JP7537719B2 - Deodorizer - Google Patents

Description

The present invention relates to a deodorizing agent for various malodors. More specifically, it relates to a deodorizing agent for unpleasant odors in the home or living space, including organic acid gases, aldehyde gases, lower fatty acid gases, etc.

In recent years, with the improvement of the quality of living environments, houses have become more airtight, but on the other hand, this leads to odors being more easily trapped, and people become more sensitive to these odors. In the home, for example, there are cigarette odors, aging odors, body odors, pet odors, toilet odors, food waste odors, cooking odors, foot and shoe odors, furniture odors, and odors from interior materials, which are major problems in creating a more comfortable living environment. Therefore, there is a demand for more advanced performance in deodorizing agents, which are one of the solutions.
Conventional methods for reducing bad odors include masking unpleasant odors with aromatics (Patent Document 1, etc.), physically adsorbing and reducing odors using porous substances such as activated carbon and zeolite (Patent Document 2, etc.), oxidizing and removing odors using generated ozone, chemically reacting with odorous substances to remove them, and using organisms to decompose and deodorize odorous substances, and various types of these methods have been commercialized.
Unpleasant odors are diverse, and the known causative substances include organic acids, aldehydes, sulfur-containing organic substances, amines, esters, alcohols, etc. Malodors are complex odors consisting of multiple components, either alone or in combination, and have various chemical and physical properties.
There are almost no deodorants that are universally and immediately effective against these odors, and in reality, deodorants that are effective against specific odor components are used alone or in combination depending on the application.

Publication number 61-196961 Japanese Patent Application Publication No. 05-103823

Among the wide variety of unpleasant substances, organic acids and aldehydes are widely contained in tobacco odors (ammonia, isovaleric acid, acetaldehyde), sweat odors (lower fatty acids), sebum odors (aliphatic aldehydes), shoe and foot odors (acetic acid, n-valeric acid, isovaleric acid), aging odors (2-nonenal), etc. Sulfur-based compounds (hydrogen sulfide, methyl mercaptan, etc.) are found in toilet odors, food waste odors, cooking odors, etc.
The deodorizing agents that are widely used for these purposes are either physical methods using porous substances (such as activated carbon or zeolite) or chemical methods using substances with reactive substituents (basic amines, etc.) against acids or aldehydes. However, each has its advantages and disadvantages. For example, they are effective immediately after use, but quickly disappear and do not last long, or they last to a certain extent but have a low deodorizing effect.

In light of the above-mentioned circumstances, the present invention was developed after extensive research into deodorants, particularly for organic acids, aldehydes, sulfur-based compounds, and the like, and it was discovered that polyvinylamine crosslinked polymer particles can deodorize and eliminate odors extremely quickly and efficiently. The present invention will be described in detail below.

The deodorant containing the polyvinylamine crosslinked polymer particles of the present invention is a solid type product, which is easier to handle than liquid or gel type products and can deodorize a wide variety of odorous components extremely quickly and efficiently.

The deodorant containing the polyvinylamine crosslinked polymer particles of the present invention is used to remove odorous components from the environment or space surrounding an article that emits odorous components. Examples of odorous components include nitrogen compounds such as ammonia and amines (e.g., trimethylamine), sulfur compounds such as hydrogen sulfide, methyl mercaptan, and dimethyl sulfide, lower fatty acids such as acetic acid, isovaleric acid, and caproic acid, and aldehydes such as formaldehyde, acetaldehyde, hexanal, octanal, nonanal, and nonenal.
The deodorants can be used in a variety of forms, depending, for example, on the particular application: They can be loosely dispersed in a tray or can be contained in a gas-permeable container or cartridge that is placed in the odor-releasing environment.
It may also be used in paper pouches of the type used to package, for example, silica gel and calcium oxide that are commonly found in moisture absorbing packaging products.
Furthermore, it can be used as an adsorption filter for odor components by supporting (holding) it on a mesh-like member made of, for example, a nonwoven sheet made of synthetic or natural fibers, paper, metal, plastic, sponge, etc. In particular, an adsorption filter in which the deodorant is supported on a mesh-like member is effective. There are no particular limitations on the method of supporting it, and examples include a method of coating it with a binder, a method of sandwiching it between multiple sheets, and the like.

This deodorizing agent can be used alone, or in combination with other deodorizing agents, such as inorganic deodorizing agents such as activated carbon, titanium oxide, zeolite, and silicates, natural product deodorizing agents such as used tea leaves and green tea extract, and organic deodorizing agents such as phosphoric acid, in any ratio.

Places where it can be used include residential spaces in the home such as the living room, kitchen, entrance, toilet, bathroom, and washroom, but there are no particular limitations and it can be used in any place where the odor components are generated and detected, such as offices, car cabins, facilities, factories, etc.

The method for producing the polyvinylamine crosslinked polymer particles of the present invention will be described below.

In the present invention, the method for producing the polyvinylamine crosslinked polymer particles is first to apply suspension polymerization, which is commonly used. That is, N-vinyl carboxylic acid amide, a polyvinyl compound, if necessary a monomer capable of copolymerizing with N-vinyl carboxylic acid amide, a specific organic solvent, a polymerization initiator, and a cationic polymer dispersant are suspended in salt water, stirred at an arbitrary intensity to generate monomer droplets, and then radical polymerization is carried out to produce the particles. The particle size of the monomer droplets is controlled by the dispersant and stirring intensity, and is 0.01 mm to 10 mm, preferably 0.1 mm to 5 mm.

Examples of N-vinyl carboxylic acid amide monomers used in the present invention include N-vinylformamide, N-methyl-N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinylpropionamide, N-methyl-N-vinylpropionamide, N-vinylbutylamide, N-vinylisobutylamide, etc., with N-vinylformamide being preferred. In addition to the N-vinyl carboxylic acid amide monomer, a monomer capable of copolymerizing with N-vinyl carboxylic acid amide may be used, and examples thereof include (meth)acrylonitrile, (meth)acrylamide, N-alkyl (meth)acrylamide, N,N'-dialkyl (meth)acrylamide, N,N'-dialkyl amino alkyl (meth)acrylamide, alkali metal salt or ammonium salt of (meth)acrylamido alkane sulfonic acid, alkali metal salt or ammonium salt of (meth)acrylic acid, hydroxyalkyl (meth)acrylate, dialkyl amino alkyl (meth)acrylate, (meth)acryloyloxy alkyl trimethyl ammonium salt, alkali metal salt or ammonium salt of (meth)acryloyloxy alkane sulfonic acid, N-vinyl pyrrolidone, diallyl dialkyl ammonium salt, vinyl pyridine, vinyl imidazole, vinyl benzyl trialkyl ammonium salt, alkali metal salt or ammonium salt of vinyl sulfonic acid, and the like. One of these may be used, or two or more may be combined. Acrylonitrile is particularly preferred.

As the polyvinyl compound, aromatic polyvinyl compounds such as divinylbenzene, trivinylbenzene, and divinyltoluene, poly(meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate, and methylene bisacrylamide can also be used. It is preferable to use aromatic divinyl compounds. Divinylbenzene is the most preferable. The addition rate is in the range of 0.1 to 50% by mass relative to the monomer, and preferably in the range of 0.1 to 20% by mass. If it exceeds 5% by mass, it becomes difficult to obtain spherical particles using only N-vinyl carboxylic acid amide, so it is preferable to use a monomer that can be copolymerized with N-vinyl carboxylic acid amide. The addition rate of the copolymerizable monomer is used in the range of 50% by mass or less relative to the total monomers. It is particularly preferable to use acrylonitrile.

Polymerization initiators include azo and peroxide polymerization initiators, such as 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis-2-amidinopropane hydrochloride, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis[2-(5-methyl-imidazolin-2-yl)propane]hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]hydrochloride, ammonium or potassium peroxodisulfate, hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, succinic peroxide, and t-butylperoxy-2-ethylhexanoate. Among these, oil-soluble initiators such as 2,2'-azobis(2,4-dimethylvaleronitrile) and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) are preferred. Two or more initiators may be used in combination. The addition rate is usually 0.02 to 5% by mass, preferably 0.05 to 2% by mass, based on the monomer.

The cationic polymer dispersant is a polymer of cationic monomers such as (meth)acryloyloxyethyltrimethylammonium chloride and dimethyldiallylammonium chloride, but copolymers of these cationic monomers and nonionic monomers can also be used. Examples of nonionic monomers include acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N,N'-dimethylacrylamide, acrylonitrile, diacetoneacrylamide, and 2-hydroxyethyl (meth)acrylate. The weight-average molecular weight of the cationic polymer dispersant is 5,000 to 2,000,000, preferably 50,000 to 1,000,000. The addition rate is usually 0.05 to 5% by mass, preferably 0.1 to 2% by mass, based on water.

Examples of salts include ammonium sulfate, sodium sulfate, ammonium chloride, sodium chloride, calcium chloride, etc., and among these, ammonium sulfate is particularly preferred. These may be used alone or in combination. The addition rate is in the range of 30 to 100% by mass relative to the water. If it is less than 30% by mass, the N-vinyl carboxylic acid amide will not separate sufficiently into two phases, and if it is 100% by mass, the effect of the salt is sufficiently obtained, and it is uneconomical to add more than 100% by mass. It is preferably 50 to 90% by mass, and more preferably 60 to 90% by mass.

The polyvinylamine crosslinked polymer particles in the present invention preferably have a porous structure, which will be described later, in order to maximize the contact area with odorous components.
Examples of organic solvents that can be used to obtain polyvinyl carboxylic acid amide crosslinked polymer particles having a porous structure include alcohols such as 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tert-butanol; esters such as methyl acetate, ethyl acetate, and propyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and ethers such as ethylene glycol dimethyl ether. In addition, organic solvents having a polar group such as butoxyethanol and ethoxyethanol can be used. These organic solvents dissolve in water to some extent, but it is possible to distribute them in the monomer phase by using a high concentration salt. The amount of these organic solvents to be added is 5 to 200% by mass, preferably 10 to 100% by mass, based on the total monomers.

The polymerization reaction is usually carried out at a temperature of 30° C. to 100° C. for 1 to 15 hours.
After the polymerization, salts, cationic polymer dispersants, organic solvents, unreacted monomers, etc. can be removed by washing with water. Residual organic solvents can also be removed by distillation or the like.

The above-mentioned manufacturing method produces polyvinyl carboxylic acid amide crosslinked polymer particles. Polyvinyl amine crosslinked polymer particles can then be obtained by hydrolysis. Hydrolysis can be carried out under either basic or acidic conditions.

There are no limitations on the base suitable for hydrolysis, so long as it can set the pH to a range of 8 to 14 during hydrolysis, and it is most preferable to use an aqueous solution of sodium hydroxide, potassium hydroxide, or ammonia. The addition rate is preferably in the range of 0.05 to 2.0, and more preferably 0.4 to 1.2 equivalents relative to the formyl groups of the polymer.

There are no limitations on the acids suitable for hydrolysis as long as they can set the pH to a range of 0 to 5 during hydrolysis. Examples include inorganic acids such as hydrohalic acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as mono- and dicarboxylic acids having 1 to 5 carbon atoms, sulfonic acid, benzenesulfonic acid, and toluenesulfonic acid. In particular, it is preferable to use hydrohalic acid and hydrogen halide gas, and it is most preferable to use hydrohalic acid. The addition rate is preferably 0.05 to 2.0 equivalents relative to the formyl groups of the polymer, and more preferably 0.4 to 1.2 equivalents.

After hydrolysis, polyvinylamine crosslinked polymer particles can be obtained by washing with water, etc.

The polyvinylamine crosslinked polymer particles in the present invention are spherical particles with a particle size in the range of 10 μm to 2 mm. The specific surface area is used as an index of the porous structure. In the present invention, if the specific surface area is 1.0 m ² /g or more, it can be said that the particle has a porous structure. Crosslinked polymer particles that do not have a porous structure have a value of 0 m ² /g or close to 0 m ² /g. The specific surface area can be determined by the BET method. For example, after the crosslinked polymer spherical particles are vacuum dried, the specific surface area can be determined by the BET one-point method using Quantachrome ChemBET3000 (manufactured by Quantachrome) and 30% nitrogen + helium.

The following provides a specific description of the production examples of the polyvinylamine crosslinked polymer particles of the present invention and their effects as a deodorant, but the present invention is not limited to the following examples.

(Production Example 1)
147.1 g of demineralized water, 96.5 g of ammonium sulfate, and 3.1 g of polyacryloyloxyethyltrimethylammonium chloride aqueous solution (polymer concentration 20 mass%, weight average molecular weight 800,000) were charged into a 500 mL four-neck flask, stirred, and dissolved to prepare a polymerization bath. 49.9 g of N-vinylformamide, 4.2 g of divinylbenzene, 6.0 g of acrylonitrile, 24.1 g of 1-propanol, and 0.18 g of azo-based polymerization initiator 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed to prepare a monomer solution. The monomer solution and the polymerization bath were mixed and stirred at 275 rpm while replacing the atmosphere in the flask with nitrogen. After 30 minutes, the temperature was raised, and polymerization was carried out at 50°C for 3 hours and then at 60°C for 1 hour. After the polymerization, the mixture was filtered, washed with water and filtered again to obtain 204.1 g of hydrous, agglomerate-free spherical polymer particles.

23.5 g of the reaction product thus obtained was placed in a four-neck flask, 23.40 g of a 48% by mass aqueous solution of sodium hydroxide was added, and hydrolysis was carried out at 80° C. for 5 hours with stirring. After washing with water and filtration, 19.7 g of hydrous polyvinylamine spherical particles were obtained. As a result of observation under a microscope, spherical particles of 50 μm to 1 mm were observed. After vacuum drying, the specific surface area of the white spherical particles was measured to be 14 m ² /g, and the particles had a porous structure. The polyvinylamine crosslinked polymer particles thus obtained are designated as Sample A.

Example 1
The sample A prepared in Production Example 1 was placed in an odor sampling bag [capacity 5 L, Tedlar bag (manufactured by AS ONE Corporation)] and used as a "test measurement", while the bag without the test product was used as a "blank". 1.5 L of formaldehyde gas adjusted to a concentration of about 50 ppm was filled into the bag, and after leaving it to stand for 15, 30, and 60 minutes, the gas was sampled using a detector tube type gas sampler GV-100 [manufactured by Gastec Corporation] and the formaldehyde concentration was measured. Each sample was measured three times, and the average values are shown in Table 1.

減少率（％）＝（ブランクの濃度－試験測定の濃度）／ブランクの濃度 (Table 1)

Reduction rate (%) = (Blank concentration - Test measurement concentration) / Blank concentration

Example 2
The same procedure as in Example 1 was repeated except that acetaldehyde was used instead of formaldehyde. The test results are shown in Table 2.

(Table 2)

Example 3
The same procedures as in Example 1 were carried out except that hydrogen sulfide was used instead of formaldehyde, the concentration was adjusted to about 4 ppm, and the standing time was changed to 30 minutes, 60 minutes, and 120 minutes. The test results are shown in Table 3.

(Table 3)

Example 4
The same procedures as in Example 3 were carried out except that hydrogen sulfide was replaced with acetic acid and the concentration was adjusted to about 20 ppm. The test results are shown in Table 4.

(Table 4)

Example 5
The sample A prepared in Production Example 1 was placed in an odor sampling bag [2 L capacity, Tedlar bag, AS ONE Corporation] and used as a "test measurement", while the one without any odor was used as a "blank". 1 L of odor components with isovaleric acid adjusted to a concentration of 38 ppm was placed in both bags, and the odors were collected in Tenax TA (GL Sciences) after standing for 15, 30, and 60 minutes, and the concentration (peak area) was measured using a gas chromatograph mass spectrometer [Shimadzu Corporation GCMS-Q2010plus] by thermal desorption. Each odor was measured three times, and the average values are shown in Table 5.

減少率（％）＝（ブランクのピーク面積－試験測定のピーク面積）／ブランクのピーク面積 (Table 5)

Reduction rate (%) = (blank peak area - test peak area) / blank peak area

Example 6
The same procedures as in Example 5 were carried out except that 2-nonenal was used instead of isovaleric acid and the concentration was adjusted to 14 ppm. The test results are shown in Table 6.

Table 6

As is clear from the test results in Tables 1 to 6, the polyvinylamine crosslinked polymer particles of the present invention have extremely good deodorizing and eliminating performance against a variety of chemical substances that are the main odor components, extremely quickly and efficiently, simply by leaving them in a particulate state in the target environment for deodorization.

Claims (2)

Specific surface area is 1.0 m ² /g or more and a particle size in the range of 10 μm to 2 mm, in an environment or space surrounding an article from which the polyvinylamine crosslinked polymer spherical particles emit odorous components (excluding packing into a column), and a reduction rate of the odorous components after 30 minutes is 31% or more, and a reduction rate of the odorous components after 60 minutes is 40% or more. A method for deodorizing and eliminating odors , comprising placing an adsorption filter having the deodorizing agent according to claim 1 supported on a mesh member in an environment or space surrounding an article which releases odorous components, and achieving a reduction rate of odorous components of 31% or more after 30 minutes and 40% or more after 60 minutes.