JP2012120637A - Deodorizing filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorizing filter effectively exerting stable deodorizing performance to phenols, pyridines, and an aldehyde-based gas such as acetaldehyde having a large contribution as an odor component, contained in various odor components, especially much in an odor component of a tobacco smoke smell.SOLUTION: This deodorizing filter contains components (A) and (B), and has a mass ratio between a hydroxyamine compound represented by formula (1) carried in the component (A) and the component (B) of (0.065-7.4):1. The component (A): particles carried with the hydroxyamine compound represented by formula (1) wherein, Ris H, a Calkyl group, or a Chydroxyalkyl group; Ris H, a Calkyl group, or a Chydroxyalkyl group; and Rand Rare each a Calkanediyl group. The component (B): porus polymer particles obtained by copolymerizing monomer components containing (B1) a crosslinkable vinyl monomer and (B2) a vinyl monomer having a nitrogen-containing aromatic ring.

Description

  The present invention relates to a deodorizing filter, and more particularly to a deodorizing filter having a function of deodorizing bad odors included in daily odors such as tobacco odor generated in a room or other space.

  While smoking cessation in public facilities is spreading, there is still a strong demand to remove tobacco odors in public facilities that do not quit smoking, indoor spaces such as households, and in automobiles. For this reason, an increasing number of air cleaners, air conditioners, and cabin filters are provided with a deodorizing function for air circulating during operation. Many of these deodorizing functions are due to activated carbon filters that adsorb and deodorize odor molecules.

  However, only the activated carbon of the activated carbon filter has a limit in the amount of adsorption, and when the amount of adsorption reaches saturation, there is a problem that odor molecules adsorbed on the activated carbon are desorbed and re-released due to adsorption equilibrium. Therefore, there is a need for a deodorizing filter that exhibits a stable deodorizing performance effectively against odor components.

  Patent Document 1 and Patent Document 2 disclose a deodorizing filter including a solid on which a hydroxyamine compound is supported in order to exert an effective and stable deodorizing performance against aldehyde-based gas, lower fatty acid, and the like. .

  Patent Document 3 discloses deodorant particles obtained by copolymerizing a monomer component containing a crosslinkable vinyl monomer and a vinyl monomer having a heteroaromatic ring. It is disclosed that the deodorizing particles exhibit an excellent deodorizing ability with respect to phenols and sulfides.

  Patent Document 4 discloses a fabric carrying a deodorant composition containing a hydrazine derivative, porous fine particles, and a binder resin. This fabric can remove chemical substances such as aldehyde, ammonia and acetic acid, and odorous substances without impairing the texture.

JP 2010-57955 A Japanese Unexamined Patent Publication No. 2007-69198 JP 2008-111090 JP JP 2005-76145 A

  However, the odor of tobacco is a complex odor mixed with various components such as pyridines and phenols in addition to ammonia, acetaldehyde and lower fatty acids, and it can be completely deodorized with conventional deodorizing filters. I could not say.

  Therefore, the present invention exhibits a stable and deodorizing performance effectively with respect to various odor components, particularly tobacco odor, and particularly pyridine components and phenols which are contained in the odor component and greatly contribute as odor components. It is an object to provide a deodorizing filter.

  As a result of intensive studies, the present inventors have obtained deodorant particles obtained by copolymerizing particles carrying a hydroxyamine compound and monomer components containing a crosslinkable vinyl monomer and a vinyl monomer having a nitrogen-containing aromatic ring. The present inventors have found that a deodorizing filter containing s is extremely effective in solving the above-mentioned problems, and have completed the present invention.

The present invention contains the following components (A) and (B), and the mass ratio of the hydroxyamine compound represented by the general formula (1) supported in the component (A) to the component (B) is 0.065. 1 to 7.4: 1.
Component (A): particles carrying a hydroxyamine compound represented by the following general formula (1)

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or It shows a hydroxyalkyl group of 1 to 5 carbon atoms, R ³ and R ⁴ represents an alkanediyl group of 1 to 5 carbon atoms which may be the same or different. ]
Component (B): Porous polymer particles obtained by copolymerizing monomer components including components (B1) and (B2)
(B1) Crosslinkable vinyl monomer
(B2) Vinyl monomer having nitrogen-containing aromatic ring

  ADVANTAGE OF THE INVENTION According to this invention, the deodorizing filter which exhibits the stable deodorizing performance effectively with respect to various odor components, especially tobacco odor, a pyridine type gas, and a phenol type gas can be provided.

(Ingredient (A))
Hydroxyamine compound The hydroxyamine compound used as the supporting component in the component (A) is represented by the general formula (1) (hereinafter, this compound is referred to as “hydroxyamine compound (1)”). In the general formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms may be either a straight chain or branched chain, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert -A butyl group etc. are mentioned. Examples of the hydroxyalkyl group having 1 to 5 carbon atoms include a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group. Among these, R ¹ is preferably a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group, or a 2-hydroxyethyl group from the viewpoint of deodorizing performance and availability, and particularly a hydrogen atom, a hydroxymethyl group, 2- A hydroxyethyl group is preferred.

R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be linear, branched, or cyclic. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec -Butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, cyclopentyl group, cyclohexyl group and the like. Examples of the hydroxyalkyl group having 1 to 5 carbon atoms include those exemplified in the description of R ¹ . Among these, R ² is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyethyl group from the viewpoint of deodorizing performance and availability, and particularly preferably a hydrogen atom.

R ³ and R ⁴ represent an alkanediyl group having 1 to 5 carbon atoms. R ³ and R ⁴ may be the same or different, but are preferably the same. Examples of the alkanediyl group having 1 to 5 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a propane-1,2-diyl group (propylene group), a tetramethylene group, and the like, and a methylene group is particularly preferable.

  Specific examples of the hydroxyamine compound (1) include, for example, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1, 3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-hydroxyethyl-1,3-propanediol, 4-amino-4-hydroxypropyl-1,7- Heptanediol, 2- (N-ethyl) amino-1,3-propanediol, 2- (N-ethyl) amino-2-hydroxymethyl-1,3-propanediol, 2- (N-decyl) amino-1 , 3-propanediol, 2- (N-decyl) amino-2-hydroxymethyl-1,3-propanediol, and the like. Among these, from the viewpoint of deodorizing performance and the like, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3- One or more selected from propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol (tris (hydroxymethyl) aminomethane), 2-amino-2-hydroxyethyl-1,3-propanediol Particularly preferred is 2-amino-2-hydroxymethyl-1,3-propanediol. These hydroxyamine compounds can be used alone or in combination of two or more.

Carrier particles Particles used as the carrier of the hydroxyamine compound (1) in the component (A) have a mass-average particle size of 100 to 100 from the viewpoint of a good deodorizing effect and prevention of powder falling off from the nonwoven fabric fibers of the filter. It is preferably 2000 μm, more preferably 200 to 800 μm, still more preferably 200 to 600 μm. In the present specification, the mass average particle size was calculated based on 6.3 of JIS K1474 (activated carbon test method), then determined the particle size distribution based on 6.4, and further calculated based on the same item b) -7). Is.

Further, from the viewpoint of a good deodorizing effect, the particles carrying the hydroxyamine compound (1) preferably have a large specific surface area. The specific surface area of the particles, as a value by BET1 point method for calculating the amount of nitrogen adsorbed is preferably 1~3000m ² / g, more preferably 500~3000m ² / g, further 500~2500m ² / g are preferred.

  Preferable examples of such particles include activated carbon, silica, silica gel, calcium silicate, zeolite, high silica zeolite, aluminum oxide, sepiolite, zinc oxide, titanium oxide, and foamed cellulose. Among these, activated carbon, silica, silica gel, and calcium silicate are preferable, and activated carbon is particularly preferable.

-Amphoteric surfactant In addition to the hydroxyamine compound (1), the amphoteric surfactant is preferably further supported with an amphoteric surfactant from the viewpoint of deodorizing effect.

  As amphoteric surfactants, amine oxide types such as alkyldimethylamine oxide (including alkylamide type); alkylbetaine types such as laurylamino fatty acid betaine; alkyldimethylamino fatty acid betaine types; amide betaine types such as lauroylamidopropylbetaine An imidazoline type such as 2-alkyl-N-carboxymethylimidazolinium betaine, 2-alkyl-N-carboxyethylimidazolinium betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine; Amidoamine types such as 2-hydroxyethyl-N-2-lauric acid amidoethyl-β-alanine, N-2-hydroxyethyl-N-2-coconut oil fatty acid amidoethyl-β-alanine; alkyldiethylenetriaminoacetate type Can be mentioned. Among these, amine oxide type amphoteric surfactants are preferable, and alkyldimethylamine oxide is preferable, and laurylamidopropylamine-N, N-dimethyl-N-oxide and lauryldimethylamine oxide are particularly preferable.

  When the amphoteric surfactant is supported, the amount used is preferably 0.05 to 2 times, more preferably 0.1 to 1 time, and more preferably 0.2 to the mass of the hydroxyamine compound (1) from the viewpoint of a good deodorizing effect. -0.5 times is preferable.

  The amount of the hydroxyamine compound (1) supported on the carrier particles is preferably 0.001 to 3 g per gram of carrier particles, from the viewpoint of the balance between the absorption capacity of the aldehyde gas and the adsorptivity of the aldehyde gas and other malodorous components. 1 g is more preferable. When the amphoteric surfactant is further supported on the carrier, the amount of amphoteric surfactant supported is preferably 0.00005 to 6 g per 1 g of carrier particles.

Supporting method In component (A), the method for supporting the hydroxyamine compound (1) and the amphoteric surfactant on the carrier is not particularly limited, but both are dissolved or dispersed in a solvent such as water or ethanol in advance. If a solution (treatment liquid) containing is prepared, this treatment liquid is attached to a carrier and dried by heating, it can be easily and uniformly supported. The content of the hydroxyamine compound (1) and the amphoteric surfactant in the treatment liquid is preferably 0.5 to 95% by mass in total from the viewpoint of good efficiency. Further, for example, when the treatment liquid is attached to the carrier by dipping, it is preferably dipped in a mass ratio of carrier: treatment liquid = 1: 0.1 to 1:10. If the heating and drying temperature is, for example, 50 to 120 ° C., the drying can be completed in a short time.

  The solvent of this treatment liquid is preferably water or ethanol, and polyhydric alcohols, pH adjusters, other organic solvents, surfactants, and the like can be appropriately added.

  Among these, examples of the polyhydric alcohols include glycerin, ethylene glycol, propylene glycol, 1,3-propanediol, butanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol. Of these, glycerin, diethylene glycol, and dipropylene glycol are preferred. The amount of the polyhydric alcohol used is preferably 0.1 to 2 g with respect to 1 g of the hydroxyamine compound (1).

(Ingredient (B))
(B1) Crosslinkable vinyl monomer The (B1) crosslinkable vinyl monomer, which is a constituent monomer component of the porous polymer particles of the component (B), is a monomer having two or more vinyl groups. For example, divinylbenzene, trivinylbenzene, ethylene glycol di (meth) acrylate and the like can be mentioned, and divinylbenzene is preferable. The larger the proportion of the crosslinkable vinyl monomer in the monomer component, the larger the BET specific surface area. The proportion of the (B1) crosslinkable vinyl monomer in all monomer components is preferably 5% by mass or more, more preferably 20% by mass or more, and further preferably 50% by mass or more. The upper limit is preferably 98% by mass or less, and more preferably 90% by mass or less.

(B2) Vinyl monomer having a nitrogen-containing aromatic ring Component monomer component monomer component of (B) porous polymer particle (B2) A vinyl monomer having a nitrogen-containing aromatic ring is a compound having a vinyl group and a nitrogen-containing aromatic ring. Any may be used. The nitrogen-containing aromatic ring means a ring containing a nitrogen atom in addition to a carbon atom as a ring constituent atom of an aromatic ring compound, for example, one having one nitrogen atom in a ring such as pyridine, pyrrole, quinoline, imidazole, pyrimidine, pyrazine And those having two nitrogen atoms in the ring, such as pyrazole. Of these, pyridine, imidazole and pyrimidine are preferred. Examples of the vinyl monomer having a nitrogen-containing aromatic ring include 2-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, 2-vinylpyrimidine, and the like, with 2-vinylpyridine and 4-vinylpyridine being preferred.

  In order to have sufficient adsorbability for malodorous components, the proportion of the vinyl monomer having a (B2) nitrogen-containing aromatic ring in all monomer components is preferably sufficiently large, preferably 1% by mass or more, and preferably 2% by mass. The above is more preferable, and 4 mass% or more is still more preferable. In the case where the absorption effect is increased by increasing the BET specific surface area of the porous polymer particles, the proportion of the vinyl monomer having a (B2) nitrogen-containing aromatic ring in all monomer components is preferably 50% by mass or less, 30 The mass% or less is more preferable.

-Mass ratio of (B1) and (B2) From the viewpoint of deodorizing performance against malodors such as phenols, the mass ratio of (B1) crosslinkable vinyl monomer and (B2) vinyl monomer having a nitrogen-containing aromatic ring is The ratio is preferably 3: 2 to 99: 1, more preferably 1: 1 to 10: 1, and particularly preferably 2: 1 to 4: 1.

(B3) Other monomer The porous polymer particles of component (B) are used as monomer components in addition to (B1) a crosslinkable vinyl monomer and (B2) a vinyl monomer having a nitrogen-containing aromatic ring. Other monomers that can be copolymerized can be used.

  Examples of such monomers include aromatic vinyl monomers, unsaturated acid esters, and unsaturated acids. Examples of aromatic vinyl monomers include styrene, α-methyl styrene, vinyl toluene, ethyl vinyl benzene, vinyl benzyl chloride, etc., and unsaturated acid esters include methyl (meth) acrylate and ethyl (meth) acrylate. , (Meth) acrylic acid propyl, (meth) acrylic acid butyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid benzyl, (meth) acrylic acid glycidyl, etc. Examples of the saturated acid include (meth) acrylic acid. Moreover, acrylonitrile, methacrylonitrile, etc. can also be used. Of these, aromatic vinyl monomers are preferred, and styrene is particularly preferred. (B3) A monomer can be used alone or in combination of two or more.

  In the present specification, (meth) acrylate means acrylate or methacrylate, and (meth) acrylic acid means acrylic acid or methacrylic acid.

  As a preferable porous polymer particle of the component (B) from the viewpoint of deodorizing performance, a copolymer of divinylbenzene and 2-vinylpyridine can be mentioned.

The BET specific surface area of the porous polymer particles of the component (B) can be arbitrarily set depending on the ratio of the (B1) crosslinkable vinyl monomer and the selection of the organic solvent used for the polymerization. . From the viewpoint of as having a high physical consumption Nioino is at 10 m ² / g or more, preferably at least ^{50m 2 / g, 200m 2 /} g or more is more preferable. The BET specific surface area is a value determined by the BET one-point method shown in the examples below.

  The particle size of the porous polymer particles is not particularly specified, and an appropriate one can be selected according to the deodorant product to be used. However, from the viewpoint of the deodorizing effect and prevention of powder falling off from the nonwoven fabric, the volume average particle size The range of 100 to 2000 μm in diameter is preferable, the range of 200 to 800 μm is more preferable, and the range of 200 to 600 μm is more preferable.

  The porous polymer particles of the component (B) can be obtained by copolymerizing the monomer (B1) and the monomer (B2) and, if necessary, a mixture of monomer components containing the monomer (B3).

(Mass ratio of component (A) to component (B))
The filter needs to contain both component (A) and component (B). The mass ratio of the hydroxyamine compound (1) and the component (B) supported in the component (A) is 0.065: 1 to 7.4: 1, and from the viewpoint of a good deodorizing effect, 0.2: 1 to 3.6: 1 is preferable, and 0.35: 1 to 1.3: 1 is more preferable.

(Ingredient (C))
Furthermore, from the viewpoint of deodorizing various odor components in the daily odor, in addition to the components (A) and (B), the component does not carry the hydroxyamine compound (1) as the component (C), You may contain the particle | grains whose BET specific surface area is 1-3000 m < ² > / g. The particles preferably have a mass average particle size of 100 to 2000 μm, more preferably 200 to 800 μm, and still more preferably 200 to 600 μm. Further, more preferably a BET specific surface area of 500~3000m ² / g, and further preferably from 500~2500m ² / g.

  Preferable examples of such particles include activated carbon, silica, silica gel, calcium silicate, zeolite, high silica zeolite, aluminum oxide, sepiolite, zinc oxide, titanium oxide, and foamed cellulose. Preferred examples include activated carbon, silica, silica gel, calcium silicate, zeolite, high silica zeolite, and sepiolite, and activated carbon is particularly preferred.

  When component (C) is contained, the total amount of carrier particles of component (A) and component (C) from the viewpoint of the balance between the absorption capacity of the aldehyde gas and the adsorptivity of the aldehyde gas and other malodorous components The mass ratio of the hydroxyamine compound (1) supported on the component (A) to 1 is preferably 1: 0.001 to 1: 3, and more preferably 1: 0.01 to 1: 1. Further, when the amphoteric surfactant is further supported on the component (A), the mass ratio of the amphoteric surfactant to the total amount of the carrier particles of the component (A) and the component (C) is 1: 0.00005 to 1: 6 is preferred.

  The ratio of component (A), component (B), and component (C) is 1 from the viewpoint of a good deodorizing effect, regardless of whether or not component (C) is contained. In this case, the total amount of the component (A) and the component (C) is preferably 0.3 to 50, more preferably 1.5 to 50, and still more preferably 2.5 to 20 in terms of mass ratio. The mass ratio of the whole component (A) to component (B) is preferably 98: 2 to 30:70, more preferably 96: 4 to 58:42, particularly from the viewpoint of a good deodorizing effect. 90:10 to 70:30 are preferred.

[Typical configuration example]
As a typical configuration example of the deodorizing filter of the present invention, there may be mentioned, for example, a composition comprising a component (A) and a component (B) immobilized on a fiber structure constituting the filter.

  Any material can be used as the material of the fiber structure constituting the filter, but non-woven fabric, paper, or a composite thereof is preferable. Nonwoven fabrics are particularly preferred from the viewpoint of deodorizing performance. Moreover, as a fiber which comprises these fiber structures, a synthetic resin fiber, an inorganic fiber, natural pulp, etc. are mentioned.

  Specific examples of nonwoven fabrics include the spunbond method, melt blow method, centrifugal force method, flash spinning method, high voltage dry spinning method, direct production method such as film method, air lay method, card method, garnet machine (anti-hair) Non-woven fabric manufactured by a dry method such as the machine method) or a wet method similar to papermaking. Adhesive method, thermal fusion method, ultrasonic bonding method, needle punch method, span Examples include the lace method and the stitch bond method.

  Specific examples of paper include thin paper (eg, tissue paper, toilet paper, napkin, towel paper), wrapping paper, coated paper (eg, art paper, coated paper), non-coated paper, printing paper, drawings. Paper, laminated paper, Japanese paper, and the like, and cardboard such as cardboard structured paper, honeycomb structured paper, white paperboard, yellow paperboard, chipboard paper, corrugated paper, banknote base paper, and backing paper are also included.

  Specific examples of the synthetic resin fiber include polypropylene fiber, polyethylene fiber, polyethylene terephthalate fiber, polyvinyl chloride fiber, and polystyrene fiber.

  Specific examples of the inorganic fiber include alumina fiber, activated carbon fiber, carbon fiber, glass fiber, zirconia fiber, and alumina / silica fiber.

  Specific examples of natural pulp include wood pulp, bast fiber, straw pulp, bagasse pulp, straw pulp, bamboo pulp and the like.

  In addition to non-woven fabric and paper, it is also possible to use molded products such as films, sheets such as resins, metals, activated carbon and the like.

〔Production method〕
As a method for producing the deodorizing filter of the present invention,
1) Step of mixing component (A) and component (B) 2) Spreading the mixture containing component (A) and component (B) uniformly on the surface of the fiber structure constituting the filter, or fiber structure 3) Sandwiching the fibers obtained in 2) with the fibers constituting the filter, separate from the fibers in which the mixture of component (A) and component (B) is dispersed or filled on the surface. The manufacturing method including the process of pinching in the shape is preferable.

  When the component (C) is further contained in the filter, when the component (A) and the component (B) are mixed in the step 1), other components such as the component (C) are mixed at the same time, and the resulting mixture is mixed. The fiber structure constituting the filter surface may be uniformly dispersed or filled. In addition to the components (A) and (B), the component (C) may be separately dispersed or filled into the fiber structure before the step 2) or after the step 2). Further, after (C) is uniformly dispersed or filled in a fiber structure different from the fiber structure in which components (A) and (B) are dispersed or filled, components (A) and ( The fiber structure sprayed or filled with B) and the fiber structure uniformly sprayed or filled with component (C) may be sandwiched together.

  From the viewpoint of uniform distribution of the deodorant base material, when mixing component (A) and component (B) in step 1), other components such as component (C) are mixed at the same time, and the resulting mixture is A production method in which the filter surface is uniformly dispersed on the fiber surface is preferable.

  When spraying or filling component (A) and component (B) in step 2), a binder solution may be sprayed to ensure that components (A) and (B) are fixed. From the viewpoint of improving odor performance, it is preferable to fix the binder solution without spraying.

Further, the number of hydroxyamine compounds (1) and the like in the filter can be increased by laminating many layers. For example, 10 to 300 g / m ² of a mixture containing components (A) and (B), or further component (C) is fixed to a nonwoven fabric of 10 to 100 g / m ² , and 2 to 10 of these nonwoven fabrics are laminated. A deodorizing filter having excellent deodorizing performance can be obtained.

  Depending on the gas targeted by the deodorizing filter of the present invention, in addition to the components (A) and (B), and also the component (C), other deodorizing agents may be used in combination. Other deodorants may be used in the treatment liquid together with the hydroxyamine compound (1) or the like, or a treatment liquid is prepared separately from the hydroxyamine compound and the like, and the same as the treatment liquid. Or may be contained in a filter when producing a filter used for the deodorizing filter of the present invention.

Examples of other deodorants include the following (1) to (11). These other deodorants may be used alone or in combination of two or more.
(1) Metal compounds such as iron oxide, iron sulfate, iron chloride, zinc oxide, zinc sulfate, zinc chloride, silver oxide, copper oxide
(2) Lactic acid, succinic acid, malic acid, citric acid, maleic acid, malonic acid, ethylenediaminepolyacetic acid, alkane (or alkene) -1,2-dicarboxylic acid, cycloalkane (or cycloalkene) -1,2-dicarboxylic acid Acids, carboxylic acids such as naphthalene sulfonic acid; fatty acid metals such as zinc undecylenate, zinc 2-ethylhexanoate, and ricinol zinc
(3) Plant extract-type deodorants such as catechin, polyphenol, green tea extract, mushroom extract, wood vinegar, bamboo vinegar
(4) Metal chlorophyllin sodium such as iron and copper, metal phthalocyanine such as iron, copper and cobalt, tetrasulfonic acid phthalocyanine such as iron, copper and cobalt, titanium dioxide, visible light responsive titanium dioxide (nitrogen doped type, etc.) ) Catalytic deodorant
(5) Cyclodextrins such as α, β, γ-cyclodextrin, its methyl derivatives, hydroxypropyl derivatives, glucosyl derivatives, maltosyl derivatives, etc.
(6) Ester oils that are said to have a bad odor retention effect such as myristic acid esters, palmitic acid esters, phthalic acid esters, adipic acid esters, sebacic acid esters, citrate esters, etc.
(7) Polymers such as acrylic acid polymer, maleic acid polymer, naphthalenesulfonic acid formalin condensate, aromatic sulfonic acid formalin condensate
(8) Acrylic acid polymers such as porous methacrylic acid polymers and porous acrylic acid polymers, aromatic polymers such as porous divinylbenzene polymers, and synthetic porous polymers such as copolymers thereof
(9) Natural porous polymers such as chitin and chitosan
(10) Metal-supported porous materials such as silver-supported zeolite, silver-supported cancrinite, silver-supported porous styrene-divinylbenzene-vinylpyridine polymer

  Other functional agents such as antibacterial agents, fungicides, antiviral agents, insect repellents, fragrances and the like can be used in combination according to various applications.

[Use]
The deodorizing filter of the present invention can be used in a field where a deodorizing effect on daily malodors such as tobacco odor, body odor, cooking oil odor and excrement odor is desired. The deodorizing filter of the present invention is particularly effective for tobacco odor, pyridine gas, and phenol gas.

  As a specific use of the deodorizing filter of the present invention, as a device using electric power, an air cleaner for home use, facility use, automobile, air conditioner, battery type deodorant, outlet type deodorant Examples of devices that do not use electric power include household and facility ventilation-type deodorant filters, stationary deodorants, and the like.

  The deodorizing filter of the present invention is integrated with a filter such as a HEPA filter for removing particles, a filter such as a catechin filter for antibacterial and antiviral purposes when mounted on an air cleaner or an air conditioner. You can also.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited by these Examples.

[Production Example 1: Production of (divinylbenzene / 2-vinylpyridine) copolymer porous particle (B) -1]
To a 4 L SUS reaction vessel, 1596 g of a 0.19 mass% aqueous solution of polyvinyl alcohol (Gohsenol EG-40, manufactured by Nippon Synthetic Chemical Co., Ltd.) was added. On the other hand, 11 g of 2,2'-azobis (2,4-dimethylazovaleronitrile) is dissolved in a mixed solution of 148 g of 2-vinylpyridine, 445 g of divinylbenzene (purity 81%) and 296 g of heptane and mixed until uniform. This was added to the reaction vessel. Using an anchor blade, the polymerization reaction was carried out at 60 ° C. for 6 hours while stirring the reaction solution at 190 rpm to obtain a dispersion of polymer particles. This dispersion was filtered and further dried to obtain 584 g of polymer particles (hereinafter referred to as “particle (B) -1”). The resulting polymer particles had a volume average particle size of 393 μm and a BET specific surface area of 237 m ² / g.

  The BET specific surface area was determined by the BET 1-point method using Flowsorb 2300 (manufactured by Shimadzu Corporation). The adsorbed gas used was 30% by volume of nitrogen and 70% by volume of helium. As a sample pretreatment, the adsorbed gas was circulated at 120 ° C. for 10 minutes. Thereafter, the cell containing the sample was cooled with liquid nitrogen, heated to room temperature after completion of adsorption, and the surface area of the sample was determined from the amount of desorbed nitrogen. The specific surface area was determined by dividing the mass of the sample.

  LA-920 (manufactured by Horiba) was used for measuring the volume average particle diameter of the polymer particles. For the average particles, ethanol was used as a dispersion medium, and the volume average particle diameter was measured with a relative refractive index of 1.20 + 0.00i.

[Production Example 2: Production of hydroxyamine compound-supported particles (A) -1]
2-Amino-2-hydroxymethyl-1,3-propanediol was dissolved in ion-exchanged water so as to have the following formulation. This aqueous solution is referred to as “treatment liquid X”.
<Treatment solution X>
2-Amino-2-hydroxymethyl-1,3-propanediol 6% by mass
Ion exchange water balance
Total 100% by mass

Activated charcoal (mass average particle diameter 400 μm, specific surface area: 1950 m ² / g): Treated liquid X was impregnated with activated carbon at a ratio of 1: 3, and dried at 80 ° C. for 2 hours. An amino-2-hydroxymethyl-1,3-propanediol-supported activated carbon (hereinafter referred to as “particle (A) -1”) was obtained.

[Production Example 3: Production of hydroxyamine compound-supported particles (A) -2]
2-Amino-2-hydroxymethyl-1,3-propanediol and laurylamidopropylamine-N, N-dimethyl-N-oxide were dissolved in ion-exchanged water so as to have the following formulation. This aqueous solution is referred to as “treatment liquid Y”.
<Processing liquid Y>
2-Amino-2-hydroxymethyl-1,3-propanediol 6% by mass
Laurylamidopropylamine-N, N-dimethyl-N-oxide 1.7% by mass
Ion exchange water balance
Total 100% by mass

Activated carbon (mass average particle diameter 400 μm, specific surface area: 1950 m ² / g): Treated liquid Y was impregnated with activated carbon at a ratio of 1: 3, and then dried at 80 ° C. for 2 hours. Activated carbon (hereinafter referred to as “particle (A) -2”) carrying amino-2-hydroxymethyl-1,3-propanediol and an amine oxide type surfactant was obtained.

Examples 1-11
Particle (A) -1 or particle (A) -2 and particle (B) -1 were mixed at a ratio shown in Table 1 and uniformly dispersed by a disperser. The obtained mixture was uniformly laminated on a needle punched nonwoven fabric (PET fiber, PP / PE fiber mixed cotton, 65 g / m ² ) so as to correspond to 280 g / m ² to obtain a deodorant sheet. This sheet was sandwiched between needle punched nonwoven fabrics and subjected to filter processing.

Examples 12-15
In addition to particles (A) -2 and particles (B) -1, activated carbon (mass average particle size 400 μm, specific surface area: 1830 m ² / g) not supporting a hydroxyamine compound is mixed in the proportions shown in Table 1. And uniformly dispersed with a disperser. The resulting mixture was uniformly laminated on a needle punched nonwoven fabric (PET fiber, PP / PE fiber blended cotton, 65 g / m ² ) so as to correspond to 280 g / m ² to obtain a deodorant sheet. This sheet was sandwiched between needle punched nonwoven fabrics and subjected to filter processing.

Comparative Example 1
A deodorizing sheet was prepared and filtered in the same manner as in Example 5 except that only the particles (A) -2 were uniformly dispersed on the nonwoven fabric.

Comparative Example 2
A deodorant sheet was produced and filtered in the same manner as in Example 5 except that only the particles (B) -1 were uniformly dispersed on the nonwoven fabric.

Comparative Examples 3-4
A deodorizing sheet was prepared and filtered in the same manner as in Example 5 except that the particles (A) -2 and the particles (B) -1 were mixed at the ratio shown in Table 1.

Comparative Example 5
Instead of particles (B) -1, (styrene / divinylbenzene) copolymer porous particles (Mitsubishi Chemical Co., Ltd .: trade name Sepa beads SP207, volume average particle size 400 μm (produced by pulverizing commercial products), specific surface area 630 m ² / g) was used in the same manner as in Example 7 except that a deodorizing sheet was prepared and subjected to filter processing.

Comparative Example 6
A deodorizing sheet was produced in the same manner as in Example 12 except that particles (A) -2 and activated carbon not supporting a hydroxyamine compound were mixed in the proportions shown in Table 1, and subjected to filter processing.

Comparative Example 7
In place of particles (A), polyethyleneimine (Epomin manufactured by Nippon Shokubai Co., Ltd .: product number P-1000 (amine number 18 mmol / g) was added to 0.083 g per gram of activated carbon (mass average particle size 400 μm, specific surface area: 1950 m ² / g) ( An amine value equivalent to 1.49 mmol / g; the same amine value as the amount of 2-amino-2-hydroxymethyl-1,3-propanediol added in solution X) was used to produce a deodorant sheet in the same manner as in Example 6. Then, filter processing was performed.

Comparative Example 8
A deodorizing sheet was prepared in the same manner as in Example 12 except that poly (divinylbenzene / 2-vinylpyridine) copolymer porous particles and activated carbon not supporting a hydroxyamine compound were mixed in the proportions shown in Table 1. Filter processing was performed.

Test Example 1 Evaluation of Odor Strength 0.5 cm of tobacco (cut from the filter portion) was burned in an evaluation box of 2 m ³ . After 5 minutes from the start of combustion, the cigarette was taken out, the deodorizing filters obtained in Examples 1 to 15 and Comparative Examples 1 to 8 were attached to a commercial air cleaner, and the medium mode (air flow 2.0 m / sec) in the evaluation box For 5 minutes. Then, the sensory evaluation of the odor in an evaluation box was performed from the smell window of the evaluation box. The sensory evaluation was performed by six odor judgers, and evaluated in 0.5 increments using the 6-step odor intensity described below, and an average value was adopted.
The results are shown in Table 1.

・ Odor intensity evaluation criteria 0: Odorless 1: Smell that can be finally detected 2: Weak odor that shows what odor is present 3: Smell that can be easily detected 4: Strong odor 5: Strong odor

[Method of evaluating comfort level]
In a 2 m ³ evaluation box, 0.5 cm of tobacco (cut from the filter part) was burned. After 5 minutes from the start of combustion, the cigarette was taken out, and the deodorizing filters obtained in Examples 1 to 15 and Comparative Examples 1 to 8 were attached to a commercial air cleaner and operated in a medium mode (air flow 2.0 m / sec). After the minute operation, the sensory evaluation of odor in the evaluation box was performed from the sniff window of the evaluation box. The sensory evaluation was performed by 6 odor judgers, and was evaluated in 0.5 increments according to the 7-step pleasantness degree described below, and an average value was adopted. The results are shown in Table 1.

<Pleasure and discomfort evaluation criteria>
-4: Extremely uncomfortable -3: Very uncomfortable -2: Uncomfortable -1: Slightly uncomfortable 0: Not pleasant or uncomfortable 1: Slightly pleasant 2: Comfortable

  From Table 1, the absolute amount of each of the component (A) and the component (B) is smaller than the comparative example 1 having the largest absolute amount of the component (A) and the comparative example 2 having the largest absolute amount of the component (B). However, it can be clearly seen that the embodiment combined at a specific ratio has a greater effect of tobacco odor deodorization.

Test Example 2 Evaluation of deodorizing effect for each odor component Tobacco 0.5 cm (cut from the filter portion) was burned in a 2 m ³ evaluation box. 5 minutes after the start of combustion, the cigarette was taken out, the deodorizing filter obtained in Example 12 and Comparative Example 6 was attached to a commercial air cleaner, and it was operated for 5 minutes in the evaluation box in the medium mode (air flow 2.0 m / sec). I let you. Thereafter, 3 L of the odor in the evaluation box was collected in a Tedlar bag. This is the original odor. This original odor was diluted with odorless air by the descending method of 3-fold, 10-fold, 30-fold, 100-fold, 300-fold, 1000-fold, 3-fold and 10-fold dilution series, respectively. 1 L of diluted odor was adsorbed on Tenax TA Adsorbent (registered trademark, manufactured by GERSTEL), separated by smell sniffing gas chromatography, and the presence or absence of odors of pyridine-based gas and phenol-based gas was determined at the analyzed dilution ratio. .
The evaluation of the presence or absence of odor was performed by three odor judgers, and the dilution ratio at which the odor of pyridine and guaiacol as phenolic gas were not felt was measured.
The results are shown in Table 2.

Test Example 3 Evaluation of deodorizing effect every hour 0.5 cm of tobacco (cut from the filter portion) was burned in an evaluation box of 2 m ³ . After 5 minutes from the start of combustion, the cigarette was taken out, the deodorizing filter obtained in Example 12, Comparative Example 6 and Comparative Example 8 was attached to a commercial air cleaner, and the medium mode (air flow 2.0 m / sec) in the evaluation box For 3 minutes, 5 minutes, 15 minutes, and 60 minutes. Then, the sensory evaluation of the odor in an evaluation box was performed from the smell window of the evaluation box.
The sensory evaluation was performed by 6 odor judgers, and evaluated in 0.5 increments by the 7-step pleasant odor intensity described below, and an average value was adopted. The results are shown in Table 3.

・ Odor intensity evaluation criteria 0: Odorless 1: Finally an odor that can be sensed 2: A weak odor that tells what smell it is 3: An odor that can be easily detected 4: An intense odor 5: An intense odor

Claims (7)

The following components (A) and (B) are contained, and the mass ratio of the hydroxyamine compound represented by the general formula (1) carried in the component (A) and the component (B) is from 0.065: 1 to 7.4. : 1 deodorant filter.
Component (A): particles carrying a hydroxyamine compound represented by the following general formula (1)

[Wherein, R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or It shows a hydroxyalkyl group of 1 to 5 carbon atoms, R ³ and R ⁴ represents an alkanediyl group of 1 to 5 carbon atoms which may be the same or different. ]
Component (B): Porous polymer particles obtained by copolymerizing monomer components including components (B1) and (B2)
(B1) Crosslinkable vinyl monomer
(B2) Vinyl monomer having nitrogen-containing aromatic ring   The deodorizing filter according to claim 1, wherein the carrier particles in the component (A) have a mass average particle diameter of 100 to 2000 µm. The deodorizing filter according to claim 1 or 2, wherein the specific surface area of the carrier particles in component (A) is 1 to 3000 m ² / g.   The deodorant according to any one of claims 1 to 3, wherein the component (A) is obtained by further supporting an amphoteric surfactant on activated carbon supporting the hydroxyamine compound represented by the general formula (1). filter.   The deodorizing filter according to any one of claims 1 to 4, wherein the component (B) is (divinylbenzene / 2-vinylpyridine) copolymer porous particles.   The deodorizing filter according to any one of claims 1 to 5, wherein the component (B) has a volume average particle diameter of 200 to 1000 µm. The deodorizing filter according to any one of claims 1 to 6, further comprising particles having a specific surface area of 1 to 3000 m ² / g not supporting a hydroxyamine compound.