TW201306921A - Aldehyde deodorant and method for producing thereof - Google Patents

Abstract

The present invention provides an aldehyde deodorant which has a high deodorizing performance for an aldehyde, is difficult to a color change by alkali and has a water resistance. Also, the object of the present invention provides deodorant processing products such as a fiber, coating, sheet, and molded article which are capable of an excellent deodorizing performance by using the deodorants. A deodorant for an aldehyde-based gas of the present invention is characterized by supporting hydrazides compounds on an aluminum/phosphorus-based amorphous carrier. Also, a preferable method for producing the deodorant for an aldehyde-based gas is a production method which comprises: a preparation step for preparing a reaction liquid comprising a water-soluble salt of aluminum and a phosphoric acid; an addition step in which alkali is added to the reaction liquid so as to make the pH value of the reaction liquid to 9 -11 and an aluminum/phosphorus-based amorphous carrier is obtained; and a supporting step for supporting hydrazides compounds on an aluminum/phosphorus-based amorphous carrier.

Description

Aldehyde deodorant and preparation method thereof

The present invention relates to a deodorant having a high deodorizing ability to an aldehyde-based gas in which a specific organic drug is carried on a novel inorganic carrier. The deodorant of the present invention is excellent in discoloration resistance especially in alkali treatment, and when used in a fiber product or the like, discoloration during processing can be avoided.

In recent years, consumer demand for deodorization, particularly for tobacco odor, has rapidly increased, and acetaldehyde is a major component of tobacco odor. In addition, as seen in sick houses/sick building syndrome, the health diseases caused by formaldehyde are also attracting attention. As the remover of these aldehyde-based gases, it is known that an aldehyde remover containing an amine compound is effective.

For example, Patent Document 1 discloses that an aldehyde-based gas in an exhaust gas can be removed by bringing an exhaust gas containing an aldehyde-based gas into contact with a liquid in which an amine compound is dissolved.

On the other hand, an aldehyde gas absorbent which supports an amine compound in an inorganic substance is known, and Patent Document 2 discloses that a decane coupling agent containing an amine group is supported on cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, or the like. An adsorbent for deodorizing a porous metal oxide is described as being applicable to an air cleaner filter or the like.

Further, in Patent Document 3, an amine sulfate based sulfonate is exemplified as an aldehyde-removing agent, and a carrier which can be carried on activated carbon, calcium citrate, zeolite, cellulose, silicone, ion exchange resin or the like can be used.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 51-44587

[Patent Document 2] Japanese Patent Laid-Open Publication No. Hei 9-173830

[Patent Document 3] Japanese Patent Laid-Open No. Hei 10-235129

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-354622

Further, in the invention described in Patent Document 1, since the liquid amine compound releases a strong unpleasant odor, it is less suitable for use in a living space such as a living room or a kitchen.

In the examples of Patent Document 2, the sulfonium coupling agent containing an amine group is carried on a cerium oxide carrier and evaporated to dryness at 120 ° C. However, there is no description or suggestion of the discoloration resistance.

Furthermore, in the invention described in Patent Document 3, there is no description about the discoloration resistance. Patent Document 3 is an invention relating to an air cleaner, and it is considered that the reason is that the air cleaner filter does not require aesthetic discoloration resistance.

Take the 2003 Japan Health Promotion Law as an opportunity, and with the establishment of smoking separation measures in the workplace or in stores, vehicles, smoking rooms or smoking areas, seats, curtains, walls, and daily routines in the smoking area. The surface that is visible to the eye, such as utensils, is smudged, and the smell of smoke emitted is considered a problem. In addition, as a countermeasure for the sick residential syndrome, wallpapers and curtains having an aldehyde deodorizing function are gradually being used. On the other hand, fabrics that have been known to be stably processed by keywords such as "non-iron" are extremely popular, and are particularly commonly used in shirts, curtains, and the like. Here, the problem is that most of the conventional amine-based aldehyde deodorants are discolored by heating, particularly alkali treatment.

For the stable processing of kapok-containing fabrics, it is well known that liquid ammonia processing or mercerization is known to use caustic soda, but these use strong alkalis, and thus the amine-based aldehyde deodorant is easy. Significant discoloration occurs, and even if it is subjected to morphologically stable processing and attached to a deodorant, there is a possibility that partial discoloration occurs during ironing, and it is not suitable for applications requiring aesthetics. Therefore, there is a need for an aldehyde deodorant which has high aldehyde deodorizing performance and is not easily discolored by alkali.

An object of the present invention is to provide an aldehyde deodorant which has high aldehyde deodorizing performance, is not easily discolored by alkali, and has water resistance. Further, the present invention provides a fiber which exhibits excellent deodorizing performance by using the deodorant or the like. Deodorant processed products such as paints, sheets, and molded articles.

The present inventors have found that an aluminum compound having a high aldehyde deodorizing property and a carrier capable of improving alkali discoloration resistance and water resistance have been found to be unpredictable in the production of aluminum/phosphorus. It is an inorganic carrier and is combined with an anthraquinone compound, particularly diterpene adipate, to have high aldehyde deodorizing performance and excellent alkali discoloration resistance and water resistance. That is, the present invention is a deodorant which combines an anthraquinone compound with an aluminum/phosphorus-based inorganic carrier which exhibits high aldehyde deodorizing performance and excellent alkali-resistant discoloration property and water resistance, in combination with an anthracene compound. A method of producing an inorganic carrier and a deodorant, and a deodorant processed article using the deodorant.

The aluminum/phosphorus inorganic carrier used in the present invention can be used as a aldehyde deodorizing property and excellent alkali discoloration resistance and water resistance when combined with an anthraquinone compound, particularly diterpene adipate. Stiner. Further, since the deodorant has high alkali discoloration resistance, it does not cause discoloration when the deodorized processed product such as a fiber product or a sheet is produced by the alkali treatment in the processing, and the appearance is not impaired, even if washing is performed. The wiping off with water does not impair the function, and the aldehyde-based gas is excellent in deodorizing performance, so that the aldehyde-based gas can be effectively removed from a sealed space such as indoors or in a vehicle.

[Formation of the Invention]

The aldehyde-based gas deodorant (hereinafter referred to as "the deodorant of the present invention") of the present invention is characterized in that an aluminum/phosphorus-based amorphous carrier is supported on a quinone compound.

The invention will be described in detail below. Further, % is % by mass, and parts are parts by mass. The pH measurement is carried out by a glass electrode at room temperature (1 to 30 ° C) using a general pH meter, and is preferably measured at 20 to 25 ° C.

○Aluminum/phosphorus inorganic carrier

The aluminum/phosphorus inorganic carrier used in the present invention is an inorganic particle of an amorphous porous body. The Al/P atomic ratio can be measured by, for example, fluorescent X-ray analysis, and dissolved by ICP (Inductively Coupled Plasma Emission Spectrometry), and the film is "amorphous" and can be crystallized by powder X-ray diffraction analysis. Peak to confirm.

Although the aluminum/phosphorus-based amorphous carrier used in the present invention has no known production method, it can be synthesized by the following means in the present invention. It can be synthesized by mixing an aqueous solution of an aluminum salt with phosphoric acid, adding a base at room temperature and atmospheric pressure, and coprecipitating it under conditions of pH 9 to 12, and making it, for example, at about 40 ° C to about 100. The coprecipitate is washed, dehydrated and dried without being ripened at a temperature of about °C.

Regarding the amount of the water-soluble salt of aluminum and the amount of phosphoric acid in the synthesis of the aluminum/phosphorus-based amorphous carrier, although the ratio of the Al/P atom is smaller, the specific surface area of the formed carrier tends to be larger, and the result is obtained. The deodorizing performance of the odorant is not only dependent on the specific surface area. As long as the ratio of Al/P atoms is in the range of 1/10 to 2/1, a carrier which is a preferable range for use as a deodorant can be obtained, and the performance of the deodorant is also improved. More preferably, it is in the range of 1/6 to 2/3.

The water-soluble salt of aluminum may, for example, be a water-soluble salt such as a sulfate, a nitrate, a chloride, an iodide or a bromide. Among them, a sulfate is preferred. Further, examples of the base used in the above synthesis include alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, aqueous ammonia, and tetramethylammonium hydroxide. Among them, sodium hydroxide which is inexpensive, easily available, and has a small change in concentration is preferred. Phosphoric acid other than orthophosphoric acid may be a phosphoric acid such as polyphosphoric acid or pyrophosphoric acid or a salt thereof, preferably orthophosphoric acid.

The step of mixing the water-soluble salt of aluminum with phosphoric acid is not particularly limited as long as it is not a step of precipitation before the addition of a base, and it may be mixed in any step. When a reaction liquid containing a water-soluble salt of aluminum and a phosphoric acid is mixed with a base, a base may be added to the reaction liquid or vice versa, but it is preferably from the viewpoint of confirming the pH at the end of the addition while adding. A method of reacting a lye under a droplet. The preferred pH at the end of the dropwise addition to ripening is 8 to 11, more preferably 9 to 10.

When the reaction liquid containing aluminum water-soluble salt phosphoric acid is mixed with a base, the obtained deodorant has a large specific surface area and a high deodorizing performance, and is preferable, but industrially, too fast. There are restrictions on the device. Therefore, it is preferred to simultaneously drip or continuously mix a reaction liquid containing a water-soluble salt of aluminum and phosphoric acid, and an alkali solution, thereby mixing and charging the reactor, whereby the deodorizing property of the deodorant is improved. .

The aldehyde deodorant of the present invention can be produced by supporting a ruthenium on an aluminum/phosphorus-based amorphous carrier. Examples of the anthracene include a monoterpene compound having one mercapto group in the molecule, a diterpene compound having two mercapto groups in the molecule, and a polyfluorene having three or more mercapto groups in the molecule. Compounds, etc.

Specific examples of the monoterpene compound may be exemplified by

R-CO-NHNH ₂ (1)

[wherein, R represents a hydrogen atom, an alkyl group, or an aryl group having a substituent] is a monoterpene compound.

In the above formula (1), examples of the alkyl group represented by R include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and anthracene group. A linear alkyl group having 1 to 12 carbon atoms such as a group, a fluorenyl group or a n-decyl group. The aryl group may, for example, be a phenyl group, a biphenyl group or a naphthyl group, and among these, a phenyl group is preferred. Further, examples of the substituent of the aryl group include a halogen atom such as a hydroxyl group, a fluorine atom, a chlorine atom or a bromine atom, and a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group and a tertiary butyl group. A linear or branched alkyl group having 1 to 4 carbon atoms such as a base or an isobutyl group.

The hydrazine compound of the above formula (1), more specifically, hydrazine laurate, strontium salicylate, formamidine, acetamidine, bismuth propionate, bismuth hydroxybenzoate, bismuth naphthalate , 3-hydroxy-2-naphthoquinone, and the like.

Specific examples of the diterpene compound may be exemplified by

H ₂ NHN-X-NHNH ₂ (2)

[wherein X represents a -CO- group or a -CO-A-CO- group; and A represents a diterpene compound represented by an alkylene group or an extended aryl group].

In the above formula (2), the alkylene group represented by A may, for example, be a methylene group, an exoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or a octyl group. A linear alkyl group having a carbon number of 1 to 12, such as a thiol group, a hydrazine group, and an eleventh group. The substituent of the alkylene group may, for example, be a hydroxyl group or the like. The aryl group may, for example, be a phenyl group, a phenyl group, a phenylene group, a fluorenyl group or a phenanthrenyl group. Among them, a phenyl group, a naphthyl group or the like is preferable. The substituent of the aryl group may, for example, be the same as the substituent of the above aryl group.

The diterpene compound of the above formula (2) may specifically be exemplified by diterpene oxalate, diammonium malonate, diterpene succinate, diterpene adipate, diterpene sebacate. , bismuth azelaic acid, dinonyl dodecanoate, diterpene maleate, diammonium fumarate, dioxonium oxydiacetate, diterpenic tartrate, diammonium malate, Diterpene phthalic acid, diterpene terephthalate, dimer acid diterpene, 2,6-naphthoic acid diterpene, etc.

Specific examples of the polyfluorene compound include polyacrylic acid hydrazine and the like. Among these, a diterpene compound is preferred, and a dibasic acid diterpene is more preferred, and a diammonium adipate is more preferred. These hydrazine compounds may be used singly or in combination of two or more kinds.

The aluminum/phosphorus inorganic carrier used in the present invention can be used as a aldehyde deodorizing property and excellent alkali discoloration resistance and water resistance when combined with an anthraquinone compound, particularly dioxane adipate (ADH). Deodorant. The detailed mechanism is still unknown, but it is considered that ADH is not excessively adsorbed but is properly supported on an aluminum/phosphorus carrier composed of amorphous, and ADH and aldehyde can exhibit higher reactivity and play higher. Stinky performance. It is also considered that an appropriate surface charge of an aluminum/phosphorus carrier composed of an amorphous substance suppresses oxidation and decomposition of ADH to suppress discoloration. However, the crystalline carrier does not achieve such an effect.

○ Method for producing aldehyde-based gas deodorant

In the method for producing an aldehyde-based gas deodorant of the present invention, when an aluminum/phosphorus-based inorganic carrier or a dispersion thereof is mixed with a hydrazine or a solution thereof or a dispersion thereof, and a solvent is used, Solvent removal to make.

In addition, the method for producing an aldehyde-based gas deodorant of the present invention preferably comprises: a preparation step of preparing a reaction liquid containing a water-soluble salt of aluminum and phosphoric acid; and an adding step of adding a base to the reaction liquid to increase the pH of the reaction liquid Between 9 and 11, an aluminum/phosphorus amorphous carrier is obtained; and a supporting step is carried out to carry the bismuth compound on the aluminum/phosphorus amorphous carrier.

The dioxane adipate which is a preferred terpenoid compound is usually a solid, and is preferably used in the form of a solution, more preferably an aqueous solution.

The aldehyde-based gas deodorant of the present invention can be produced by stirring an inorganic powder at room temperature to less than 70 ° C, adding a hydrazine compound, and thoroughly mixing the mixture. Alternatively, the aldehyde-based gas deodorant of the present invention can be produced by stirring an inorganic powder at a temperature lower than the decomposition temperature of the hydrazine compound, adding a quinone compound, and sufficiently mixing. In these production methods, the aldehyde-based gas deodorant of the present invention is preferably produced at a temperature of from room temperature to less than 70 °C.

Further, the aldehyde-based gas deodorant of the present invention can also be produced by stirring the inorganic powder at room temperature to below 60 ° C, adding it by dropping or spraying a solution of the quinone compound, and mixing it well. The mixture can be further dried. The drying is preferably 60 to 120 ° C, more preferably 80 to 110 ° C, and can be carried out under reduced pressure. Further, the processing time of the drying step varies depending on the drying temperature, the processing amount, and the apparatus, and there is an optimum time. Therefore, it may be set according to conditions.

Further, the aldehyde-based gas deodorant of the present invention can be produced by stirring a dispersion of an inorganic powder at room temperature to less than 70 ° C, adding a hydrazine compound, and sufficiently mixing the mixture. The mixture can also be further dried. The drying is preferably 60 to 120 ° C, more preferably 80 to 110 ° C, and can be carried out under reduced pressure. Further, the processing time of the drying step varies depending on the drying temperature, the processing amount, and the apparatus, and there is an optimum time. Therefore, it may be set according to conditions.

Further, the aldehyde-based gas deodorant of the present invention can be produced by stirring a dispersion of an inorganic powder at room temperature to less than 70 ° C, adding a solution of a quinone compound or a dispersion thereof, and sufficiently mixing the mixture. . The mixture can also be further dried. The drying is preferably 60 to 120 ° C, more preferably 80 to 110 ° C, and can be carried out under reduced pressure. Further, the processing time of the drying step varies depending on the drying temperature, the processing amount, and the apparatus, and there is an optimum time. Therefore, it may be set according to conditions.

In the production methods exemplified above, the method of adding the inorganic powder and the quinone compound may be reversed. In other words, the aldehyde-based gas deodorant of the present invention is produced by stirring a solution of a quinone compound or a dispersion thereof at room temperature to less than 70 ° C, adding an inorganic powder, and sufficiently mixing the mixture. The other manufacturing methods exemplified in the above can also be carried out in the same manner.

Among these production methods, a method of producing a solution using a quinone compound is more preferable.

The solution of the quinone compound used in the present invention may be an aqueous solution or an organic solvent such as an alcohol or methanol, and is preferably an aqueous solution having the highest solubility. The dispersion of the inorganic powder may be an aqueous solution or an organic solvent such as an alcohol or methanol, and is preferably an aqueous solution.

The aldehyde-based gas deodorant of the present invention has an aluminum/phosphorus-based inorganic carrier, and the more the amount of the quinone-based compound is, the better the deodorizing effect is, and the better the load is. It is not effective to be completely supported on the carrier, so the preferred loading amount is 100 parts by mass relative to the carrier, and the terpenoid is 0.1 to 500 parts by mass, more preferably 3 to 100 parts by mass, still more preferably 10 parts by weight. ~50 parts by mass. The carrier used for the aldehyde-based gas deodorant preferably has a BET specific surface area of from 100 to 600 m ² /g, more preferably from 150 to 500 m ² /g, particularly preferably from 150 to 400 m ² /g.

○ mixed with other deodorants

The aldehyde-based gas deodorant of the present invention is very effective for an aldehyde-based gas, and examples of the aldehyde-based gas include acetaldehyde, formaldehyde, propionaldehyde, butyraldehyde, and nonenal. Further, the aldehyde-based gas deodorant of the present invention may be used together with an aldehyde gas deodorant other than the aldehyde-based gas deodorant of the present invention. Examples of the aldehyde gas deodorant include ammonium sulfate, polyallylamine hydrochloride, ethylenediaminetetraacetic acid (EDTA), sodium salt, triethanolamine, pyridine, dimethylformamide, casein, and urea. Thiourea, sodium caseinate, glycine, hexamethylenetetramine, guanidine nitrate, bis(hydroxylamine sulfate), and the like.

The method of using the aldehyde-based gas deodorant of the present invention may be an aldehyde-based gas alone, but may be mixed with a deodorant other than the aldehyde-based gas (deodorant composition) or used together. . Further, the aldehyde-based gas deodorant or deodorant composition of the present invention can also be used to improve deodorization by mixing magnesium silicate clay.

As a specific example of mixing or using together with the aldehyde-based gas deodorant of the present invention, an alkaline gas deodorant which deodorizes an alkaline gas such as ammonia or trimethylamine is used. As the alkaline gas deodorant, a tetravalent metal phosphate compound which is insoluble or poorly soluble in water can be exemplified. Preferred examples of the tetravalent metal phosphate compound include zirconium phosphate, titanium phosphate, tin phosphate, and the like. These compounds are crystalline materials and amorphous materials having various crystal systems such as α-form crystal, β-form crystal, γ-type crystal, and sodium superionic conductor (NASICON) crystal, and those having gas adsorbability can be used in the present invention. The aldehyde-based gas deodorant is mixed or used in combination.

Further, the aldehyde-based gas deodorant of the present invention may be mixed with or used for a sulfur-based gas deodorant for deodorizing a sulfur-based gas such as hydrogen sulfide or methyl mercaptan. For example, the aldehyde-based gas deodorant of the present invention may be mixed with a tetravalent metal phosphate compound, zinc oxide, or zinc ruthenate carrying at least one metal ion selected from the group consisting of copper, zinc, and manganese. And use it. Among the metal ions supported on the tetravalent metal phosphate compound, particularly copper ions, hydrogen sulfide or the like has a high deodorizing effect and is preferable.

When the metal ion is to be supported on the tetravalent metal phosphate compound, the tetravalent metal phosphate compound may be brought into contact with the salt solution of the metal ion, and then carried by ion exchange or the like.

The amount of metal ions supported can be arbitrarily adjusted as needed, as long as it is within the ion exchange capacity of the tetravalent metal phosphate compound.

Further, in the case of zinc oxide, copper ruthenate and zinc antimonate, those having a large specific surface area have a high deodorizing performance and are preferable.

Further, the aldehyde-based gas deodorant of the present invention can be used in combination with or used in an organic acid gas deodorant for removing malodor of acetic acid, isovaleric acid, butyric acid or the like. For example, a deodorant composition can be prepared by mixing hydrated zirconia and hydrous titanium oxide with the aldehyde-based gas deodorant of the present invention.

The shape of the deodorant or deodorant composition of the present invention described above is not particularly limited, and is preferably in the form of a powder. The average particle diameter is preferably from 0.01 to 50 μm, more preferably from 0.02 to 20 μm. When the average particle diameter is 0.01 μm or more, handling is easy, and the problem that re-agglomeration easily occurs can be suppressed. In addition, when it is 50 μm or less, it is dispersed in a surface treatment agent such as an adhesive and post-processed fibers, etc., and is easily dispersed uniformly in the surface treatment agent, and when added to the molding resin, the molding machine filter can be suppressed. Blockage, poor dispersion and other issues.

Further, the aldehyde-based gas deodorant or the deodorant composition of the present invention may be granulated depending on the purpose of use. At this time, the deodorant may be granulated for each component, or the deodorant composition may be granulated. The method for producing the granules may be any method of granulating a general powder. For example, there is a method of using a alumina gel, clay, or the like as an adhesive to form a granulated body. The particle size can be variously adjusted depending on the hardness, density, pulverization strength, and the like of the granulated body, and is preferably 0.1 to 3 mm in terms of ease of handling.

○Processing method of deodorized processed product using aldehyde gas deodorant Fiber post-processing method

The deodorant of the present invention can be used in combination with an adhesive resin which is generally used for surface treatment of fibers such as acrylic or urethane resins, nonwoven fabrics, and sheets. At this time, a dispersing agent, a surfactant, an antifoaming agent, a water retaining agent, a preservative, a viscosity adjuster, and the like may be added as needed, and dispersed by a sand mixer, a disperser, a ball mill or the like. The mixture of the adhesive resin and the deodorant solid content is preferably, the solid content of the deodorant is 100 parts by mass, and the solid content of the adhesive resin is 10 to 300 parts by mass. When the solid content of the adhesive resin is 10 parts by mass or more, the deodorizing dispersion is sufficiently loaded on the fibers, the nonwoven fabric, the sheet, and the like, and the deodorizing agent is prevented from falling off to deteriorate the deodorizing performance. When the solid content of the adhesive resin is 300 parts by mass or less, when the fiber, the nonwoven fabric, the sheet or the like is processed, the deodorant is not completely covered with the resin, and the deodorizing performance can be sufficiently exhibited.

[Examples]

Hereinafter, the present invention will be more specifically described, but is not limited thereto. In addition, % is % by mass.

The particle size measurement method is a particle size analysis result of a volume-based deodorant particle in which ultrasonic waves are dispersed in deionized water by a laser diffraction type particle size distribution system, and a median diameter is used. Further, the measurement of the specific surface area was measured by a nitrogen adsorption BET method.

○ Determination of deodorizing performance

In the measurement of the deodorizing performance, 0.02 g of the deodorant sample was placed in a vinyl fluoride bag (the film of the vinyl fluoride was processed into a bag shape, hereinafter referred to as Tedlar Bag), and 2 liter of acetaldehyde-containing gas was injected thereinto. The air was placed at room temperature for 2 hours. Two hours later, the concentration of acetaldehyde gas remaining in the Tedlar Bag was measured by a gas detecting tube (manufactured by GASTEC Co., Ltd., using the same company below), and the blank test was subtracted from the gas reduction per gram of deodorant. The amount obtained by reducing the amount was used to calculate the deodorizing capacity (unit ml/g, ml refers to the gas volume in the standard state), and the blank test was performed using an empty Tedlar Bag. The results of these measurements are shown in Table 2.

○ Water resistance test of deodorant

1 g of the deodorant sample was placed in 100 ml of deionized water at 20 ° C and stirred for 1 hour, filtered through a microfilter having a pore size of 5 μm, and further washed with 1000 ml of deionized water. Thereafter, it was dried at 120 ° C for 2 hours in conjunction with a filter, and fine powder on the filter was taken, and the deodorizing performance against acetaldehyde gas was measured. The measurement results of the deodorizing performance after the water treatment are shown in Table 2.

<Evaluation of alkali discoloration resistance 1>

The alkali discoloration evaluation method using 0.1 N-NaOH is as follows: The deodorant sample is processed to a pulp/polymer by impregnation method using a urethane adhesive KB-3000 (manufactured by Toagosei Co., Ltd.) A propylene (PP) nonwoven fabric was processed to a processing capacity of about 1 g/m ² and dried at 120 ° C for 30 minutes to prepare a deodorant processing cloth. 0.5 g of a 0.1 N-NaOH aqueous solution was dropped on the processing cloth at 200 cm ² , placed in a 9 cm ² petri dish, and allowed to stand at room temperature under direct sunlight for 24 hours, and then a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd.) The color difference meter SZ-Σ80) measures the color (L, a, b), respectively. Thereafter, the color difference ΔE was obtained by comparing the colors before and after the test. The results are shown in the column of NaOH in Table 2. Further, N means a unit indicating a solution concentration, which is also called a normality or a predetermined concentration, and is equivalent to a molar ratio of a base such as NaOH to a molar concentration.

<Evaluation of alkali discoloration resistance 2>

The method for assessing the discoloration resistance of N,N-dimethyl-2-aminoethanol, which is generally used as a basic fiber auxiliary, is as follows: Deodorant sample is used by using a urethane adhesive KB- The immersion method of 3000 (manufactured by Toagosei Co., Ltd.) was processed onto a pulp/PP nonwoven fabric to a processing amount of about 1 g/m ² , and dried at 120 ° C for 30 minutes to prepare a deodorant processing cloth. A few drops of N,N-dimethyl-2-aminoethanol were dropped on a 200 cm ² piece of the processing cloth, placed in a 9 cm ² petri dish, and allowed to stand at room temperature under direct sunlight for 24 hours, and then reused. A color difference meter (Nippon Denshoku Industrial Co., Ltd. color difference meter SZ-Σ80) measures color (L, a, b), respectively. Thereafter, the color difference ΔE was obtained by comparing the colors before and after the test. The results are shown in the column of the aminoethanol of Table 2.

<Synthesis Example 1>

In a 2 L-capacity glass round bottom flask, 63.0 g of Al ₂ (SO ₄ ) ₃ ‧16H ₂ O was dissolved in 400 ml of deionized water. Further, 104.5 g of phosphoric acid (H ₃ PO ₄ ) was added, and deionized water was added to make the total amount 600 mL. This was used as a reaction liquid, and the mixture was continuously stirred at a liquid temperature of 20 ° C using a half-moon impeller (300 ° rpm) (Al/P loading ratio (atomic ratio, hereinafter the same) = 1/4).

81 g of NaOH was dissolved in 400 ml of deionized water, and the solution was added to the reaction liquid at a rate of 40 ml/min by a metering pump, and the pH was reached at the time when the pH value indicated by the glass electrode immersed in the reaction liquid reached pH=10, and further, Stir at a liquid temperature of 20 ° C for 30 minutes.

The formed precipitate (gel) was filtered through a microfilter having a pore size of 0.8 μm placed on a Buchner funnel, and washed with deionized water from above the cake to be washed until the conductivity of the filtrate was 200 μS/cm or less. .

After washing, the obtained cake was pulverized and dried in a dryer at 120 ° C for 2 hours. The dried powder was pulverized in a mortar to obtain a fine powder of aluminum/phosphorus amorphous carrier A. According to the powder X-ray diffraction analysis, it was confirmed that the carrier A was amorphous.

<Synthesis Example 2>

In a 2 L-capacity glass round bottom flask, 63.0 g of Al ₂ (SO ₄ ) ₃ ‧16H ₂ O was dissolved in 400 ml of deionized water. Further, 261.2 g of 75% phosphoric acid (H ₃ PO ₄ ) was added, and deionized water was added to make the total amount 600 mL. This was used as a reaction liquid, and the mixture was continuously stirred at a liquid temperature of 20 ° C by a half-moon impeller rotating at 300 rpm (Al/P loading ratio = 1/10).

203 g of NaOH was dissolved in 400 ml of deionized water, and the solution was added to the reaction liquid at a rate of 40 ml/min by a metering pump, and the pH was reached at the time when the pH indicating value of the glass electrode immersed in the reaction liquid reached pH=10, and further, Stir at a liquid temperature of 20 ° C for 30 minutes.

The formed precipitate (gel) was filtered through a microfilter having a pore size of 0.8 μm placed on a Buchner funnel, and washed with deionized water from above the filter cake to be washed until the conductivity of the filtrate was 200 μS/cm or less.

After washing, the obtained cake was pulverized and dried in a dryer at 120 ° C for 2 hours. The dried powder was pulverized in a mortar to obtain a fine powder of aluminum/phosphorus-based amorphous carrier B. According to the powder X-ray diffraction analysis, it was confirmed that the carrier B was amorphous.

<Synthesis Example 3>

In a 2 L-capacity glass round bottom flask, Al ₂ (SO ₄ ) ₃ ‧16H ₂ O 63.0 g was dissolved in 400 ml of deionized water. Further, 76.1 g of 75% phosphoric acid (H ₃ PO ₄ ) was added, and deionized water was added to make the total amount 600 mL. This was used as a reaction liquid, and the mixture was continuously stirred at a liquid temperature of 20 ° C by a half-moon type impeller rotating at 300 rpm (Al/P loading ratio = 1/1).

21 g of NaOH was dissolved in 400 ml of deionized water, and the solution was added to the reaction liquid at a rate of 40 ml/min by a metering pump, and the pH was reached at the time when the pH indicating value of the glass electrode immersed in the reaction liquid reached pH=10, and further, Stir at a liquid temperature of 20 ° C for 30 minutes.

The formed precipitate (gel) was filtered through a microfilter having a pore size of 0.8 μm placed on a Buchner funnel, and washed with deionized water from above the filter cake to be washed until the conductivity of the filtrate was 200 μS/cm or less.

After washing, the obtained cake was pulverized and dried in a dryer at 120 ° C for 2 hours. The dried powder was pulverized in a mortar to obtain a fine powder of aluminum/phosphorus amorphous carrier C. According to the powder X-ray diffraction analysis, it was confirmed that the carrier C was amorphous.

<Synthesis Example 4>

In a 2 L-capacity glass round bottom flask, 63.0 g of Al ₂ (SO ₄ ) ₃ ‧16H ₂ O was dissolved in 400 ml of deionized water. Further, 104.5 g of phosphoric acid (H ₃ PO ₄ ) was added, and deionized water was added to make a total amount of 600 mL (solution 1). In a container different from this, 81 g of NaOH was dissolved in 400 ml of deionized water (solution 2). While continuously stirring at a liquid temperature of 20 ° C with a half-moon impeller rotating at 300 rpm while dropping each of the solution 1 and the solution 2, the pH indicating value of the glass electrode was confirmed by a metering pump at a rate of 40 ml/min. After pH=10, after completion of the dropwise addition, the mixture was further stirred at a liquid temperature of 20 ° C for 30 minutes (Al/P loading ratio = 1/4).

The formed precipitate (gel) was filtered through a microfilter having a pore size of 0.8 μm placed on a Buchner funnel, and washed with deionized water from above the filter cake to be washed until the conductivity of the filtrate was 200 μS/cm or less.

After washing, the obtained cake was pulverized and dried in a dryer at 120 ° C for 2 hours. The dried powder was pulverized in a mortar to obtain a fine powder of aluminum/phosphorus-based amorphous carrier D. According to the powder X-ray diffraction analysis, it was confirmed that the carrier D was amorphous.

<Example 1>

4.0 g of dioxane adipate was added to 16.0 g of deionized water, and the mixture was completely dissolved by stirring at 60 ° C to obtain a 20% aqueous solution of diammonium adipate. A 20% aqueous solution of dioxane adipate was mixed in 0.8 g of aluminum/phosphorus amorphous carrier A, mixed in a mortar for 10 minutes, dried at 120 ° C for 120 minutes, and then pulverized and dried in a mortar. , deodorant A with a fine powder.

<Example 2>

A fine powder deodorant B was obtained in the same manner as in Example 1 except that the aluminum/phosphorus amorphous carrier B was used as a carrier.

<Example 3>

A fine powder deodorant C was obtained in the same manner as in Example 1 except that the aluminum/phosphorus amorphous carrier C was used as the carrier.

<Example 4>

A fine powder deodorant D was obtained in the same manner as in Example 1 except that the aluminum/phosphorus amorphous carrier D was used as a carrier.

<Comparative Example 1>

Only the ADH which does not use the carrier is used alone as the deodorizer U.

<Comparative Example 2>

A fine powder deodorant V was obtained in the same manner as in Example 1 except that a commercially available silicone rubber (Sylysia 730 manufactured by FUJI SILYSIA CHEMICAL Co., Ltd.) was used as the carrier.

<Comparative Example 3>

A commercially available zeolite (ZSM-type zeolite EX-122 manufactured by Mizusawa Chemical Co., Ltd.) was used as a carrier, and was produced in the same manner as in Example 1 to obtain a fine powder deodorant W.

<Comparative Example 4>

Adding oxalic acid and a 75% phosphoric acid aqueous solution to an aqueous solution of zirconium oxychloride, further adjusting the pH to 2.7 with caustic soda, and then heating and refluxing at 98 ° C for 12 hours, then filtering, washing, drying, and pulverizing the precipitate, that is, Get NASICON type zirconium phosphate. A fine powder deodorant X was obtained in the same manner as in Example 1 except that the NASICON-type zirconium phosphate was used as a carrier.

<Comparative Example 5>

After adding a 15% aqueous solution of zirconium dichloride to a 75% phosphoric acid aqueous solution and aging at 120 ° C for 12 hours, the precipitate was filtered, washed with water, dried, and pulverized to obtain α-type zirconium phosphate. A fine powder deodorant Y was obtained in the same manner as in Example 1 except that the α-type zirconium phosphate was used as a carrier.

<Comparative Example 6>

4.0 g of the amine hydrazine hydrochloride was added to 16.0 g of deionized water and stirred to completely dissolve to obtain a 20% aqueous solution of the amine hydrazine hydrochloride. A 20% aqueous solution of the amine hydrazine hydrochloride was mixed in 0.8 g of the aluminum/phosphorus amorphous carrier D, mixed in a mortar for 10 minutes, dried at 120 ° C for 120 minutes, and then pulverized and dried in a mortar. , a deodorant Z of a fine powder.

In Synthesis Examples 1 to 4, the ratio of Al to P in the obtained carrier was not related to the Al/P ratio at the time of charging, and was about Al/P = 1/1 (atomic ratio), and for the specific surface area, It is seen that the smaller the Al/P ratio at the time of loading, the larger the specific surface area tends to be. Further, in the synthesis example 4 in which the solution containing the Al raw material and the phosphoric acid raw material and the alkali solution were simultaneously dropped, the specific surface area was larger than that of the synthesis example 1 in which the Al/P ratio was the same.

From this result, it was found that the deodorant of the present invention is excellent in alkali discoloration resistance and water resistance, and has high deodorizing performance against aldehyde.

[Industrial availability]

The aldehyde-based gas deodorant of the present invention is excellent in deodorizing performance of an acetaldehyde monomer, and is excellent in alkali discoloration resistance and water resistance. Therefore, it can be preferably used in applications requiring a beautiful appearance such as a fiber product or a sheet. .

Claims (10)

An aldehyde-based gas deodorant characterized in that an aluminum/phosphorus-based amorphous carrier is supported on an anthracene compound. An aldehyde-based gas deodorant according to the first aspect of the invention, wherein the aluminum/phosphorus-based amorphous carrier has a BET specific surface area of from 100 m ² /g to 600 m ² /g. An aldehyde-based gas deodorant according to the first or second aspect of the invention, wherein the oxime compound is supported in an amount of from 3 to 100 parts by mass based on 100 parts by mass of the aluminum/phosphorus-based amorphous carrier. The aldehyde-based gas deodorant according to any one of claims 1 to 3, wherein the anthracene compound is a diterpene compound. The aldehyde-based gas deodorant according to any one of claims 1 to 4, wherein the hydrazine compound is dioxane adipate. The aldehyde-based gas deodorant according to any one of claims 1 to 5, wherein the aluminum/phosphorus-based amorphous carrier has an Al/P atom ratio of the aluminum salt to the phosphoric acid of 1/10 to 2/1. The range is obtained by reacting in an aqueous reaction solution, and the BET specific surface area is 100 m ² /g or more and 600 m ² /g or less. A method for producing an aldehyde-based gas deodorant according to any one of claims 1 to 6, which comprises a preparation step of preparing a reaction liquid containing a water-soluble salt of aluminum and phosphoric acid; and an adding step for the aforementioned reaction Adding a base to the liquid so that the pH of the reaction liquid reaches between 9 and 11, thereby preparing an aluminum/phosphorus amorphous carrier; and carrying the step of supporting the aluminum/phosphorus amorphous carrier Compound. The method for producing an aldehyde-based gas deodorant according to the seventh aspect of the invention, wherein the ratio of the water-soluble salt of aluminum to the phosphoric acid in the reaction liquid is in the range of 1/10 to 2/1 of the atomic ratio of Al/P. The method for producing an aldehyde-based gas deodorant according to claim 7 or 8, wherein in the adding step, the reaction liquid and the base are simultaneously dropped. The method for producing an aldehyde-based gas deodorant according to any one of claims 7 to 9, wherein the water-soluble salt of aluminum is aluminum sulfate, and the phosphoric acid is orthophosphoric acid.