention into a processing machine. For example, when the deodorant antibacterial fiber product of the present invention is, for example, in the form of a sheet, the tensile strength of MD in the dry state is preferably a high value of 400 cN / 25 mm or more. A method for measuring the tensile strength will be described in Examples described later. As the wet paper strength agent, for example, polyamidoamine / epichlorohydrin resin can be used. The wet paper strength agent is preferably blended in an amount of 0.01 to 5% by weight, particularly 0.1 to 2.0% by weight, based on the fiber material, from the viewpoint of obtaining sufficient wet strength.

As the metal-substituted cancrinite-like mineral, it is preferable to use one represented by the following composition formula (1).
_{sM (1) x O y ·} tM (2) 2 O · Al 2 O 3 · uSiO 2 · vR m Q n · wH 2 O (1)
In the formula, M (1) represents a metal having antibacterial properties, M (2) represents one or more elements selected from the group consisting of Na, K and H, and R represents Na, K, Ca and Mg. Q represents one or more elements selected from the group, Q represents one or more atomic groups selected from the group consisting of CO ₃ , SO ₄ , NO ₃ , OH and Cl, and s represents 0 <s ≦ 3, t is 0 ≦ t ≦ 3 (where s + t = 0.5 to 3), u is 0.5 ≦ u ≦ 6, v is 0 <v ≦ 2, w is w ≧ 0, x is 1 ≦ x ≦ 2, y satisfies 1 ≦ y ≦ 3, m satisfies 1 ≦ m ≦ 2, and n satisfies 1 ≦ n ≦ 3.

In the formula (1), M (1) is preferably Ag, Zn or Cu, particularly Ag, because of its high deodorizing ability against sulfur-containing malodors. M (1) may be one type or a combination of two or more types. When M (1) is a combination of two or more, the term of sM (1) _x O _y is described separately for each term corresponding to each element. For example, when M (1) is composed of metal elements D and D ′, sM (1) _x O _y is s ₁ D _x1 O _y1 · s ₂ D _x2 O _y2 (where x1 + x2 = x, y1 + y2 = y S ₁ + s ₂ = s). The same applies to the other terms.

M (2) is preferably Na and / or H from the viewpoint of high deodorizing ability and economical efficiency. From the same viewpoint as M (2), R is preferably one or more metal elements selected from the group consisting of Na, Ca and Mg, and more preferably Na. Q is preferably CO ₃ and / or NO ₃ from the viewpoint of ease of particle shape control.

  s is preferably 0 <s ≦ 2 and more preferably 0 <s ≦ 1 from the viewpoint of high deodorizing ability and economical efficiency. t is preferably 0 ≦ t ≦ 2, more preferably 0 ≦ t ≦ 1, from the viewpoint of maintaining a good pH of an aqueous dispersion of a metal-substituted cancrinite-like mineral (a 1 wt% aqueous dispersion described later). . s + t is preferably 0.5 to 1.8, more preferably 0.6 to 1.5. u is preferably 0.5 ≦ u ≦ 5, more preferably 0.5 ≦ u ≦ 4, from the viewpoint of high deodorizing ability. From the viewpoint of ease of particle shape control, v is preferably 0 <v ≦ 1.5, more preferably 0 <v ≦ 1. w is the content (molar ratio) of water contained in the metal-substituted cancrinite-like mineral, and varies depending on the form of the metal-substituted cancrinite-like mineral, for example, in the form of powder or slurry. x and y and m and n are arbitrarily determined according to the combination of M (1) and O and according to the combination of R and Q, respectively.

It metal-substituted cancrinite-like mineral that specific surface area is preferably less than 1 m ² / g or more 70m ² / g, more preferably from 1~65m ² / g, a 30~65m ² / g Is more preferable. If the specific surface area is within this range, the metal having antibacterial properties can be appropriately fixed or supported, and an excellent deodorizing ability against sulfur-containing malodors can be exhibited. The specific surface area of the metal-substituted cancrinite-like mineral can be adjusted to a predetermined range by appropriately acid-treating raw material aluminosilicate particles (aluminosilicate particles used as a raw material), for example, as described later. The specific surface area is measured using a flowsorb 2300 type (manufactured by Shimadzu Corporation). The sample is 0.1 g, and a mixed gas of N ₂ / He = 30/70 (volume ratio) is used as the adsorption gas.

  From the viewpoint of enhancing the deodorizing ability of sulfur-containing malodor, the metal-substituted cancrinite-like mineral preferably has a 1 wt% aqueous dispersion having a pH of 7 or more, more preferably 8 or more, and 9 or more. It is more preferable that The pH of the 1% by weight aqueous dispersion of metal-substituted cancrinite-like mineral is determined by the method described later.

  In metal-substituted cancrinite-like minerals, the M (1) component exhibits deodorizing ability by adsorbing sulfur-containing malodors. Therefore, it is preferable that a large amount of the M (1) component is present in the vicinity of the surface of the metal-substituted cancrinite-like mineral from the viewpoint of developing an excellent deodorizing power. The surface concentration of the M (1) component is determined by the molar ratio of the M (1) component atom to the Si atom [M (1) / Si] or the molar ratio of the M (1) component atom to the Al atom measured by ESCA [ M (1) / Al]. M (1) / Si is preferably 0.021 or more, more preferably 0.040 or more. Further, M (1) / Al is preferably 0.025 or more, more preferably 0.040 or more. The measurement by ESCA can be performed using ESCA-1000 manufactured by Shimadzu Corporation after forming a sample into a thin piece by a press. The element on the sample surface is measured [M (1) component atom, Si, Al], and the surface atom concentration ratio (molar ratio) is determined from the peak area of the obtained element.

  The metal-substituted cancrinite-like mineral has an average particle size of 0.1 to 1000 μm, particularly 0.4 to 600 μm, particularly 1 to 100 μm, and the point that the deodorizing speed is increased and the powder fluidity is improved. It is preferable from the point. The average particle diameter is measured at a relative refractive index of 1.16 using, for example, a laser diffraction / scattering particle size distribution measuring device (LA-920 manufactured by Horiba, Ltd.).

  The metal substituted cancrinite-like mineral may be amorphous or crystalline. From the viewpoint of improving the deodorizing ability of sulfur-containing malodors, it is preferably crystalline. The metal-substituted cancrinite-like mineral is obtained as an aggregate of acicular crystals, plate crystals, columnar crystals, etc. depending on the production conditions. Further, these crystals may be aggregated to form a spherical, tetrabod-like, massive aggregate, or the like, or a secondary aggregate thereof.

  The needle-like form refers to those having a thickness of 500 nm or less and a length of 2.0 or more in aspect ratio with respect to the thickness. The plate-like form means one having a thickness of 300 nm or less and a plate diameter of 2.0 or more in aspect ratio with respect to the thickness. The columnar form means that the thickness is 50 nm or more and the length is 1.0 or more and less than 2.0 in terms of the aspect ratio with respect to the thickness.

Metal-substituted cancrinite-like mineral, for example, the composition of the anhydride, aM during _{2 O · Al 2 O 3 ·} bSiO 2 · cR m Q n ( wherein, M represents Na and / or K, R is Na, Q represents one or more elements selected from the group consisting of K, Ca and Mg, Q represents one or more atomic groups selected from the group consisting of CO ₃ , SO ₄ , NO ₃ , OH and Cl, and a represents A raw material aluminosilicate in which 0.5 ≦ a ≦ 3, b is 0.5 ≦ b ≦ 6, c is 0 <c ≦ 2, m is 1 ≦ m ≦ 2, and n is 1 ≦ n ≦ 3) In addition, it is obtained by subjecting to acid treatment using 0 to 300 meq (0 to 300 meq / 100 g) of acid per 100 g of the raw material aluminosilicate and ion exchange with antibacterial ions. preferable.

In the above formula, M is preferably Na. When M consists of Na and K, aM ₂ O is represented by a′Na ₂ O · a ″ K ₂ O (where a ′ + a ″ = a). The same applies to the other terms. R is preferably one or more elements selected from the group consisting of Na, Ca and Mg, and more preferably Na. Q is preferably CO ₃ and / or NO ₃ . a is preferably 0.5 ≦ a ≦ 2.5, more preferably 0.5 ≦ a ≦ 2. b is preferably 0.5 ≦ b ≦ 5, more preferably 0.5 ≦ b ≦ 4. c is preferably 0 <C ≦ 1.5, more preferably 0 <c ≦ 1. m and n are arbitrarily determined according to the combination of R and Q.

  The specific surface area of the raw material aluminosilicate is preferably about the same as that of the metal-substituted cancrinite-like mineral. The average particle diameter is also preferably about the same as that of the metal-substituted cancrinite-like mineral. Further, the form is not particularly limited, but for example, the same form as the metal-substituted cancrinite-like mineral is preferable.

There is no particular limitation on the method for producing the raw material aluminosilicate. For example, a method in which an alumina raw material and a silica raw material are reacted in an alkaline solution in the presence of CO ₃ ²⁻ , SO ₄ ²⁻ , NO ₃ ⁻ , Cl ^{− and the} like can be mentioned. Examples of the alumina raw material include aluminum oxide, aluminum hydroxide, and sodium aluminate. Sodium aluminate is particularly preferable. Examples of the silica raw material include silica sand, silica stone, water glass, sodium silicate, silica sol and the like. Water glass is particularly preferable. Alternatively, as a raw material for both the alumina raw material and the silica raw material, for example, clay minerals such as kaolin, montmorillonite, bentonite, mica and talc, and aluminosilicate minerals such as mullite may be used. Examples of the raw material for CO ₃ ^2- include carbon dioxide, sodium carbonate, potassium carbonate, potassium sodium carbonate, calcium carbonate, and magnesium carbonate. Sodium carbonate is particularly preferred. Examples of the raw material of SO ₄ ^2- include sulfuric acid, sodium sulfate, potassium sulfate, and potassium sodium sulfate. In particular, sulfuric acid and sodium sulfate are suitable. NO ₃ ^- as a raw material, such as nitric acid, sodium nitrate, potassium nitrate, and the like. Nitric acid and sodium nitrate are particularly suitable. Cl ^- The raw materials, for example, hydrochloric acid, sodium chloride, potassium chloride and the like. In particular, hydrochloric acid and sodium chloride are suitable. Examples of the alkali of the alkaline solution include oxides such as sodium oxide and potassium oxide; hydroxides such as sodium hydroxide and potassium hydroxide; carbonates such as sodium carbonate, potassium carbonate and potassium carbonate; sodium hydrogen carbonate and carbonate Hydrogen carbonate such as potassium hydrogen can be used. Oxides such as calcium oxide and magnesium oxide; hydroxides such as calcium hydroxide and magnesium hydroxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; bicarbonates such as calcium bicarbonate and magnesium bicarbonate Etc. may be used.

The raw material aluminosilicate can be obtained by mixing and reacting the above-mentioned various compounds in a predetermined ratio. About the ratio of a mixing | blending, it determines suitably according to the composition of the desired raw material aluminosilicate obtained. Preferably, the charge ratio of the component that is the raw material of the raw material aluminosilicate is expressed as M ₂ O, Al ₂ O ₃ , SiO ₂ , R _m Q _n based on the constituent elements of each component, As a molar ratio, M ₂ O / SiO ₂ is preferably 0.01 to 100, more preferably 0.05 to 80, and Al ₂ O ₃ / SiO ₂ is preferably 0.01 to 10, more preferably 0. 0.05 to 8, R _m Q _n / SiO ₂ is preferably 0.01 to 100, more preferably 0.05 to 80, and H ₂ O / M ₂ O is preferably 0.01 to 100, More preferably, it is 0.05-80.

  The reaction temperature at the time of producing the raw material aluminosilicate is preferably 15 to 300 ° C. from the viewpoint of increasing the crystallinity of the raw material aluminosilicate, stabilizing the form, and reducing the chemical and pressure load on the reaction vessel. More preferably, it is 60-150 degreeC, More preferably, it is 80-130 degreeC. The reaction time is preferably 2 hours or more and 48 hours or less from the viewpoint of complete crystallization reaction. As described above, the raw material aluminosilicate is usually obtained as an aqueous dispersion (slurry). The solid content concentration of the aqueous dispersion is preferably 0.1 to 50% by weight.

Subsequently, the obtained raw material aluminosilicate is acid-treated using 0 to 300 meq (0 to 300 meq / 100 g) of acid per 100 g of the raw material aluminosilicate. The acid treatment is performed to adjust the pH of the slurry when the M (1) component is fixed or supported on the raw material aluminosilicate by ion exchange. In that case, it is preferable to adjust pH of a slurry to pH 7 or less from a viewpoint of expression of the ion exchange property of M (1) component. The acid treatment is also performed for adjusting the specific surface area. The acid treatment amount is preferably 6 to 300 meq / 100 g, more preferably 5 to 250 meq / 100 g, and still more preferably 20 to 140 meq / 100 g from the viewpoint of improving the deodorizing ability. In addition, the case where acid treatment is performed using 0 meq / 100 g of acid means the case where acid treatment is not performed. For example, when the raw material aminosilicate has a specific surface area of 1 m ² / g or more and less than 70 m ² / g, the raw material aminosilicate may not be subjected to acid treatment. For the acid treatment, it is preferable to use a strong acid such as hydrochloric acid, sulfuric acid, or nitric acid, and it is particularly preferable to use hydrochloric acid or nitric acid. The acid treatment is performed by adding the aqueous solution containing the acid to the raw material aluminosilicate gradually or all at once and bringing the acid into contact with the raw material aluminosilicate. The addition rate is preferably 0.01 to 100 ml / min, more preferably 0.1 to 10 ml / min with respect to 100 g of the raw material aluminosilicate. In the acid treatment, the raw material aluminosilicate is preferably made into a slurry. The solid content concentration of the slurry is preferably 1 to 50% by weight from the viewpoint of ensuring the fluidity of the reaction mixture and preventing the unevenness of the acid treatment to improve the treatment efficiency. The temperature during the acid treatment is preferably 60 to 150 ° C., more preferably 80 to 120 ° C., from the viewpoint of improving the specific surface area and reducing the chemical and pressure load on the reaction vessel. The acid treatment may be performed with appropriate stirring. The acid treatment time is preferably 0.01 to 100 hours, more preferably 0.1 to 10 hours after the acid and the raw material aluminosilicate are brought into contact with each other. After the acid treatment, it is preferable that the reaction mixture is appropriately aged, for example, at 60 to 150 ° C. for about 0.1 to 1 hour.

  The raw material aluminosilicate after the acid treatment is ion-exchanged with metal ions having antibacterial properties. Alternatively, raw material aluminosilicate having a desired specific surface area may be ion-exchanged as it is without acid treatment. In the ion exchange, for example, the raw material aluminosilicate after acid treatment is suspended in water, and a compound containing the metal (hereinafter referred to as a metal-containing compound) or an aqueous solution of the compound is added thereto, or in an aqueous solution of the metal-containing compound. It can be carried out by immersing the raw material aluminosilicate in As described above, the raw material aluminosilicate does not have to be ion-exchanged after acid treatment. For example, if a metal-containing compound coexists during acid treatment, the raw material aluminosilicate is subjected to acid treatment and ion exchange at the same time. It can be carried out. The metal-containing compound is not particularly limited as long as it is a water-soluble metal-containing compound containing a desired metal, and for example, a nitrate, sulfate, chloride or the like containing a desired metal can be used. The ion exchange is usually performed with the raw material aluminosilicate suspended in water and stirring. From the viewpoint of improving the efficiency of ion exchange, the solid content concentration of the aqueous suspension of the raw material aluminosilicate is preferably 1 to 50% by weight. The temperature at the time of performing ion exchange is not particularly limited. Preferably it is 20-120 degreeC, More preferably, it is 80-110 degreeC. The ion exchange time is preferably 0.01 to 2 hours, more preferably 0.02 to 1 hour, after the raw material aluminosilicate and the metal-containing compound are brought into contact with each other. The amount ratio of the raw material aluminosilicate to the metal-containing compound in the ion exchange is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 10 parts by weight, with respect to 100 parts by weight of the raw material aluminosilicate. More preferably, it is 0.5 to 5 parts by weight. After the ion exchange, it is preferable that the reaction mixture is appropriately aged, for example, at 60 to 150 ° C. for about 0.1 to 10 hours.

  Most preferably, the metal component in the metal-containing compound is fixed or supported on the cancrinite-like mineral by ion exchange as described above. However, instead of or in addition to ion exchange, the metal component in the metal-containing compound may be fixed or supported on the cancrinite-like mineral by an impregnation method or a precipitation method. In the production process of metal-substituted cancrinite-like minerals, (a) after obtaining raw material aluminosilicate, (b) after acid treatment, and (c) after ion exchange, raw material aluminosilicate is treated with impurities, etc. You may wash | clean suitably for the purpose of removing. In particular, it is preferable to wash after the final stage of the raw material aluminosilicate manufacturing process, for example, after obtaining the raw material aluminosilicate and after ion exchange. The washing can be performed by, for example, filtering and washing a water suspension of the raw material aluminosilicate. Although the filter used for filtration is not specifically limited, For example, a Nutsche type, a filter press type, etc. can be used.

In the present invention, in place of the metal-substituted cancrinite-like mineral described above, a portion of M in the cancrinite-like mineral represented by the following composition formula (2) is substituted with a metal having antibacterial properties ( Hereinafter, a second metal-substituted cancrinite-like mineral can also be used.
s ₁ M ₂ O.Al ₂ O ₃ .u ₁ SiO ₂ .v ₁ R _m1 Q _{n1 .w 1} H ₂ O (2)
In the formula, M represents one or more elements selected from the group consisting of Na, K and H, R represents one or more elements selected from the group consisting of Na, K, Ca and Mg, and Q represents CO _3. Represents one or more atomic groups selected from the group consisting of, SO ₄ , NO ₃ , OH and Cl. s ₁ is 0 <s ₁ ≦ 1, u ₁ is 1 ≦ u ₁ ≦ 50, v ₁ is 0 <v ₁ ≦ 2, w ₁ is w ₁ ≧ 0, m1 is 1 ≦ m1 ≦ 2, n1 is 1 ≦ n1 ≦ 2 is satisfied.

  Hereinafter, the second metal-substituted cancrinite-like mineral will be described. However, the explanation regarding the metal-substituted cancrinite-like mineral described above is appropriately applied to points that are not particularly described regarding the mineral. The second metal-substituted cancrinite-like mineral corresponds to a cancrinite-like mineral represented by the composition formula (2) in which a part of M is substituted with a metal having antibacterial properties. The amount of substitution of the metal having antibacterial properties in the cancrinite-like mineral represented by the composition formula (2) is 0.1 to 30% by weight, particularly from the viewpoint of expression of desired deodorizing ability and antibacterial ability, and economy. It is preferably 0.1 to 10% by weight. The amount of these metals can be measured by fluorescent X-ray measurement.

  In the second metal-substituted cancrinite-like mineral, it is preferable that aluminum contained in the second metal-substituted cancrinite-like mineral is in an amorphous state by elution with an acid. By elution of aluminum, many fine pores are formed in the second metal-substituted cancrinite-like mineral, and the deodorizing ability is further enhanced. The elution of aluminum by acid will be described later.

The second metal-substituted cancrinite-like mineral, it is suitable deodorizing rate and wider consumption thereof having a specific surface area of 70~800m ² / g, especially 80~600m ² / g, especially 100 to 500 m ² / g This is preferable from the viewpoint of developing an odor spectrum.

The acid amount of the second metal-substituted cancrinite-like mineral is preferably 20 meq / 100 g or more, particularly 100 meq / 100 g or more, particularly 170 meq / 100 g or more from the viewpoint of improving the deodorizing ability of the alkaline malodorous gas. . “Acid amount” refers to the total amount of acid sites of the second metal-substituted cancrinite-like mineral. The amount of acid was determined by stirring 0.5 ml of a sample in 100 ml of 0.01 mol / l NaOH aqueous solution for 1 hour, centrifuging the obtained sample suspension (10000 rpm × 5 minutes), and collecting 25 ml of the supernatant, The fractionated solution is titrated with 0.01 mol / l HNO ₃ to determine the amount of consumed NaOH, and calculated based on the obtained amount of NaOH.

  The average particle diameter of the second metal-substituted cancrinite-like mineral is preferably 1 to 500 μm, more preferably 1 to 300 μm, and still more preferably 1 to 100 μm. Within such a range, an appropriate deodorization rate can be obtained, and the handleability can be improved.

In the cancrinite-like mineral represented by the composition formula (2), M is preferably Na and / or H from the viewpoint of high deodorizing ability and economical efficiency. When M consists of Na and H, s ₁ M ₂ O is represented by s ′ _l Na ₂ O.s ′ ₂ H ₂ O (wherein s ′ _l + s ′ ₂ = s ₁ ). From the same viewpoint as M, R is preferably Na. Q is preferably CO ₃ or NO ₃ from the viewpoint of ease of particle shape control.

From the viewpoint of improving the deodorizing ability of the alkaline malodorous gas, s ₁ is preferably 0 <s ₁ ≦ 0.5, and more preferably 0 <s ₁ ≦ 0.25. u ₁ is preferably 1 ≦ u ₁ ≦ 40, more preferably 1 ≦ u ₁ ≦ 30, from the viewpoint of improving the deodorizing ability of the acidic malodorous gas. v ₁ is preferably 0 <v ₁ ≦ 1, more preferably 0 <v ₁ ≦ 0.6, and still more preferably 0 <v ₁ ≦ 0.3, from the viewpoint of expressing high deodorizing ability. w ₁ is the content (molar ratio) of water contained in the precursor, and varies depending on the presence form of the precursor, for example, powder form, slurry form, and the like. m1 and n1 are arbitrarily determined according to the combination of R and Q.

  The second metal-substituted cancrinite-like mineral is, for example, a raw material aluminosilicate that is acid-treated to form a cancrinite-like mineral, and the obtained cancrinite-like mineral is suspended in water, and there is an antibacterial metal. It is preferably produced by adding an aqueous solution of a water-soluble salt and performing ion exchange. As another method, it can also be suitably produced by performing ion exchange in the presence of an antibacterial metal water-soluble salt at the time of acid treatment of the raw material aluminosilicate.

The raw material aluminosilicate used for the second metal-substituted cancrinite-like mineral is represented by the following composition formula (3).
_{a 1 M 2 O · Al 2} O 3 · b 1 SiO 2 · c 1 R m1 Q n1 · zH 2 O (3)
In the formula, M, R, Q, m1 and n1 are the same as defined in the composition formula (2), a ₁ is 0.1 ≦ a ₁ ≦ 3, b ₁ is 0.2 ≦ b ₁ ≦ 6, c ₁ satisfies 0 <c ₁ ≦ 2, and z satisfies z ≧ 0. The method for producing the raw material aluminosilicate particles is not particularly limited. For example, a method in which an alumina raw material and a silica raw material are reacted in an alkaline solution in the presence of CO ₃ ²⁻ , SO ₄ ²⁻ , NO ₃ ⁻ , Cl ⁻ , etc. Is mentioned.

It is preferable to use a strong acid such as hydrochloric acid, sulfuric acid or nitric acid as an acid used when the raw material aluminosilicate is acid-treated to obtain a cancrinite-like mineral. In particular, it is preferable to use hydrochloric acid or nitric acid. By acid-treating the raw material aluminosilicate, not only M ₂ O and R _m1 Q _n1 existing in the pores of the raw material aluminosilicate are eluted, but also a part of Al forming the skeleton is eluted. As a result, the specific surface area, pore volume, and acid point increase, and the second metal-substituted cancrinite-like mineral finally obtained is in an amorphous state as described above. What is necessary is just to adjust the grade of an acid treatment suitably so that the 2nd metal substituted cancrinite-like mineral finally obtained may have a desired property. The acid treatment is performed by adding the aqueous solution containing the acid to the raw material aluminosilicate gradually or all at once, and bringing the acid into contact with the raw material aluminosilicate. The addition rate is preferably 0.01 to 100 ml / min, more preferably 0.1 to 10 ml / min with respect to 100 g of the raw material aluminosilicate.

  The cancrinite-like mineral obtained by acid treatment of the raw material aluminosilicate is preferably aged at 60 to 150 ° C. for about 0.1 to 10 hours. The slurry is then filtered and washed with water to remove excess ionic components. Subsequently, the cancrinite-like mineral separated by filtration is suspended in water, and an aqueous solution of a water-soluble salt of a metal having antibacterial properties is added and aged for a predetermined time under heating to a predetermined temperature. Thereby, the objective 2nd metal substituted cancrinite-like mineral is obtained.

  The deodorant antibacterial fiber product of the present invention can take various forms depending on the production method. For example, it may take a form such as a sheet form, a fragmented form thereof, a granular form, or a three-dimensional molded article form. These forms can be obtained by producing the deodorant antibacterial fiber product of the present invention by a wet method. When the deodorant antibacterial fiber product of the present invention is in the form of a sheet, the sheet may be in the form of a single layer containing a metal-substituted cancrinite-like mineral, or in the form of a laminated sheet in which a plurality of sheets are laminated. It may be. When the sheet is in the form of a single layer, the sheet is produced by a wet papermaking method using a slurry containing fiber material and metal-substituted cancrinite-like mineral particles as raw materials. In the case of a laminated sheet, an example of the sheet is a sheet having the form shown in FIG. The deodorant antibacterial fiber product 1 shown in FIG. 1 has two rectangular pulp sheets of the same size, that is, between the first pulp sheet 2 and the second pulp sheet 3 than these pulp sheets 2 and 3. It is a laminated sheet formed by interposing a rectangular inner layer sheet 4 having a short length in the width direction. The inner layer sheet 4 is a sheet of a fiber material containing particles of a metal-substituted cancrinite-like mineral, and this sheet is the same as the single-layer sheet described above. The inner layer sheet 4 is a mixed paper of metal-substituted cancrinite-like minerals, and is sandwiched between two pulp sheets 2 and 3 at the center in the width direction. The inner layer sheet 4 and the pulp sheets 2 and 3 are laminated by papermaking.

  In the side parts 1a and 1b of the deodorant antibacterial fiber product 1, the inner layer sheet 4 is not interposed over the entire length direction, and two pulp sheets 2 and 3 are laminated on the side part. It has a two-layer structure. By joining the pulp sheets 2 and 3 in the side portions 1a and 1b to each other, both end portions of the deodorant antibacterial fiber product 1 are sealed, and the metal-substituted cancrinite-like mineral is removed from the side end portions. Is prevented. The widths of the side portions 1a and 1b are preferably 0.1 to 20 cm, more preferably 1 to 6 cm, which sufficiently prevents the metal-substituted cancrinite-like mineral from falling off and sufficiently functions the metal-substituted cancrinite-like mineral. It is preferable from the point of expression.

  As described above, the sheet of the fiber material containing the metal-substituted cancrinite-like mineral (that is, the single-layer sheet and the inner-layer sheet described above) is a wet papermaking using a slurry containing the fiber material and particles of the metal-substituted cancrinite-like mineral as a raw material. Manufactured by law. From the viewpoint of increasing the adhesion amount of the metal-substituted cancrinite-like mineral to the fiber material, it is preferable to add a flocculant to the slurry. As the aggregating agent, for example, polyacrylamide or an acrylic (methacrylic) copolymer (molecular weight: 5 to 50 million) is preferably used. Particularly preferred are polyacrylamide and acrylic (methacrylic) copolymers (molecular weight: 10 million to 30 million). In the deodorized antibacterial fiber product of the present invention, the flocculant is blended in an amount of 0.01 to 0.04% by weight, particularly 0.01 to 0.035% by weight, based on the fiber material. This is preferable from the viewpoint of sufficiently increasing the amount of minerals deposited and increasing the strength of the deodorant antibacterial fiber product of the present invention.

  The amount of the metal-substituted cancrinite-like mineral in the slurry is preferably 0.1 to 10% by weight, particularly 0.5 to 5.0% by weight, based on the fiber material. The amount of clay mineral is preferably 0.1 to 30% by weight, particularly 0.1 to 10% by weight, based on the fiber material. The flocculant is preferably added from the viewpoint of increasing the adhesion amount of the metal-substituted cancrinite-like mineral and clay mineral to the fiber material. From the viewpoint of productivity, the amount of the flocculant is 0.001 relative to the fiber material. It is preferable that it is -1.0weight%, especially 0.001-0.04weight%. The amount of wet paper strength agent is preferably 0.1 to 5% by weight, particularly 0.1 to 2.0% by weight, based on the fiber material. The concentration of the fiber material in the slurry is preferably 0.5 to 5.0% by weight, particularly 1.0 to 3.0% by weight.

The adhesion rate of metal-substituted cancrinite-like minerals on sheets obtained by wet papermaking (that is, the single-layer sheet and inner-layer sheet described above) should be as high as 25% or more, particularly 50% or more depending on the selection of the flocculant. Can do. The reason for this is largely due to the shape of the metal-substituted cancrinite-like mineral as described above. Although it depends on the specific application, the sheet preferably has a basis weight of 10 to 100 g / m ² , particularly 13 to 70 g / m ² .

  When the deodorant antibacterial paper product of the present invention is in the form of a sheet, it can be used by cutting it into small pieces. For example, a fragmented deodorized antibacterial paper product can be used as a constituent material of an absorbent body in an absorbent article described later.

  As described above, the deodorized antibacterial paper product of the present invention may take a granular or three-dimensional molded form in addition to the sheet form. In the case of a granular form, it can be obtained by extruding a high-concentration slurry of a fiber material containing a metal-substituted cancrinite-like mineral in a strand form from an extruder and cutting it into a predetermined size. When it is in the form of a three-dimensional molded product, it can be made into various container shapes such as a bottle shape, a cup shape, and a tray shape. In order to produce such a three-dimensional molded product, it is preferable to use a pulp molding method. The details of the pulp mold method are described in, for example, WO99 / 42661 relating to the previous application of the present applicant.

  The deodorant antibacterial fiber product of the present invention is effective for deodorization and antibacterial in various situations. For example, when the deodorant antibacterial fiber product of the present invention is in the form of a sheet or a broken piece thereof, the constituent material of absorbent articles such as disposable diapers, sanitary napkins, absorbent pads, wallpaper, sheets, indentation sheets, It is useful as a bag sheet, a shoebox sheet, a mat, a shoe insole, a mask, a filter, an insole sheet for wrapping food. In addition, when the deodorant antibacterial fiber product of the present invention is in the form of beads, pellets or the like, it is useful as a deodorant for pets such as cat sand. When the deodorant antibacterial fiber product of the present invention is in the form of a three-dimensional molded product, it is useful as an antibacterial deodorant storage case or the like formed into a box shape, for example.

  When the deodorant antibacterial fiber product of the present invention is in the form of a sheet, when the sheet is used as a constituent material of an absorbent article, the sheet is, for example, between the top sheet and the absorbent, the absorbent, or the It can distribute | arrange between an absorber and a back surface sheet. Alternatively, the sheet can be coated with an absorbent material such as pulp or superabsorbent polymer to form an absorbent body, and the absorbent body can be used for absorbent articles. The top sheet is disposed on the side facing the user's skin when the absorbent article is used, and is generally liquid permeable. The absorber is disposed between the top sheet and the back sheet, and is generally liquid retaining. The back sheet is disposed on the side opposite to the top sheet, that is, on the side far from the user's skin with the absorbent body in between, and is generally water-repellent or liquid-impermeable.

  FIG. 2 shows a state where the absorbent body of the absorbent article is coated with the deodorant antibacterial sheet of the present invention as an example in which the deodorant antibacterial sheet of the present invention is applied to the absorbent article. The absorbent body 10 is composed of superabsorbent polymer particles and pulp fibers. The absorbent body 10 is covered with the deodorant antibacterial sheet 1 so that the one side part 1a and the other side part 1b of the deodorant antibacterial sheet 1 are overlapped. Under this state, the absorbent body 10 is sandwiched between a front sheet and a back sheet (not shown) to form an absorbent article. Therefore, in this embodiment, the deodorizing antibacterial sheet 1 is arranged between the top sheet and the absorbent body and between the back sheet and the absorbent body in the absorbent article. In this case, if any part of the absorbent article contains an adsorbent of sulfur compounds such as hydrogen sulfide and mercaptans, which are representative of bad odor, the metal in the metal-substituted cancrinite-like mineral Since the antibacterial fall of the metal resulting from a coupling | bonding with a sulfur compound is prevented effectively, it is preferable at the point of antibacterial durability. In addition, the deodorizing ability of the metal-substituted cancrinite-like mineral is improved. Zinc oxide is a typical example of the sulfur compound adsorbing substance. For example, the sulfur compound adsorbing substance can be attached to the deodorizing antibacterial sheet of the present invention, or can be contained in the absorber.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to such examples. In the following examples, “%” means “% by weight” unless otherwise specified.

[Example 1]
94 g of sodium hydroxide is dissolved in 1000 ml of ion exchange water, 130 g of nitric acid (61%), sodium aluminate solution (Na ₂ O = 19.8%, Al ₂ O ₃ = 25.9%, H ₂ O = 127 g of water glass (Na ₂ O = 9.8%, SiO ₂ = 29.6%, H ₂ O = 60.6%) was added to a solution in which 124 g) was mixed over 1 minute. The reaction was carried out at 100 ° C. for 8 hours. After the reaction, the produced aluminosilicate particles were washed by filtration and dried at 105 ° C. for 12 hours to obtain raw material aluminosilicate particle powders. The obtained raw material aluminosilicate particles had a porous spherical shape in which acicular crystals were assembled. As a result of performing X-ray diffraction using a powder X-ray diffractometer [RINT2500, manufactured by Rigaku Corporation], the diffraction pattern is JCPDS No. It corresponded to 38-513. The resulting raw material aluminosilicate particles are a particulate form of sea urchin shaped composition was _{Na 2 O · Al 2 O 3} · 2SiO 2 · 0.4NaNO 3 · 0.7H 2 O. The specific surface area was 40 m ² / g.

100 g of the obtained raw material aluminosilicate particles were suspended in 900 ml of ion-exchanged water and kept at 100 ° C. While stirring, a predetermined amount of 61% nitric acid was dropped at a rate of 1 ml / min for acid treatment. Next, an aqueous silver nitrate solution in which 3.94 g of silver nitrate was dissolved in 30 g of ion-exchanged water was added, and ion exchange was performed by maintaining at 100 ° C. for 1 hour. Then, it filtered, washed with water, and dried at 105 degreeC for 12 hours, and obtained white Ag substitution cancrinite-like mineral. Ag-substituted cancrinite-like mineral obtained is a particulate form of sea urchin type, composition _{0.05Ag 2 O · 0.9Na 2 O ·} Al 2 O 3 · 2SiO 2 · 0.4NaNO 3 · 0.7H ₂ O. The specific surface area was 44.7 m ² / g, and the average particle size was 8.3 μm. The pH of the 1% aqueous dispersion was 10.04. The concentration of Ag on the surface was Ag / Si = 0.075 and Ag / Al = 0.070.

  The obtained Ag-substituted cancrinite-like mineral was suspended in ion exchange water. Furthermore, blended pulp of NBKP and LBKP, synthetic zeolite 4A type (manufactured by Shilton B Mizusawa Chemical Co., Ltd.), wet paper strength agent (Kaimen WS547 manufactured by Nippon PMC Co., Ltd.), polyacrylamide polymer flocculant (Acofloc A95, Mitsui Chemicals Aqua Polymer Co., Ltd.) ) Was added and mixed to obtain a slurry. A blended pulp whose CSF was adjusted to 550 ml by beating was used. The weight ratio of NBKP / LBKP in the blended pulp was 90/10.

  The concentration of blended pulp in the slurry is 2%, the concentration of Ag-substituted cancrinite-like mineral is 2% with respect to the blended pulp, the concentration of zeolite is 5% with respect to the blended pulp, and the concentration of wet strength is in the blended pulp. In contrast, the concentration of the polymer flocculant was 0.5% with respect to the blended pulp.

Using this slurry as a raw material, wet paper making was performed using a round net paper machine to obtain a deodorized antibacterial paper which is a deodorant antibacterial fiber product. The basis weight was 16 g / m ² . The amount of Ag-substituted cancrinite-like mineral in the deodorized antibacterial paper was 1% with respect to the blended pulp, and the amount of zeolite was 2.5% with respect to the blended pulp. The amount of wet paper strength was 0.45% for blended pulp and the amount of flocculant was 0.018% for blended pulp.

As shown in FIG. 3, an air-through nonwoven fabric surface sheet 11 having a basis weight of 20 g / m ² is provided on one side of the obtained deodorized antibacterial paper 12, and a basis weight of 350 g / m ^{2 is provided on} the other side. An absorbent body 13 composed of particles of pulp and a superabsorbent polymer having a basis weight of 120 g / m ² was arranged, and both sides of the deodorized antibacterial paper 12 and the absorbent body 13 were covered with an absorbent paper 14 having a basis weight of 15 g / m ² . . A liquid-impermeable back sheet 15 having a basis weight of 15 g / m ² was superposed on the back surface of the coated absorbent body 13. Thus, an absorbent pad having a length of 400 mm and a width of 150 mm was obtained. The nonwoven fabric, pulp, superabsorbent polymer, absorbent paper, and liquid-impermeable sheet are the same as the materials used in the relief (registered trademark) urine pad (trade name) manufactured by Kao Corporation. The thing of was used.

[Examples 2 and 3 and Comparative Examples 1 and 2]
A deodorized antibacterial paper and an absorbent pad were obtained in the same manner as in Example 1 except that the composition of the slurry was changed to the values shown in Table 1.

[Evaluation]
The adhesion rate of the Ag-substituted cancrinite-like mineral contained in the obtained deodorized antibacterial paper was measured by the following method. The softness, tensile strength (dry and wet) of the deodorized antibacterial paper, productivity on the round net paper machine, and workability on the processing machine were measured and evaluated by the following methods. Furthermore, about the obtained absorbent pad, the deodorization rate and antibacterial ability of hydrogen sulfide were measured and evaluated by the following methods. These results are shown in Table 1.

[Adhesion rate of Ag-substituted cancrinite-like minerals]
From the amount of Ag-substituted cancrinite-like mineral in the slurry and the amount of Ag-substituted cancrinite-like mineral contained in the deodorized antibacterial paper, the adhesion rate of the Ag-substituted cancrinite-like mineral was determined. The amount of the Ag-substituted cancrinite-like mineral contained in the deodorized antibacterial paper was obtained from the measured amount by measuring the amount of Ag with an ICP emission analyzer after wet decomposing the deodorized antibacterial paper.

〔soft〕
The softness was evaluated by (i) measured values of bulk softness and (b) sensory evaluation. Each measurement / evaluation method is as follows.

(A) Bulk softness The deodorized antibacterial paper is cut into a size of 30 mm in the flow direction and 150 mm in the width direction to obtain five rectangular test pieces. From this test piece, a cylinder with a diameter of 45 mm is formed with the short side direction (30 mm direction) as the height direction. The overlapping width in the circumferential direction of the cylinder is about 9 mm. The upper and lower ends of the overlapped portion are connected to the MAX stapler HD-10D, needle No. Fix with 10-1M. The maximum load when the cylindrical measurement sample obtained in this way is compressed in the direction of the cylinder height is measured by a compression tester, and the value is determined as the value of the bulk softness in the flow direction (MD). To do. The compression tester used was RTA-100 manufactured by Orientec Co., Ltd. The compression speed is 10 mm / mim. The bulk softness in the width direction (CD) is the same as the method for measuring the bulk softness in the flow direction (MD) by cutting the deodorized antibacterial paper into a large 150 mm in the flow direction and 30 mm in the width direction. Measure with

(B) Sensory evaluation A test piece obtained by cutting the deodorized antibacterial paper into a size of 300 mm in the flow direction and 200 mm in the width direction is obtained. This test piece is put in a box so that it cannot be seen, and 10 monitors are touched with the test piece to evaluate the flexibility. The test piece of Comparative Example 1 is used as a reference for flexibility, and the comparative evaluation is performed by setting 4 as the case where it is more flexible than Comparative Example 1, 3 as the same case, 2 when it is hard, and 1 when it is very hard. The case where this average value was 3.5 to 4 was evaluated as ◯, the case where 2.5 to 3.4 was evaluated as Δ, and the case where it was 2.4 or less as ×.

[Dry tensile strength]
The deodorized antibacterial paper was cut into a strip having a width of 25 mm and a length of 100 mm, and then quickly mounted on a universal compression tensile tester (RTM-25 manufactured by Oriental Co.), and the strength at break was measured. The measurement conditions were a tensile speed of 300 mm / min and a test piece gripping interval of 50 mm. Measurements were made in two directions: the paper machine flow direction (MD) and the direction perpendicular to the flow direction (CD).

[Tensile strength when wet]
After immersing the deodorized antibacterial paper of the same size as the test piece used for measuring the tensile strength during drying in a large amount of water for 5 seconds, drain the water for 10 seconds, and then break in the same manner as the tensile strength during drying The strength of was measured.

[Productivity on the round net paper machine]
Continuous production was performed on a round net paper machine, and the state was judged. The case where no trouble such as paper breakage or paper dust occurred during continuous production was evaluated as ◯, the case where trouble occurred occasionally △, and the case where trouble occurred frequently was evaluated as ×.

[Machinability by processing machine]
Using the absorbent pad assembly line (processing machine), the absorbent pad was continuously produced and the state was judged. The case where no trouble such as running out of paper occurred during the transport of the deodorized antibacterial paper and the production was not interrupted was evaluated as ◯, the case where it was interrupted occasionally was evaluated as △, and the case where trouble occurred frequently was evaluated as ×. When the deodorizing antibacterial paper has a dry tensile strength (MD) of 400 cN / 25 mm or less, troubles such as running out of paper may occur during processing.

[Deodorization rate of hydrogen sulfide]
An absorbent pad adjusted to a size of 100 × 100 mm was placed in a conical flask with a stopper with a capacity of 500 ml, and hydrogen sulfide gas whose concentration was adjusted to 3.5 ppm (initial concentration) was injected therein. The hydrogen sulfide concentration in the Erlenmeyer flask after 10 minutes passed was measured with a gas detector tube (manufactured by Gastec Corporation, 4LT for hydrogen sulfide), and the measured value / initial concentration × 100 was defined as the deodorization rate.

[Antimicrobial activity]
Artificial urine mixed with E. coli was injected into the absorbent pad and stored in an environment at 30 ° C. for 24 hours. This absorbent pad was immersed and stirred in an excess amount of physiological saline than its saturated absorption amount. The physiological saline was filtered, and the number of bacteria in the filtrate was measured. About the measured number of bacteria, the antibacterial effect was evaluated according to the following criteria based on Comparative Example 1. -: The growth of bacteria is suppressed as compared with the base. +: Bacteria grow or have the same number as the base.

  As is clear from the results shown in Table 1, the deodorized antibacterial paper of each example (product of the present invention) is soft, has sufficient dry tensile strength, and is productive on a paper testing machine. It can also be seen that there is no problem in workability by the processing machine. In contrast, the deodorized antibacterial paper of Comparative Example 1 is inferior in softness, and it can be seen that trouble may occur in production with a papermaking tester.

It is a perspective view which shows one Embodiment of the deodorizing antibacterial fiber product of this invention. It is a perspective view which shows the state which coat | covered the absorber with the deodorizing antibacterial fiber product shown in FIG. It is sectional drawing of the width direction of the absorption pad produced in the Example and the comparative example.

Explanation of symbols

1 Deodorant antibacterial fiber products 2, 3 Pulp sheet 4 Inner layer sheet

Claims (5)

A deodorant antibacterial fiber product including a cancrinite-like mineral containing a metal having antibacterial properties, clay mineral, flocculant, wet paper strength agent, softwood bleached kraft pulp and hardwood bleached kraft pulp ,
The weight ratio of softwood bleached kraft pulp / hardwood bleached kraft pulp is 95/5 to 50/50,
Containing 0.01 to 20% by weight of the cancrinite-like mineral and 1 to 30% by weight of the clay mineral with respect to the fiber material containing softwood bleached kraft pulp and hardwood bleached kraft pulp,
The fiber material containing softwood bleached kraft pulp and hardwood bleached kraft pulp contains 0.01 to 0.04 wt% of the flocculant and 0.01 to 5 wt% of the wet paper strength agent,
The clay mineral is zeolite;
A deodorant antibacterial fiber product having a Canadian standard freeness (JIS P8121) of 400 to 600 ml of blended pulp of bleached kraft pulp and hardwood bleached kraft pulp . The deodorant antibacterial fiber product according to claim 1 , wherein the cancrinite-like mineral is represented by the following composition formula (1).
_{sM (1) x O y ·} tM (2) 2 O · Al 2 O 3 · uSiO 2 · vR m Q n · wH 2 O (1)
(In the formula, M (1) represents a metal having antibacterial properties, M (2) represents one or more elements selected from the group consisting of Na, K and H, and R represents Na, K, Ca and Mg. Q represents one or more elements selected from the group consisting of: Q represents one or more atomic groups selected from the group consisting of CO ₃ , SO ₄ , NO ₃ , OH and Cl, and s represents 0 <s ≦ 3. , T is 0 ≦ t ≦ 3 (where s + t = 0.5-3), u is 0.5 ≦ u ≦ 6, v is 0 <v ≦ 2, w is w ≧ 0, x is 1 ≦ (x ≦ 2, y satisfies 1 ≦ y ≦ 3, m satisfies 1 ≦ m ≦ 2, and n satisfies 1 ≦ n ≦ 3) The deodorant antibacterial fiber product according to claim 1 or 2 , wherein the deodorized antibacterial fiber product is in the form of a sheet, a fragmented form thereof, a granular shape or a three-dimensional molded product, and is manufactured by a wet method. A laminate sheet in which a pulp sheet is laminated on each surface of a wet papermaking sheet containing the cancrinite-like mineral, and the laminated sheet is free of the wet papermaking sheet over at least one side thereof. The deodorant antibacterial fiber product according to any one of 1 to 3 .   The absorbent article which arrange | positioned the deodorizing antibacterial fiber product of the sheet form between the surface sheet and the absorber, the absorber, or between the absorber and the back sheet.

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