JPH0421283Y2 - - Google Patents

Description

[Detailed explanation of the idea]

a. Field of Industrial Application The present invention relates to shoe insoles, and particularly to novel improvements for obtaining a structure with excellent adsorption and deodorizing properties. b. Prior art Papers with adsorption and deodorizing properties used in this type of shoe insole that have been used in the past include:
Various configurations have been proposed, but these proposals can be roughly divided into paper containing activated carbon, non-woven paper, and paper that has deodorizing properties by impregnating untreated ordinary paper with a chemical deodorant. There are some things that have been added. Typical conventional examples of these are papers containing adsorbent substances, in which pulp is mixed with finely powdered activated carbon as an adsorption medium, and papers containing adsorbent substances (specially (Disclosed in Publication No. 53-6611) have been proposed. c. Problems to be solved by the invention Conventional paper having adsorption and deodorizing properties was constructed as described above, and therefore had various problems as described below. (1) First, paper containing activated carbon becomes black in color.
Although it has excellent adsorption properties for sulfur-based compounds, it has low adsorption properties for ammonia-based compounds, and when used in shoe insoles, it has a short lifespan and needs to be replaced soon. (2) There is also a structure using a nonwoven fabric made of organic fibers, but since it contains a water-absorbing swelling agent, it has excellent water absorption, but it does not have deodorizing properties and is not suitable as a shoe insole. (3) Furthermore, shoe insoles are also used in which multiple magnets are embedded in the surface of a rubber plate to promote blood flow to the soles of the feet, but because the base material is a rubber plate, they have a high adsorption capacity. and almost no deodorizing properties. The present invention was devised to solve the above-mentioned problems, and particularly aims to provide a shoe insole with excellent adsorption and deodorizing properties. d Means for solving the problem The shoe insole according to the present invention uses adsorbent/deodorizing paper containing 20 to 70% sepiolite as the inner core material, and at least the front and back surfaces of the adsorbent/deodorizing paper absorb moisture. It is covered with a mesh sheet made of polyvinyl alcohol, which has a polyvinyl alcohol property. e Effect In the shoe insole according to the present invention, the adsorption/deodorizing paper contains 20 to 70% of the total sepiolite, so the numerous pores in the crystal structure of sepiolite provide excellent adsorption and deodorization. effect can be obtained. Sepiolite is highly effective in deodorizing ammonia, trimethylamine, etc.
Stuffiness and deodorization of shoe insoles can be effectively obtained. In particular, conventionally used chemical deodorants,
For example, the paper used in the present invention coated with the product name Daimushyu (manufactured by Dainichiseika Co., Ltd.) is extremely effective in deodorizing. The reason for this is not fully understood, but it is probably because the chemical deodorant is adsorbed and retained on sepiolite, resulting in some kind of synergistic effect. f. Embodiments Hereinafter, preferred embodiments of the shoe insole according to the present invention will be described in detail with reference to the drawings. What is indicated by the reference numeral 1 in the drawing is an adsorption/deodorization paper as a core material in the shape of a shoe, and the outer surface including the front and back surfaces of this adsorption/deodorization paper 1 is coated with a material made of hygroscopic polyvinyl alcohol. A net sheet 2 is provided to cover it. The adsorption/deodorizing paper 1 is composed of sepiolite, cellulose pulp, etc., and this sepiolite can be roughly divided into two types of occurrence. One of them occurs as an evaporite type deposit, and the other occurs as a secondary ore deposit. Sepiolite, which is produced as a secondary deposit, is
This is a deposit that is secondary crystallization due to movement of silicic acid dissolved in water into cracks and faults in dolomite deposits, and is called Mountain Leather.
They are called Mountain cork, Mountain wood, etc. Known production areas include Spain, Turkey, Nevada in the United States, and Hunan Province in China. The composition of these natural sepiolites varies depending on the region of production, but for example, in the case of Spanish sepiolite,
52-55% _SiO2 , 15-25% MgO, 10% water of crystallization
~12%. In addition, in the case of Chinese products, SiO ₂ is 37-43% and CaO is
12-16%, MgO 17-20%, crystal water 15-20%
It is becoming. Sepiolite, as it is called Mountain Leather, is an extremely flexible mineral, and this property is due to the fact that its crystal structure has tunnels, and water molecules exist in the tunnels between and within the fibers. as crystal water, and SiO ₄
This is thought to be due to the synergistic effect of the inversion of the tetrahedron. Its adsorption performance is due to the above-mentioned tunnel structure and because it has zeolite-like water of crystallization. The pore volume based on tunnels within the crystal is at most about 0.1 ml/g, which is about 250 m ² /g. In particular, the pores around 200 Å are characteristic, and the pore volume is as large as 0.8 ml/g. The pores in this region are called
They are called transitional pores, and unlike micropores, which adsorb gaseous molecules, they have the property of sucking up liquid substances through capillary action with the smallest diameter. This transitional pore part has approximately 700
Since there is no significant change when heated to about ℃, this is considered to be pores caused by voids formed between each fiber. Furthermore, as for the production form of this sepiolite, it is in the form of mud plates made of fibers and powders, so
After mining, processing such as crushing and crushing is required. Next, the characteristics table of processed sepiolite and natural zeolite, which is often used as an adsorbent, is as follows.
It is as shown in Table 1.

[Table] Sepiolite, which is the main component of the paper according to the present invention, can be used in either fibrous or powdered form. In the case of fibrous material, it must be crushed using a turbo mill, hammer mill, etc. to avoid damaging the fibers as much as possible. The fibers are then dissociated and made into flexible fibers. Also, in the case of a powdered material, it is ground into a powder of 100 to 300 meshes using a turbo mill, hammer mill, or the like. This powder can be used as is, but in order to improve its adsorption properties, it is calcined for 20 to 30 minutes in an atmosphere of 500 to 600 °C.
It is more effective to use a product that has been activated after completely removing attached water. Therefore, in reality, cellulose pulp is mixed with the above-mentioned sepiolite powder or fibrous material,
This mixing is performed wet using a paper beater, a pulper, etc., and a general paper machine is used for sheet forming. In this case, the mixing ratio of sepiolite and cellulose is preferably 40 to 400 parts by weight of cellulose pulp to 100 parts by weight of sepiolite,
This is because if cellulose is less than 40 parts by weight, sepiolite will disperse in water and form a highly viscous suspension, which will have a clogging effect on cellulose fibers during the papermaking process. As a result, the aqueous properties are inhibited, and the papermaking speed is extremely reduced or papermaking becomes impossible. Moreover, contrary to the above, when the ratio of cellulose increases to 400 parts or more, the content of sepiolite in the paper decreases, and the adsorptivity becomes extremely low. In addition, in order to compound and strengthen the deodorizing properties of the adsorption/deodorizing paper according to the present invention, a chemical deodorizing agent (for example, an organic acid-based composite manufactured by Dainichiseika Chemical Co., Ltd.) is added to the inside of the paper.
The solution can be applied to the paper by spraying onto the surface or by impregnation. Furthermore, the adsorption/deodorizing paper according to the present invention has excellent properties as a support material for deodorizing agents and aromatic substances, so it can maintain its effectiveness for a long time by post-processing the aromatic agent on the surface. I can do it. Next, a specific example for manufacturing the adsorption/deodorizing paper according to the present invention will be described. Example 1 Sepiolite fibrous material was pulverized and defibrated, and the data shown in Table 2 was obtained as a result of rotor classification sieving test.

[Table] Add 150 parts of cellulose pulp and 2.5 parts of organic binder to 4000 parts of sepiolite fiber.
of water and prepared a homogeneous slurry using a laboratory heater. This was made into paper using a hand-made paper machine and dehydrated and dried to obtain paper with a thickness of 0.8 mm and a density of 0.42 g/cm ³ . Example 2 Powdered sepiolite was calcined for 20 minutes in an atmosphere of 500 to 600°C and ground to a fine powder of 100 to 300 meshes, and 100 parts of this sepiolite was mixed with 230 parts of cellulose pulp and an organic yarn binder.
2.5 parts were mixed with 4000 parts of water and the same procedure as in Example 1 was carried out to obtain paper with a thickness of 0.8 mm and a density of 0.45 g/cm ³ . Example 3 To the composition obtained in Example 2, 5 parts of a chemical deodorant (Dainichiseika Daimushyu, organic acid composite type, powder form) was mixed with a beater, and the same composition as in Example 1 was prepared. Thickness 0.8mm, density 0.45 depending on operation
A paper of g/cm ³ was obtained. Example 4 The paper obtained in Example 2 was impregnated with a 1% solution of a chemical deodorant (Dainichiseika Daimushyu, organic acid composite type, liquid) and dried to obtain a sample containing this chemical deodorant. paper was obtained. In order to understand the deodorizing properties of the paper, characteristic tests for ammonia, trimethylamine, and hydrogen sulfide were conducted using the following method, and a remarkable deodorizing effect was confirmed. Characteristic Test A (Deodorization of Ammonia) As test paper for deodorization, a) the paper obtained in Example 2, b) a chemical deodorizer [trade name Daimushyu (manufactured by Dainichiseika Co., Ltd.)] was applied to commercially available Kent paper. Approximately 250 ml of 1% solution of
c) The paper obtained in Example ² was impregnated with about 300 g/m ² of the chemical deodorant liquid and dried to prepare a paper with a size of 50 x 100 mm each.
The test paper was of the size of After collecting 10μ of 28% ammonia water into a 300ml Erlenmeyer flask and gasifying it completely, put one of the test papers mentioned above, store it at 25℃, and after a specified period of time, use Kitagawa gas. The residual concentration of ammonia in the flask was measured using a detection tube. Characteristic test B (deodorization of trimethylamine) Collect 10μ of a 0.6% trimethylamine aqueous solution into a 300μ capacity Erlenmeyer flask, completely gasify it, then put one of the test papers mentioned above and store it at 25℃. After a predetermined period of time had elapsed, the residual concentration of trimethylamine in the flask was measured using a Kitagawa gas detection tube. Characteristic test C (deodorization of hydrogen sulfide) In a 300 μ capacity Erlenmeyer flask, add 1 ml of 800 ppm sodium hydrogen sulfide aqueous solution and 0.1 N sulfuric acid.
ml to generate hydrogen sulfide, then add one of the test strips mentioned above, store it at 25℃, and after a predetermined period of time, use a Kitagawa gas detection tube to detect hydrogen sulfide in the flask. The residual concentration was measured. The deodorizing results of test strips a), b) and c) for each of the aforementioned chemicals (ammonia, trimethylamine and hydrogen sulfide) are shown in Tables 3 and 4.
As shown in Table and Table 5.

【table】

【table】

[Table] g Effects of the invention Since the shoe insole according to the invention is constructed as described above, the following effects can be obtained. (1) Since it uses crushed and defibrated sepiolite fibrous material, it has countless pores and has sufficient adsorption and deodorizing properties, as well as deodorizing and aromatic properties. It can support chemical deodorants and aromatic substances, and in addition to adsorption and deodorization, it can also have sufficient deodorizing and aromatic effects. (2) Therefore, deterioration of the shoe insole can be prevented, and the adsorption and deodorizing effects can be maintained for a long period of time.

[Brief explanation of drawings]

1 and 2 are a perspective view and a cross-sectional view taken along the line A--A in FIG. 1 to show the shoe insole according to the present invention. 1 is an adsorption/deodorizing paper as a core material, and 2 is a mesh sheet.

Claims (1)

[Scope of utility model registration request] Sepiolite is used as the core material for 20~70% of the total
%, coat or impregnate at least one side of the adsorbent/deodorizing paper with a chemical deodorizer, and cover at least one side of the adsorbent/deodorizing paper with a hygroscopic polyvinyl alcohol net sheet. A shoe insole characterized by being covered.