WO2004089092A1 - Deodorant antibacterial powder preparation, process for producing the same and product using the powder preparation - Google Patents

Abstract

A deodorant antibacterial powder preparation of 1 to 40 μm average particle diameter produced by hydrating calcium oxide obtained by firing seashells; a deodorant antibacterial powder preparation comprising 5 to 95 mass% of the above powder and 95 to 5 mass% of tea powder or powder of used tea leaves having an average particle diameter of 1 to 40 μm; or a deodorant antibacterial powder preparation comprising 5 to 95 mass% of calcium hydroxide powder of 1 to 40 μm average particle diameter and 95 to 5 mass% of tea powder or powder of used tea leaves having an average particle diameter of 1 to 40 μm. These deodorant antibacterial powder preparations can exert striking deodorant antibacterial effects against various odors and bacteria and can find advantageous application in a wide spectrum of fields.

Description

 Description Deodorant and antibacterial powder formulation, manufacturing method and product using this powder formulation

 The present invention relates to a deodorant / antibacterial powder preparation having a high-performance deodorant and antibacterial effect against various odors and various bacteria, a method for producing the same, and a product using the powder preparation. Background art

 In recent years, new building materials, furniture, wallpaper, leather for automobiles, textile products, food packaging materials, feed bags and household goods using synthetic resins have become widespread. However, in such new building materials and furniture, volatile substances such as formaldehyde generated from the new building materials and furniture itself or adhesives and paints have recently become a major problem as a cause of sick house syndrome. Therefore, reduction of volatile substances such as formaldehyde is demanded. Also, from the viewpoint of comfort, antibacterial agents that exhibit antibacterial properties against various bacteria represented by pathogenic Escherichia coli O-157 and are safe in use are desired. On the other hand, in the field of food packaging materials and feed bags, thermoplastic films are widely used.However, from the viewpoint of the preservation of the contents, antibacterial agents that are safe and exhibit antibacterial and antifungal properties are strong. It has been demanded. There is also a need for a household deodorant that is effective in deodorizing toilet odors and cigarette odors.

As a safe deodorant / antibacterial agent, one using shells has been proposed. For example, a deodorant containing calcium carbonate powder obtained by crushing shells (for example, see Japanese Patent Application Laid-Open No. 2000-1-1) No. 4,569,932), an antibacterial agent containing scallop shell powder (for example, see Japanese Patent Application Laid-Open No. 2001-198983), scallop Bacterial inhibitors (see, for example, Japanese Patent Application Laid-Open No. 2002-2555714) have been proposed which are obtained by baking crushed shells. However, both the deodorant performance and antibacterial performance were not sufficient. Disclosure of the invention

 The present invention has been made in view of the above circumstances, and provides a deodorant and antibacterial powder which has a high-performance deodorant and antibacterial effect against various odors and various bacteria and can be used in a wide range of fields. It is intended for that purpose.

 The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, obtained as a hydrate of calcium oxide obtained by calcining a shell, having a specific average particle size. Calcium hydrate powder was found to be effective in deodorizing and antibacterial. The present invention has been completed based on such findings.

 That is, the gist of the present invention is as follows.

 (1) A deodorant and antibacterial powder preparation having an average particle size of 1 to 40 μm, obtained by hydrating calcium oxide obtained by baking shells.

 (2) A deodorant / antibacterial powder preparation comprising 5 to 95% by mass of the powder of (1) and 95 to 5% by mass of a tea powder or a tea husk powder having an average particle size of 1 to 40 μm.

 (3) Deodorant consisting of 5 to 95% by mass of calcium hydroxide powder having an average particle size of 1 to 40m and 95 to 5% by mass of tea powder or tea husk powder having an average particle size of 1 to 40μm Powder formulation.

(4) A method for producing calcium oxide by calcination of a shell at 800 to 1300 ° C. and hydrating the calcium oxide to produce a deodorant / antibacterial powder formulation. to 0. 1 5 mass _^0/0 solution p H are provided methods for producing the deodorant antimicrobial powder preparation characterized by hydrating to so that Do and 9-1 3.

(5) In the production method of the above (4), the calcined product obtained by calcining the shell is pulverized so as to have a particle size of 100 μm or less. A method for producing a deodorant / antibacterial powder formulation, characterized by adding 0.2 to 1 liter of calcium oxide to hydrate it.

 (6) A synthetic resin composition comprising 0.1 to 30% by mass of the deodorant / antibacterial powder preparation according to any one of the above (1) to (3).

 (7) Deodorant of any of the above (1) to (3) · Deodorant surface treated with a surface treatment agent containing an antibacterial powder formulation · Antibacterial leather, deodorant · Antibacterial powder Deodorant and antibacterial leather with a formulation content of 1 to 30% by mass based on the dry weight of the surface treatment agent.

 (8) A paint comprising 0.1 to 35% by mass of the deodorant / antibacterial powder unprepared product of any of the above (1) to (3) on a dry mass basis.

 (9) A fiber treating agent comprising the deodorant / antibacterial powder preparation of any of the above (1) to (3) in an amount of 1 to 80% by mass on a dry mass basis.

 (10) Deodorant according to any of the above (1) to (3) · Deodorant treated with a treating agent containing an antibacterial powder preparation · Antibacterial fiber, deodorant · Antibacterial powder preparation Deodorant and antibacterial fiber with a blending amount of 1 to 70% by mass based on the dry weight of the treating agent.

 (11) A deodorant and antibacterial film comprising the synthetic resin composition of the above (6). (1 2) A deodorant / antibacterial foaming material obtained by foaming the synthetic resin composition of (6).

(13) The deodorant and antibacterial herbicidal sheet _c comprising the synthetic resin composition of (6) above (14) The deodorant and antibacterial powder preparation of any of (1) to (3) above A nonwoven fabric made of a thermoplastic resin composition containing a deodorant having an average particle size of 1 to 10 μπι and an antibacterial powder formulation of 0.5 to 20% by mass.

(1 5) Average particle calcium hydrate powder oxidation of diameter 3 to 20 mu m, formed by back treating fibers with a dry weight 1~5 0 g / m ² against the fiber deodorant antibacterial properties Imparted fiber. (16) A car seat or a car ceiling material formed of the deodorant / antibacterial property imparting fiber according to (10) or (15).

 (1) Deodorant described in any of (1) to (3) above · Antibacterial powder formulation and deodorant consisting of calcium oxide hydrate powder having an average particle size of 1 to 40 µm · Antibacterial Plywood comprising a mixed powder formulation. BEST MODE FOR CARRYING OUT THE INVENTION

 Examples of the shell used in the deodorant / antibacterial powder preparation of the present invention include shells such as scallop, clam, clam, oyster, turtle, abalone and mussel. Of these, scallop and oyster shells, which are industrially processed at a high rate, are preferred because they are easily available, and furthermore, they have a low impurity content and can effectively use a large amount of waste. Therefore, scallop shells are preferred. Calcium oxide obtained by sintering shells contains trace metals such as zinc, iron, and magnesium, and thus is suitable for imparting antibacterial properties.

 The shell is baked at 800 to 130 ° C for 3 to 6 hours after washing the shell with water. After firing, remove fine sand etc. from the fired product and add water to hydrate calcium oxide. After hydration, the precipitate is cooled to about 5 to 40 ° C to obtain a precipitate.The precipitate is separated by a centrifuge or a filter, and the obtained precipitate is dried and classified. A calcium oxide hydrate having a predetermined average particle size is obtained.

It is important to perform the above calcination at a high temperature from the viewpoint of improving the deodorizing and antibacterial performance of the obtained calcium oxide, and if the calcination temperature is less than 800 ° C, the calcination will not be performed sufficiently. Deodorization · Antibacterial performance may decrease. Baking at a temperature exceeding 130 ° C does not improve deodorant / antibacterial performance, but only wastes energy. The firing conditions are good Best is 900 to 1200 ° 0 for 3 to 5 hours. The calcined product is preferably ground to a particle size of 100 μm or less after removing sand and the like. For the pulverization, a pole mill, a jet mill or the like can be used. Further, it is preferable that the amount of water added during the hydration be 0.2 to 1 liter per 1 kg of the fired product.

 The calcium oxide hydrate obtained by the above-mentioned calcination and hydration has a pH of 0.05 to 0.15 mass% aqueous solution of 9 to 13, preferably 10 to 13; High deodorant · Important for showing antibacterial performance. For example, when using scallop shells, the fired product obtained by firing at a temperature of 800 to 1300 ° C is ground to a particle diameter of 100 Atm or less, and water is added to 1 kg of the ground material for 0 kg. By hydrating by adding at a rate of 2 to 1 liter and setting the cooling temperature after hydration to 5 to 40 ° C., calcium oxide hydrate having the above pH can be obtained.

 In the present invention, the calcium oxide hydrate powder needs to have an average particle size of 1 to 40 m. Although it depends on the use, it is usually preferably 2 to 30 m, more preferably 3 to 20 zm, and still more preferably 5 to 15 μm. When the average particle size is less than 1 m, the calcium oxide hydrate powder is liable to agglomerate, making it difficult to handle, and difficult to pulverize to less than 1 zm. If the average particle size exceeds 40 μm, the surface area of the calcium oxide hydrate powder becomes small, so that deodorizing and antibacterial performance is not exhibited, and those having a particle size significantly exceeding 40 μπι are included. As a result, it becomes a foreign substance during mixing.

 The average particle size of the calcium oxide hydrate powder can be adjusted by adjusting the milling time of a ball mill or the milling pressure and milling time by a jet mill.

In the present invention, calcium oxide hydrate powder, tea powder or tea husk powder It is preferable to mix the compounds because the range of substances to be deodorized and antibacterial is expanded. Specifically, not only formaldehyde, which causes so-called sick houses, but also household odors such as ammonia and acetic acid odors and tobacco odors can be deodorized.

 Examples of the tea include various teas such as green tea, oolong tea, black tea, barley tea, and Poor tea. Green tea, black tea, and oolong tea are preferable because of their excellent deodorant and antibacterial properties. One type of tea may be used alone, or two or more types may be used in combination. Further, tea powder and tea husk powder which may be used as a mixture may be obtained by drying tea or tea husk and then pulverizing the mixture with a bowl mill / jet mill. These powders preferably have an average particle size of 1 to 40 μπι, and preferably 5 to 35 μπι from the viewpoint of improving dispersibility, deodorization and antibacterial performance. The adjustment of the average particle size of the tea powder or the tea husk powder can be performed in the same manner as the adjustment of the average particle size of the calcium oxide hydrate powder.

The use ratio of the calcium oxide hydrate powder and the tea powder or the tea husk powder is preferably 5 to 95% by mass of the calcium oxide hydrate powder and 95 to 5% by mass of the tea powder or the tea husk powder. This usage rate is adjusted according to the odor to be deodorized and the type of bacteria to be antibacterial. For example, for acidic odors such as formaldehyde, acetic acid, and hydrogen sulfide, it is effective to increase the use ratio of calcium oxide hydrate powder, and vice versa for other odors. In addition, in applications where it is desired to avoid coloring, it is preferable to reduce the use ratio of tea powder or tea husk powder, but if it is less than 5% by mass, the deodorizing effect against ammonia odor and tobacco odor is not sufficient. Further, when the use ratio of the tea powder or the tea husk powder exceeds 95% by mass, the deodorizing effect on formaldehyde-acetic acid decreases. Regarding the antibacterial performance, tea powder or tea husk powder shows antibacterial activity against a wide range of bacteria such as Bacillus subtilis, Staphylococcus aureus and Escherichia coli, but Staphylococcus aureus and E. coli For enterobacteria, it is effective to increase the proportion of calcium oxide hydrate powder used.

 Instead of mixing with the above-mentioned calcium oxide hydrate powder, the above-mentioned tea powder or tea husk powder can also be mixed with an industrially produced calcium hydroxide powder. The average particle size of the calcium hydroxide powder needs to be 1 to 40 μm, similarly to the average particle size of the calcium oxide hydrate powder. Although it varies depending on the application, it is usually preferably 2 to 30 μπι, more preferably 3 to 20 μm, and still more preferably 5 to 15 μπι. The proportion of calcium hydroxide powder and tea powder or tea husk powder used is the same as the proportion of calcium oxide hydrate powder and tea powder or tea husk powder used. Can be adjusted.

 The deodorant / antibacterial powder preparation of the present invention, namely, calcium oxide hydrate powder, mixed powder of calcium oxide hydrate powder and tea powder or tea husk powder, and calcium hydroxide hydrate and tea powder or tea husk powder By mixing the mixed powder with the synthetic resin, it can be used for deodorizing and antibacterial in various products formed of the synthetic resin. In this case, the compounding ratio of the deodorant / antibacterial powder preparation is preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, and even more preferably 0.5 to 10% by mass. If the content is less than 0.1% by mass, deodorizing and sterilizing effects cannot be expected. If the content exceeds 30% by mass, the skin may be adversely affected.

The synthetic resin only needs to be one that is not poor in alkali resistance. When used for food packaging bags, feed bags, etc., polyethylene, polypropylene, PVC (polyvinyl chloride), polyvinylidene chloride, etc. may be used. For the wallpaper, polyvinyl chloride and soft polyolefin are preferably used. In the case of food packaging bags, breeding bags and wallpaper, a film-like one is used, and the thickness varies depending on the application, but is preferably 15 to 100 μm. Injection molded products include not only polyolefin-based resins such as polyethylene and polypropylene, but also styrene-based resins such as ABS (acrylonitrile-butadiene styrene) resin and polystyrene resin, and heat-resistant materials such as polyacrylonitrile resin and polyphenylene sulfide resin. A plastic resin is preferably used. In the case of molding methods other than injection molding, thermoplastic cured resins such as phenolic resin, melamine resin, epoxy resin and urea resin are used. Further, a thermoplastic elastomer such as an ethylene-propylene copolymer or a styrene-butadiene copolymer can also be used.

 When the deodorant / antibacterial powder preparation of the present invention is used as a deodorant / antibacterial fiber treatment agent for fiber products such as polyester fiber, rayon fiber, ataryl fiber and polypropylene fiber, it should be blended with a backing agent. Is preferred in terms of ease of use. In particular, it is suitably used as a deodorant for car sheets, furniture sheets, and carpets. As a base of the treatment agent, acryl-based resin, synthetic rubber latex, or the like can be used. The treating agent is a mixture of this base and a deodorant / antibacterial powder formulation.

 The amount of the deodorant / antibacterial powder formulation in the treating agent is preferably 1 to 80% by mass, more preferably 5 to 65% by mass, based on the dry mass of the treating agent. If the amount is less than 1% by mass, the deodorizing and antibacterial effect is poor. If it exceeds 80% by mass, the treating agent becomes hard when compounding the antibacterial powder formulation, and the texture of the fiber product is increased. Will be impaired. The average particle size of the deodorant / antibacterial powder preparation needs to be 1 to 40 m, preferably 2 to 30 m, more preferably 3 to 20 μπι, and still more preferably 5 to 40 μπι. ~ 15 μπι.

The amount used as a back treatment agent depends on the required characteristics, but is preferably 1 to 50 g Zm ^{2 in} terms of dry mass, more preferably 5 to 30 g / m ² . If the amount is less than 1 g / m ² , the deodorizing performance is not sufficient, and if it exceeds 50 g / m ² , the fiber may become hard and the cost increases. The treating agent can be widely used as a treating agent for nonwoven fabrics made of a thermoplastic resin composition containing polyethylene, polypropylene, rayon, nylon, vinyl, polyester and the like.

 When the deodorant / antibacterial powder preparation of the present invention is used as a deodorant for leather (antibacterial agent), the deodorant / antibacterial powder preparation is mixed with a polyurethane resin or the like to form a surface treatment agent, What is necessary is just to apply by a one coater or a roll coater. Examples of the leather include PVC leather, polyurethane leather, thermoplastic thermoplastic elastomer leather, and natural leather. Other than the natural leather, the skin layer is formed on the base layer, and examples of the material forming the base layer include PVC, urethane, and olefin-based thermoplastic elastomers. In order to improve the deodorant / antibacterial effect, the substrate layer may also contain a deodorant / antibacterial powder preparation. Deodorization in surface treatment agents

• The amount of the antibacterial powder formulation is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, based on the dry mass of the surface treating agent. If the amount is less than 1% by mass, the deodorizing and antibacterial effects are poor, and if it exceeds 30% by mass, the physical properties of the epidermal layer deteriorate.

The deodorant / antibacterial powder formulation of the present invention mixed with a soft urethane foam used as a cushioning material for various chairs, sofas and automobile seats is suitably used as a deodorant / antibacterial cushioning material. In addition to the above-mentioned flexible urethane foam, a foamed material obtained by foaming a polyolefin resin such as a thermoplastic polyolefin such as polyethylene or polypropylene, a polystyrene resin, or a hard urethane is used as a heat insulating material for household goods and buildings. used. The deodorant / antibacterial powder formulation of the cushioning material / foaming material is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, based on the dry weight of the cushioning material / foaming material. . When the amount is less than 1% by mass, deodorizing and antibacterial effects are poor, and when the amount exceeds 30% by mass, cushioning properties and heat insulating properties are reduced. I do. The foam material can be manufactured by a known method.

 The deodorant / antibacterial powder preparation of the present invention can also be blended into a herbicidal sheet. C The deodorant / antibacterial herbicidal sheet is made of the same material as the above-described food packaging bag and the like. A film containing an antimicrobial powder formulation (thickness is not limited, but preferably about 20 to 50 / im) is cut into a yarn and knitted, and manufactured by a known method be able to. Deodorant and antibacterial weed control sheet is suitable for applications such as shores of farmland, open fields, and underlaying of pots. Further, the deodorant / antibacterial herbicidal sheet may be a nonwoven fabric made of polypropylene or the like and a deodorant / antibacterial powder formulation mixed therein.

 Applications of the deodorant / antibacterial powder formulation of the present invention include building materials, automobile-related applications, and household products.Specifically, as building materials, tatami upholstery, tatami core, waterproof and moistureproof Used in films, glass protective films, plywood, decorative plywood, particle boards, fiber boards, chipboards, glulam, panels, bran, shoji paper, etc., or used as a finishing material for flooring be able to. Automotive applications include ceiling materials, interior paints, and air conditioner filters. Household products include cushion canes, cushioning materials, curtains, tape-no-cloths, and various types of bedding.

Further, the deodorant antimicrobial powder formulations of the present invention, those combined distribution in flooring wax, and _c can be suitably used as a deodorant antimicrobial wax, deodorant antimicrobial powder of the present invention Formulations include deodorant and antibacterial paint, especially antibacterial

It can be suitably used by blending it with paint for OA equipment, paint for household appliances, paint for furniture, and the like.

Paints, solvent-based榭脂and aqueous resin, the deodorant antimicrobial powder formulations of the present invention, 0.1 to 3 5 can be obtained by mass% compounded _c In this case a dry weight basis, deodorant Antibacterial powder preparations should have an average particle size in the range of 1 to 40 μπι However, the average particle diameter is preferably 1 to 20 μπι, more preferably 3 to 15 m. If the average particle size is less than 1 m, the powder is likely to agglomerate, and if it exceeds 40 / im, the coating film tends to have irregularities. Further, the maximum particle size is preferably 50 m or less in order to obtain a smooth surface.

 Examples of the solvent-based resin include acryl resin, urethane resin, alkyd resin and amino resin, and these may be used alone or in a combination of two or more. . Examples of the water-based resin include vinyl acetate-based emulsion, acrylic-based emulsion, urethane-based emulsion, water-soluble acrylic resin, water-soluble urethane resin, water-soluble epoxy resin, and water-soluble alkyd resin. Or two or more of them may be used in combination. .

 The objects to be coated with these paints include metal, glass, resin, paper, ceramics and wood, and can be arbitrarily selected.

 The coating method includes brush coating, spray coating, electrostatic coating, powder coating, and the like, and can be selected as appropriate. These paints are provided with antibacterial properties and deodorant properties without impairing the physical properties of ordinary paints.

 As described above, the deodorant / antibacterial nonwoven fabric can be obtained by adding a deodorant / antibacterial powder formulation by a usual method at the stage of spinning the raw material fibers of the nonwoven fabric, in addition to the method using the fiber treatment material. it can. The amount of the deodorant / antibacterial powder formulation should be 0.5 to 20% by mass from the viewpoints of deodorant / antibacterial effect and moldability. The method for producing the nonwoven fabric is not particularly limited, and the nonwoven fabric can be produced by a known method such as a dry method or a wet method. Specific examples of the production method include a mechanical joining method such as entanglement of fibers using a needle punch machine or sewing using a thread, and an adhesion method using heat, pressure, or a binder.

In this case, the deodorant and antibacterial powder formulation is extruded as fine fibers. The average particle size is preferably from 1 to 10 μm, and more preferably from 2 to 5 μηι. If the average particle size is less than 1 μπι, the powder tends to agglomerate, which causes a problem in processing. When the average particle size exceeds 10 m, the yarn is easily cut at the time of spinning, and it is difficult to obtain fine fibers.

 As a raw material fiber of the nonwoven fabric, polyethylene, polypropylene, nylon, and the like are preferably used, but are not particularly limited as long as the raw material can be mixed with a deodorant / antibacterial powder preparation. Example

 Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1

 After washing the scallop shell with water, it was baked at 110 ° C. for 4 hours, and fine sand was removed using a mesh size 5 mm sieve to obtain a baked product lkg. To this was added 0.5 liters of water to hydrate the calcium oxide, cooled to 25 ° C, the precipitate was separated using a suction filter, and the separated product was dried at 120 ° C for 5 minutes. Let dry over time. The dried product was classified by an air separator to obtain a calcium oxide hydrate powder (deodorant, antibacterial powder formulation) having an average particle size of 9 / m.

1 mass _^0/0 formaldehyde aqueous solution in an Erlenmeyer flask having an inner volume of 3 00 millimeter Li Tsu Torr placed 1.5 microliters, p H in the calcium hydrate powder oxide 0. 05 g (1 gZ liter aqueous solution 1 2.5) was added and left at .24¾ for 120 minutes, and the formaldehyde concentration in the flask was measured with a Kitagawa detector. Further, an anti-mold test was performed by the method described below. Table 1 shows the results.

Example 2

Green tea leaves are dried to a moisture content of 0.5% by mass. And coarsely pulverized with a ball mill and jet mill.

30 m tea powder was obtained. A deodorant / antibacterial mixed powder formulation obtained by mixing 50% by mass of this tea powder and 50% by mass of the calcium oxide hydrate powder obtained in Example 1 (pH at 1 g / liter aqueous solution is 1%). 1) The formaldehyde concentration was measured in the same manner as in Example 1 using 0.05 g. In addition, antifungal tests were conducted. Table 1 shows the results.

Example 3

 The same procedure as in Example 2 was repeated except that calcium hydroxide having an average particle size of 4 μm (pH in a 1 g Z-liter aqueous solution was 11) was used in place of the calcium oxide hydrate powder. An odor / antibacterial mixed powder preparation was obtained, and the formaldehyde concentration was measured in the same manner. In addition, an antifungal test was performed. Table 1 shows the results.

Example 4

 The deodorant and antibacterial mixed powder preparation obtained in Example 2 was mixed with a polycarbonate resin (Dainichi Seika Kogyo Co., Ltd., Rezamin D6205) to prepare a deodorant-antibacterial surface treatment agent. . The blending amount of the mixed powder preparation was 20% by mass based on the dry mass of the surface treating agent. On a surface of a PVC leather having a soft polyvinyl chloride layer formed on a plain fabric of a blended fiber of 65% by mass of polyester fiber and 35% by mass of rayon fiber, the above surface was coated with a bar coater. The treating agent was applied and dried to obtain a deodorant / antibacterial treated leather having a surface treatment layer having a thickness of about 10 μm. A sample of 5 cm × 5 cm was cut out from this leather, and the formaldehyde concentration was measured in the same manner as in Example 1. Table 1 shows the results.

Example 5

The deodorant / antibacterial mixed powder preparation obtained in Example 3 was blended with Acryl Margeillon (Crosslen, manufactured by Ganz Kasei Co., Ltd.) to prepare a fiber treatment agent. The blending amount of the mixed powder preparation was 15% by mass based on the dry mass of the fiber treatment agent. The above fiber treating agent was laminated on a polyester base fabric by a roll coater and dried to obtain a sheet having a fiber treating agent layer (backing material) having a thickness of about 100 μηι. A sample of 5 cm × 5 cm was cut out from this sheet, and the formaldehyde concentration was measured in the same manner as in Example 1. Table 1 shows the results.

Example 6

 5 cm x 5 cm sample cut from the deodorant / antibacterial leather prepared in Example 4 and 5 microliters of 4 mass% ammonia aqueous solution

After placing it in a 300 milliliter Erlenmeyer flask and leaving it at 25 ° C for 120 minutes, the ammonia concentration in the flask was measured with a Kitagawa detector.

It was 145 mass ppm.

Example 7

 1 part by mass of the calcium oxide hydrate powder obtained in Example 1 and a linear low-density polyethylene (Idemitsu Petrochemical Co., Ltd., I DEM I TSULL 0 13 4, melt flow rate: 1.2) (gZlO component) was mixed with 99 parts by mass and then kneaded at 200 ° C with a kneading twin-screw extruder (kneading unit = 40 mmφ) to obtain a resin composition. This resin composition was subjected to inflation formation using an extruder (extrusion unit = 50 mmφ) to produce an inflation film having a width of 60 mm and a thickness of 40 μm. A sample of 5 cm × 5 cm was cut out from this film, and the formaldehyde concentration was measured in the same manner as in Example 1.

Example 8

The calcium oxide hydrate powder obtained in Example 1 was mixed with a solvent-based urethane-fat solution in an amount of 5% by mass on a dry mass basis to prepare a paint. Next, this paint was spray-painted on an ABS (acrylonitrile-butadiene-styrene) plate with a thickness of 2 mm using a spray gun (manufactured by Iwata Paint Co., Ltd.). Cut out a 5 cm x 5 cm sample from this ABS plate and run W 200 The formaldehyde concentration was measured as in Example 1. Table 1 shows the results.

Example 9

 The calcium oxide hydrate powder, the polyol component, the isocyanate component, the blowing agent, the catalyst and the foam stabilizer obtained in Example 1 were blended in the proportions shown below, and the calcium oxide hydrate powder was obtained by a conventional method.・ An antibacterial urethane foam containing 5% by mass was prepared. A sample of 5 cm × 5 cm × 5 cm was cut out from this urethane foam, and the formaldehyde concentration was measured in the same manner as in Example 1. Table 1 shows the results. Ingredients>

Polyol (manufactured by Dow Poly Urethane Co., # 300 000) 100 parts by mass Isocyanate (manufactured by Dow Poly Urethane Co., T-80) 40 parts by mass Blowing agent (water) 2.9 parts by mass Amine-based catalyst (manufactured by Air Products) , 33 LV) 3 parts by mass Amine-based catalyst (AT33, manufactured by Air Products) 3 parts by mass Tin-based catalyst (Nichito Kasei, T-1 9) 3 parts by mass L 6 202) 3 parts by mass Calcium oxide hydrate powder 8 parts by mass Example 10

The calcium oxide hydrate powder obtained in Example 1 was classified to obtain a powder having an average particle size of 3 μm, which was blended with a polypropylene resin (Ml = 50 g // 10 minutes), calcium hydrate oxide powder to obtain a master one batch containing 40 weight _^0/0. 5 parts by mass of this master patch was mixed with 95 parts by mass of a polypropylene resin (Ml = 50 gZ10 minutes) to prepare a composition containing 2% by mass of calcium oxide hydrate powder. This composition is put into an extruder, melt-kneaded at a resin temperature of 220 ° C., and the kneaded material is put into a die (200 E). ), Stretched with high-speed air, and thinned to produce continuous filament filaments. In addition, Ml (melt index) was measured at 230 ° C and a load of 2.16 kgf (2.1.8 N) in accordance with JISK6921.

 The filaments were randomly accumulated to form a sheet. The sheet was passed between an embossing roll and a smoothing roll, and hot-embossed at 140 ° C. to produce a nonwoven fabric.

The resulting nonwoven fabric had an average fiber diameter of 2 2. 4 ^ m, an average basis weight 5 0 g Roh m ^2. A sample of 5 cm × 5 cm was cut out from this nonwoven fabric. The formaldehyde concentration was measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1

 In Example 1, the concentration of formaldehyde was measured without using calcium oxide hydrate powder. In addition, an antifungal test was performed. The results are shown in Table 1. c Comparative Example 2

 In Example 1, the formaldehyde concentration was changed in the same manner as in Example 1 except that the calcium oxide hydrate powder was changed to magnesium hydroxide having an average particle size of 1 μπι (ρ で in a 1 gZ liter aqueous solution was 7). It was measured. In addition, an antifungal test was performed. Table 1 shows the results.

Comparative Example 3

A powder having an average particle diameter of 30 μπι obtained in Example 1 except that the calcination temperature was 600 ° C and the hydration step after calcination was not performed (1 g / liter aqueous solution) For ρ 8 at 8), the formaldehyde concentration was measured in the same manner as in Example 1. In addition, an antifungal test was performed. The results are shown in Table 1 _c Comparative Example 4

In Example 5, except that no deodorant / antibacterial mixed powder formulation was used, The formaldehyde concentration was measured in the same manner as in Example 5. Table 1 shows the results. Comparative Example 5

 In Example 6, the same as in Example 4, except that the deodorant and antibacterial treated leather was replaced with the same deodorant PVC leather that did not contain the antibacterial mixed powder formulation. When the ammonia concentration was measured, it was 230 ppm by mass.

 [Anti-mold test]

 1. Test strain: Fungal fungi

2. Media used:

 ① Medium 1: Glucose inorganic salt medium

 Gunore course 300 g

 Ammonium nitrate 30 g

 Potassium monophosphate 0 g

 Magnesium sulfate 0 5 g

 Potassium chloride 0 25 g

 Ferrous sulfate '0 0 0 2 g

 Deionized water 000 ml

 ② Medium 2: Glucose inorganic salt agar medium

 Gunore course 30.0 g

 Ammonium nitrate 3.0 g

 Phosphoric acid ream 1.0 g

 Magnesium sulfate 0.5 g

 0.25 g of potassium chloride

 Ferrous sulfate 0.02 g

 Deionized water 1 000 ml

Agar 25.0 g 3. Preparation of spore solution:

 Mucor filamentous fungi were allowed to form spores on PDA (potato dextrose agar medium) plates (cultured at 28 ° C for one week), and the spore / mycelium suspension was added using 10 milliliters of sterile water. Was prepared.

 Next, this was filtered through sterile absorbent cotton, and spores were precipitated by centrifugation, and re-suspended in the above medium 1 (without agar, glucose inorganic salt medium) at 20 milliliters to prepare a spore liquid.

 4. Installation of test pieces and inoculation

On the medium 2 (glucose mineral salts agar), 5 g Z liters aqueous deodorant antimicrobial powder formulation used in Examples 1 3 and Comparative Example 1 to 3 (0.5 mass _^0/0) 1 Milliliters were spread on the plate.

 The spore solution was sprayed on the test piece by spraying to such an extent that fine water droplets were formed, and the plate was sealed with a paraffin film, followed by culturing in a thermostatic chamber. Spraying was performed using a nebulizer and a double ball, and the culture conditions were culture temperature of 30 ° C, humidity of 95%, and culture period of 4 weeks.

 5. Observation of fungal growth:

 Two weeks after the inoculation, the degree of mycelial growth on the test plate surface was visually observed.

6. Judgment of the result:

 The change over time in the growth status of the hypha was determined according to the following criteria.

 [Growth criteria]

 I: No growth of hyphae is observed with the naked eye

 + Z—: Slight hyphal growth is observed

 +: Hyphal growth is observed

: Remarkable hyphal growth and sporulation are observed table 1

 ND; not detected. Example 11

Calcium oxide hydrate powder (deodorant / antibacterial powder formulation) having an average particle size of 10 μιη was mixed with Acryl Emulsion (Crosslen, manufactured by Ganz Kasei Co., Ltd.) to prepare a fiber treatment agent. Deodorant · The compounding amount of the antibacterial powder preparation was 50% by mass based on the dry mass of the fiber treatment agent. The polyester base fabric, by a roll coater one laminating the fiber treatment agent, 1 0 0 ° and dried for 30 minutes at C, deodorant to fiber treatment agent is 2 4 g ² coating on a dry weight A polyester base fabric with antibacterial properties was manufactured. A sample of 5 cm × 5 cm was cut out from this base cloth, and the formaldehyde concentration was measured in the same manner as in Example 1. As a result, the concentration was less than 0.5 ppm by mass.

Example 1 2 Calcium oxide hydrate powder (deodorant / antibacterial powder formulation) having an average particle size of 5 μπι was mixed with Acryl Emulsion (Crosslen, manufactured by Ganz Chemical Co., Ltd.) to prepare a fiber treatment agent. Deodorant 配合 The amount of the antibacterial powder preparation is 50 mass based on the dry weight of the fiber treatment agent. /. And The above fiber treating agent was laminated on a polyester base fabric with a roll coater and dried at 100 ° C. for 30 minutes, and the fiber treating agent was applied at a dry mass of 26 g / m ² to remove the fiber treating agent. Odor. An antibacterial polyester fabric was produced. A sample of 5 cm × 5 cm was cut out from this base cloth, and the formaldehyde concentration was measured in the same manner as in Example 1. As a result, it was less than 0.5 ppm by mass.

Example 13

Calcium oxide hydrate powder (deodorant / antibacterial powder formulation) having an average particle size of 10 was mixed with Acryl Emulsion (Crosslen, manufactured by Ganz Kasei Co., Ltd.) to prepare a fiber treatment agent. Deodorant · The amount of the antibacterial powder formulation was 50% by mass based on the dry mass of the fiber treatment agent. The above fiber treatment agent is laminated on a polyester base fabric with a roll coater and dried at 100 ° C. for 30 minutes, and the fiber treatment agent is applied at a dry weight of 5 g / m ² to remove deodorant. · Manufactured polyester fabric with antibacterial properties. A sample of 5 cm × 5 cm was cut out from this base cloth, and the formaldehyde concentration was measured in the same manner as in Example 1. As a result, it was less than 0.5 ppm by mass.

Example 14

Calcium oxide hydrate powder (deodorant and antibacterial powder formulation) with an average particle size of 10 m is blended with Acryl emulsion (Crosslen, manufactured by Ganz Kasei Co., Ltd.), and the concentration of calcium oxide hydrate powder is 2 mass%. % Dispersion was prepared. This dispersion was applied to a 30 cm x 30 cm x 12 mm plywood using a sprayer, and calcium oxide hydrate powder was applied at 2 g Z 900 cm ² in formua. Plywood with reduced generation of rudder was manufactured. The amount of formaldehyde emission of this plywood was measured by the method specified in JISA 1991, and was found to be 0.2 mg / liter. On the other hand, the untreated plywood of the same material had a formaldehyde emission of 0.5 mg Z liter.

Comparative Example 6

90 mass% water, calcium oxide hydrate powder with an average particle size of 8 μm (deodorant. Antibacterial powder formulation) A dispersion mixed at a ratio of 10 mass% is wet-bead milled (Ashiza Finetech Co., Ltd.) ), And wet-milled with LMZ-2) to obtain calcium oxide hydrate powder (deodorant / antibacterial powder formulation) having an average particle size of 0.6 μππι. This deodorant 'antibacterial powder formulation' was blended with Acryl Emulsion (Crosslen, manufactured by Ganz Kasei Co., Ltd.) to prepare a 'fiber treatment agent'. The amount of the deodorant and antibacterial powder preparation was 50% by mass based on the dry weight of the fiber treatment agent. The polyester Le system base fabric by a roll coater by laminating the fiber treatment agent, 1 0 0 ° and dried for 30 minutes at C, deodorant to fiber treatment agent is 2 7 g Zm ² coating on a dry weight 'An antibacterial polyester fabric was manufactured. With this base cloth, the deodorant / antibacterial powder preparation was agglomerated and could not withstand actual use.

Comparative Example 7

 Calcium oxide hydrate powder (deodorant / antibacterial powder formulation) with average particle size of 45 μππι obtained by classifying calcium oxide hydrate powder (deodorant / antibacterial powder formulation) with an average particle size of 8 μπι Was mixed with Acryl Emulsion (Cross Len, manufactured by Ganz Kasei Co., Ltd.) to prepare a fiber treatment agent. Deodorizing · The blending amount of the antibacterial powder preparation was 50% by mass based on the dry weight of the fiber treatment agent. An attempt was made to laminate the above fiber treatment agent on a polyester base fabric using a roll coater, but the fiber treatment agent was separated into solid and liquid and could not be laminated.

Comparative Example 8 Calcium oxide hydrate powder (deodorant / antibacterial powder formulation) having an average particle size of 10 μππ was blended with Acryl Emulsion (Crosslen, manufactured by Ganz Kasei Co., Ltd.) to prepare a fiber treatment agent. Deodorant · The compounding amount of the antibacterial powder preparation was 50% by mass based on the dry mass of the fiber treatment agent. The fiber treatment agent was laminated on a polyester base fabric using a roll coater 1, dried at 100 ° C for 30 minutes, and the fiber treatment agent was applied in a dry mass of 0.5 g Zm ² . Deodorization An antibacterial polyester base fabric was manufactured. A sample of 5 cm × 5 cm was cut out from this base cloth, and the formaldehyde concentration was measured in the same manner as in Example 1. As a result, it was 2 ppm by mass.

Comparative Example 9

Calcium oxide hydrate powder (deodorant / antibacterial powder formulation) having an average particle size of 10 μιη was blended with Acryl Emulsion (Croslen, Ganz Kasei Co., Ltd.) to prepare a fiber treatment agent. Deodorant · The compounding amount of the antibacterial powder preparation was 50% by mass based on the dry mass of the fiber treatment agent. The above-mentioned fiber treating agent was laminated on a polyester base fabric with a roll coater and dried at 100 ° C. for 30 minutes, and the fiber treating agent was applied at a dry mass of 58 g / m ^2. An odor- and antibacterial-imparting polyester-based fabric was manufactured. A sample of 5 cm × 5 cm was cut out from this base cloth, and the formaldehyde concentration was measured in the same manner as in Example 1. Although this concentration was less than 0.5 mass ppm, the texture of the obtained deodorant 'antibacterial property-imparting polyester-based fabric was confirmed to be extremely hard and could not withstand actual use. Industrial applicability

 The deodorant / antibacterial powder of the present invention has a high-performance deodorant and antibacterial effect against various odors and various bacteria, and can be used in a wide range of fields.

Claims

The scope of the claims 1. A deodorant and antibacterial powder formulation with an average particle size of 1 to 40 m, obtained by hydrating calcium oxide obtained by baking shells. 2. Deodorant and antibacterial powder comprising 5 to 95% by mass of the powder according to claim 1 and 95 to 5% by mass of a tea powder or a tea husk powder having an average particle diameter of 1 to 40 μπι. Preparation. 3. Calcium hydroxide powder having an average particle diameter of 1 to 40 μπι 5 to 95 mass ⁰ X », and tea powder or tea husk powder having an average particle diameter of 1 to 40 μπι 95 to 5 mass. Deodorant consisting of / ₀ • Antibacterial powder formulation. 4. A method for producing calcium oxide by calcination of shells at 800 to 130 ° C. and hydrating the oxidizing power to produce a deodorant / antibacterial powder formulation, comprising the steps of: 0 5 to 0.1 5 weight _^0/0 solution p H are provided methods for producing the deodorant antimicrobial powder formulation, characterized by Uni hydrated by a 9-1 3. 5. The production method according to claim 4, wherein the calcined product obtained by calcining the shell is pulverized so as to have a particle size of 100 μm or less, and 1 kg of the pulverized material is crushed. A method for producing a deodorant / antibacterial powder preparation, characterized by adding 0.2 to 1 liter of water to hydrate calcium oxide. 6. A synthetic resin composition containing 0.1 to 30% by mass of the deodorant / antibacterial powder preparation according to any one of claims 1 to 3. 7. A deodorant that has been surface-treated with a surface treatment agent containing the deodorant or antibacterial powder preparation according to any one of claims 1 to 3, and is an antibacterial leather, and has a deodorant and antibacterial property. Deodorant in which the amount of the powdery formulation is 1 to 30% by mass based on the dry mass of the surface treatment agent. Antibacterial leather. 8. A paint comprising the deodorant / antibacterial powder preparation according to any one of claims 1 to 3 in an amount of 0.1 to 35% by mass on a dry mass basis. 9. A fiber treating agent comprising the deodorant / antibacterial powder preparation according to any one of claims 1 to 3 in an amount of 1 to 80% by mass on a dry mass basis. 10. Deodorant according to any one of claims 1 to 3 · Deodorant treated with a treating agent containing an antibacterial powder formulation · Antibacterial fiber, deodorant · Antibacterial Deodorant and antibacterial fibers with a blending amount of the active powder formulation of 1 to 70% by mass based on the dry weight of the treating agent. 11. A deodorant / antibacterial film comprising the synthetic resin composition according to claim 6. 12. A deodorant / antibacterial foam obtained by foaming the synthetic resin composition according to claim 6. 13. A deodorant / antibacterial herbicidal sheet comprising the synthetic resin composition according to claim 6. 14. Deodorant and antibacterial powder according to any one of Claims 1 to 3 A nonwoven fabric made of a thermoplastic resin composition, comprising a deodorant having an average particle size of 1 to 10 m and an antibacterial powder formulation of 0.5 to 20% by mass. 1 5. Average particle size. 3 to 2 0 m calcium hydrate powder oxidation of, formed by back treating fibers with a dry weight 1~ 5 0 g / m ² against the fiber deodorant 'antimicrobial property imparting fiber. 16. A car seat or automobile ceiling material formed of the deodorant / antibacterial property imparting fiber according to claim 10 or 15. 17. The deodorant according to any one of claims 1 to 3, an antibacterial powder, and a deodorant comprising a calcium oxide hydrate powder having an average particle diameter of 1 to 40 μm. Plywood containing a mixed powder formulation.