JP2007020931A - Sanitary material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sanitary material capable of adding high deodorant performance to ammonia, hydrogen sulfide and methyl mercaptan as main components of urine and stool, and simultaneously performing excellent water absorbing property, deodorization, and antibacterial activity by coating an antibacterial agent and a deodorant together. <P>SOLUTION: The sanitary material has a structure coated with amorphous metal silicates or metal silicates and an antibacterial agent on the secondary particle surface of high water-absorbent polymers. Metal silicate powder is agitated and mixed to the high absorbent polymer powder and then dissolved in an organic solvent such as an alcohol or added with a dispersed binder under beating, and then the organic solvent such as the alcohol is dried and removed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to sanitary materials. In more detail, deodorant and water absorption, and hygiene with excellent antibacterial properties characterized by a structure in which the secondary particle surface of the superabsorbent polymer is coated with metal silicate or metal silicate and antibacterial agent Regarding materials.

  Superabsorbent polymers are widely used in sanitary materials such as sanitary products and disposable diapers by taking advantage of their excellent water absorption. However, as a sanitary material, deodorization is also an important need, but superabsorbent polymers have a certain degree of deodorization ability only for ammonia, but hydrogen sulfide, which is abundant in urine and feces, and methyl mercaptan Low effect on sulfurous odors such as

  Therefore, a method in which a superabsorbent polymer is mixed with a deodorant can be considered. At that time, the deodorant is required to be effective not only for ammonia, but also for sulfurous malodors such as hydrogen sulfide and methyl mercaptan, and a level that does not fall off from the opening of the pulp sheet For example, a large particle size. However, the deodorant has a problem that the deodorizing ability is greatly reduced as compared with the powder when the particle size is granulated to about 1 mm which is the minimum particle size that can be produced without dropping from the pulp sheet. In addition, it is difficult to produce a deodorant to a suitable particle size of about 0.2 to 0.5 mm, which is a suitable particle size of a superabsorbent polymer, and when it is made about 1 mm or more that can be produced, both are uniformly mixed. There are also difficult problems.

  The present invention provides the following formula (1)

（但し、式中、Ｍ^２＋はＺｎおよび／またはＣｕ、Ｍ^３＋はＡｌおよび／またはＦｅをそれぞれ示し、ｘ，ｍおよびｎはそれぞれ次の範囲を満足する。０≦ｘ＜０．４，好ましくは０．１≦ｘ≦０．２５，１≦ｍ≦４，０≦ｎ＜１０）で表される金属ケイ酸塩で被覆された構造を特徴とする消臭性と吸水性に優れた衛生材料を提供する。さらには、下記式（２）

(In the formula, M ²⁺ represents Zn and / or Cu, M ³⁺ represents Al and / or Fe, and x, m, and n satisfy the following ranges, respectively, 0 ≦ x <0.4, preferably Is characterized by a structure coated with a metal silicate represented by 0.1 ≦ x ≦ 0.25, 1 ≦ m ≦ 4, 0 ≦ n <10). Provide material. Furthermore, the following formula (2)

（但し、式中、δは格子欠陥を示し、ｘは次の範囲を満足する。０＜ｘ≦０．３、好ましくは０．０５＜ｘ≦０．２）で表される抗菌剤と式（１）の金属ケイ酸塩とで吸水性ポリマー粒子表面を被覆した構造を特徴とする消臭、抗菌、吸水性に優れた衛生材料を提供する。

(Wherein δ represents a lattice defect and x satisfies the following range: 0 <x ≦ 0.3, preferably 0.05 <x ≦ 0.2) and the formula A sanitary material excellent in deodorizing, antibacterial, and water-absorbing characteristics characterized by a structure in which the surface of water-absorbing polymer particles is coated with the metal silicate of (1).

  According to the present invention, high deodorization performance can be imparted to ammonia, hydrogen sulfide, and methyl mercaptan, which are the main components of urine and stool. For example, the product of the present invention in which a superabsorbent polymer is coated with 20% cupric silicate can deodorize 97% of 189 ppm ammonia gas and 100% of 102 ppm hydrogen sulfide gas. Furthermore, by coating together with an antibacterial agent and a deodorant, excellent water absorption, excellent deodorant properties, and antibacterial properties can be exhibited at the same time, which is extremely effective as a sanitary material.

  The highly water-absorbing polymer used in the present invention is a polymer having a characteristic that it is difficult to remove water even when it is subjected to water absorption and pressure at least about 50 times its own weight. The composition includes synthetic polymers such as starch, cellulose, polyacrylic acid, polyvinyl alcohol, polyacrylamide, and polyoxyethylene. Structurally, these water-soluble polymers are crosslinked to form 3 It is a dimensionized product and is appropriately subjected to a hydrophilic treatment. Generally, it is called a highly water-absorbing polymer or a highly water-absorbing resin.

  The product form of the superabsorbent polymer includes powder, film, fiber, etc., but in the present invention, powder is used. The secondary particle size of the powder is not particularly limited, but a hygienic material is preferably about 100 μm to 1000 μm, particularly preferably about 150 μm to 750 μm.

  The deodorant of the formula (1) used in the present invention is an amorphous (amorphous) metal silicate crystal, and as the metal, zinc and / or copper, particularly preferred is its superior deodorant. Because of its high odor ability, it is a composite silicate of zinc and aluminum or copper and aluminum. [Japanese Patent Application No. 2005-044242 by the same inventor as the present inventor] By using the metal silicate of the formula (1), ammonia, trimethylamine can be added to a highly water-absorbing polymer that exhibits deodorant activity effective only for ammonia. Of course, basic odors such as hydrogen sulfide, methyl mercaptan and other sulfur odors, isovaleric acid, acetic acid and other acidic odors, styrene and other aromatic odors, acetaldehyde and other aldehyde odors Excellent deodorizing performance can be added to the bad odor.

  The deodorant of the formula (1) used in the present invention uses powder as the form, and the average secondary particle diameter is preferably 5 μm or less, particularly preferably 2 μm or less.

  The deodorant of the present invention is produced from, for example, water glass (No. 1, No. 2, No. 3 water glass) and water-soluble salts of metals such as zinc, copper, aluminum and iron (chloride, nitrate, sulfate, etc.). The selected metal salt aqueous solution can be coprecipitated (substantially at a pH of 3 or more and 8 or less) with an approximately equivalent amount, and then the water washing, filtration, drying, pulverization, and the like can be appropriately selected and employed.

  The production of the sanitary material according to the invention starts with 1 to 100%, preferably 5 to 50%, particularly preferably 10 to 30% of the deodorant of formula (1) based on the weight of the superabsorbent polymer. The powder and the superabsorbent polymer are mixed uniformly using a stirrer such as a high-speed mixer or a Henschel mixer. Next, under stirring, an organic solvent, preferably a binder to alcohols such as methanol, ethanol, isopropyl alcohol, preferably an organic binder such as cellulose (CMC, HPC, MC, etc.), vinyl acetate, acrylic, etc. After the binder is dissolved or dispersed, it is added. The amount of the binder used is preferably 1 to 20% based on the weight of the deodorant. Thereafter, the organic solvent is removed by drying, and if necessary, fine powders of about 50 to 150 μm or less are removed with a sieve or the like so that the surface of the superabsorbent polymer of the present invention is coated with a highly active deodorant. Sanitary materials can be obtained. The preferred amount of the organic solvent used is 20 to 50% based on the weight of the superabsorbent polymer, and the optimum amount is within the range where the granulated product is not sticky, and the amount with the highest viscosity is a guideline. The state can be understood and the amount of the organic solvent can be determined by the method. Although it is not impossible to use water in place of the organic solvent, the superabsorbent polymer coagulates by absorbing water, and the particles adhere to each other to form coarse particles, which easily causes a problem of deviating from an appropriate size. Moreover, there is a drawback that the cost of removing the absorbed water is higher than that of the organic solvent.

  The range of the preferable secondary particle diameter of the sanitary material of the present invention is about 100 to 1000 μm, particularly preferably about 150 to 750 μm, and these ranges can be adjusted by passing through a sieve.

  The sanitary material of the present invention can impart not only deodorization performance but also antibacterial properties. Various antibacterial agents can be coated on the superabsorbent polymer, but preferably the following formula (2)

（但し、式中、δは格子欠陥を示し、ｘの範囲は次の通りである。０＜ｘ＜０．３、好ましくは０．０５≦ｘ≦０．２）で表される酸化亜鉛系固溶体である。この固溶体の優れた点は、単に抗菌性に優れているだけでなく、イオウ系、脂肪酸等の酸性悪臭に対しても優れた消臭効果を持つ点である。抗菌剤の添加量は、高吸水性ポリマーの重量に基づいて、０．１〜１０％、好ましくは０．５〜５％である。

(Wherein δ represents a lattice defect and the range of x is as follows: 0 <x <0.3, preferably 0.05 ≦ x ≦ 0.2) It is a solid solution. The excellent point of this solid solution is that it not only has excellent antibacterial properties but also has an excellent deodorizing effect against acidic malodors such as sulfur and fatty acids. The addition amount of the antibacterial agent is 0.1 to 10%, preferably 0.5 to 5%, based on the weight of the superabsorbent polymer.

  Hereinafter, the present invention will be described specifically by way of examples.

Starch / polyacrylate-based superabsorbent polymer (manufactured by Sanyo Chemicals, trade name: Sunwet, particle size distribution: 150 μm or less = 0.5%, 250-500 μm = 10.9%, 250-500 μm = 65%, 500 ˜710 μm = 23.6%) 50 g and amorphous cupric aluminum silicate hydrate of the following composition and physical properties produced by the following method: (Cu _0.76 Al _0.16 ) O. 3.1 SiO ₂ .nH ₂ O [BET specific surface area = 302 m ² / g, 50% cumulative average secondary particle size = 1.4 μm] 10 g was put into a 300 ml beaker, stirred for about 2 minutes with a chemistor, mixed, 16 ml of ethanol solution in which 0.5 g of hydroxypropylcellulose was dissolved was added little by little, and stirring was continued for about 5 minutes. The granulated sample was taken out, dried in an oven at about 80 ° C. for 30 minutes, and then passed through a 150 μm sieve to remove fine particles. The obtained granulated product was subjected to a water absorption test and a deodorization test.

No. 3 water glass aqueous solution of 0.5 mol / liter in terms of Na ₂ O, mixed aqueous solution of aluminum sulfate and cupric sulfate (Al ³⁺ = 0.08 mol / liter, Cu ²⁺ = 0.38 mol / liter) With a metering pump at a flow rate of about 100 ml / min and 100 ml / min, respectively, 1 liter of water is previously added to a reaction vessel with a capacity of 5 liters and continuously supplied, and the reaction pH ranges from about 5.5 to 6.0. The flow rate of water glass was finely adjusted and controlled, and the reaction temperature was kept at about 30 to 35 ° C., and the reaction was continued until it reached about 5 liters. The reaction product was filtered, washed with water, dried in an electric oven at 120 ° C. for 12 hours, and then pulverized with an atomizer.

  Water absorption test: 0.1 g of a sample is put in a commercially available tea bag (weight is about 0.385 g), impregnated with water (about 26 ° C.), absorbed for 10 minutes, taken out, and attached to the tea bag. The water was wiped off with a tissue and the weight was measured. A tea bag without a sample was treated in the same manner, and the weight was measured. This value was used as a blank, and was subtracted from the amount of water absorbed when the sample was added.

  Deodorizing power test: 0.1 g of sample was placed in a 1 liter vacuum gas collection bottle, evacuated with an aspirator for 5 minutes, ammonia gas was introduced from a gas cylinder adjusted to an ammonia concentration of 195 ppm, the cock was closed, After 5 minutes, the remaining ammonia concentration was measured using a gas detector tube. Hydrogen sulfide and methyl mercaptan were also measured by the same method. The results are shown in Table 2. The concentrations of hydrogen sulfide and methylcaptan used are 105 ppm and 210 ppm, respectively.

  In Example 1, the same operation was performed except that the amount of the deodorant was changed from 10 g (20% with respect to the water-absorbing polymer) to 5 g (10% with respect to the water-absorbing polymer). Tables 1 and 2 show the results of the measured water absorption test and deodorization test.

In Example 1, the same operation was performed except that the deodorant was changed to the following substance. Chemical composition of deodorant: {(Zn) _0.7 Al _0.2 } O.3.2SiO ₂ .nH ₂ O [BET specific surface area = 278 m ² / g, 50% cumulative average secondary particle size = 0. 72 μm]. The deodorant was produced in the same manner as in Example 1 except that the metal solution was zinc chloride and aluminum sulfate (Zn = 0.35 mol / liter, Al = 0.1 mol / liter), and the reaction pH was about 5.6-6. Except for changing to 0.0, the same procedure as in Example 1 was performed. Tables 1 and 2 show the water absorption and deodorant test results.

In a beaker having a capacity of 300 ml, 50 g of the superabsorbent polymer used in Example 1, cupric silicate: CuO.3.2SiO ₂ .nH ₂ O [BET specific surface area = 296 m ² / g, After adding 5 g of 50% cumulative average secondary particle size = 1.4 μm], 15 ml of methanol in which 1 g of carboxymethylcellulose sodium salt was dissolved was added with stirring, and granulated by stirring for about 7 minutes. The granulated product was taken out, put in an oven, dried at 80 ° C. for 1 hour, and then passed through a 100 μm sieve to remove fine powder. Tables 1 and 2 show the water absorption and deodorization test results for this product. Production of the deodorant was carried out in the same manner as in Example 1 except that the metal solution was changed to a 0.5 mol / liter cupric sulfate aqueous solution and the reaction pH was changed to about 5.7 to 6.0. The same was done.
[Comparative Example 1]

Tables 1 and 2 show the results of measuring the water absorption and deodorizing power of the highly water-absorbing polymer used in Example 1.
[Comparative Example 2]

  The deodorant used in Example 1 was kneaded with water in which 5% by weight of carboxymethylcellulose sodium salt was dissolved using a kneader and then granulated using an extruder having a diameter of 1.2 mm. Table 2 shows the results of a deodorizing power test using a 2 mm granulated product (0.02 g corresponding to a weight of 20% with respect to the water-absorbing polymer).

表１から、本発明品の吸水力は高吸水性ポリマーの能力を保持しており、したがって、高性能である。

From Table 1, the water-absorbing power of the product of the present invention retains the ability of a highly water-absorbing polymer, and therefore has high performance.

表２から、本発明品は、高吸水性ポリマーより極めて優れた消臭力を示すことが判る。

From Table 2, it can be seen that the product of the present invention exhibits a deodorizing power much superior to that of the superabsorbent polymer.

In Example 1, in the step of coating the secondary particle surface of the superabsorbent polymer with a deodorant, the chemical composition: Zn _0.8 Al _0.2-δ O [BET specific surface area = 45 m ² / g, 50% Zinc oxide having a cumulative average secondary particle size = 0.7 μm], an aluminum-based solid solution [Japanese Patent No. 3465248, the invention of the present inventors, Japanese Patent Laid-open No. Hei 8-291101] other than using 2 g of deodorant Was carried out in the same manner as in Example 1. After adding 100 times weight of water to the obtained coating, E. coli or Staphylococcus aureus was inoculated and stored at 35 ± 1 ° C. for 24 hours, and the number of bacteria before and after storage was measured. Table 3 shows the results of comparing the same test by adding bacteria to water alone.

表３から、本発明品は抗菌性が高いことが判る。

From Table 3, it can be seen that the product of the present invention has high antibacterial properties.

Claims (4)

The following formula (1) wherein the secondary particle surface of the superabsorbent polymer is 1 to 50% by weight of the superabsorbent polymer weight

(In the formula, M ²⁺ represents Zn and / or Cu, M ³⁺ represents Al and / or Fe, and x, m, and n satisfy the following ranges, respectively: 0 ≦ x <0.4,1 A hygienic material excellent in deodorizing property and water absorption, characterized by a structure coated with a metal silicate represented by ≦ m ≦ 4, 0 ≦ n <10). The sanitary material according to claim 1, wherein M ³⁺ of the metal silicate of formula (1) is Al and the range of x is 0.05 ≦ x ≦ 0.25. Following formula (2)

(In the formula, δ represents a lattice defect, and x satisfies the following range: 0 <x ≦ 0.3). The antibacterial agent represented by 0.1 to 10% by weight of the superabsorbent polymer weight The hygienic material according to claim 1, wherein the secondary particle surface of the superabsorbent polymer is coated with the metal silicate represented by the formula (1) in an amount of After stirring and mixing the metal silicate powder represented by the formula (1) with the superabsorbent polymer powder, a binder dissolved or dispersed in an organic solvent such as alcohol is added with stirring, and then organic such as alcohol is added. The method for producing a sanitary material according to claim 1, wherein the solvent is removed by drying.