JPWO2016060124A1 - Manufacturing method of deodorizing material - Google Patents

Abstract

Provided is a method for producing a deodorizing material which can easily provide a deodorizing material having excellent deodorizing performance. The method for producing a deodorizing material according to the present invention includes the following steps, and includes producing a deodorizing material having a breathable base material, a porous adsorbing material, and a binder binding the porous adsorbing material to the breathable base material. A method: adding a water-soluble polymer to the slurry containing the porous adsorbent; mixing a slurry containing the water-soluble polymer; adding the binder to the mixed slurry; and Applying the slurry containing the binder to the breathable substrate.

Description

  The present invention relates to a method for producing a deodorizing material.

  In the air, there are many chemical substances that can irritate various mucous membranes such as nasal mucosa, ocular mucosa, pharyngeal mucosa, and skin. Among them, volatile organic compounds (VOC) such as toluene, xylene, ethylbenzene, and styrene emanating from building materials, furniture, and daily necessities (Volatile Organic Compounds (VOC)), and highly volatile organic compounds (VV Volatile Organic Compounds) such as formaldehyde and acetaldehyde (VVOC) )) Is considered a cause of chemical sensitivity and sick house syndrome, and is therefore subject to emission regulations. VOC emissions have been declining year by year due to regulations, but health damage due to VOCs still exists, and regulations on VOC emissions have been further tightened around the world.

  According to the revised Building Standards Law enacted in July 2003, the amount of formaldehyde used in building materials was also restricted. However, the amount of acetaldehyde used as an alternative substance has been increasing rapidly in recent years. In April 2003, the Ministry of Health, Labor and Welfare issued VOC guidelines for 13 substances. Among 13 substances, the ratio of acetaldehyde exceeding the guideline value (0.03ppm) (about 40% over) (reference: 20% over toluene, over 11% over 11 other substances) is overwhelmingly large. It is a difficult substance to reduce.

  One of the means for removing these chemical substances is adsorption by a porous material such as activated carbon. For example, Patent Documents 1 and 2 disclose deodorant materials in which carbon particles such as Bincho charcoal are bonded to a polyurethane foam with an emulsion-based binder.

  Patent Documents 3 to 5 disclose deodorizing materials obtained by bonding an adsorbent such as activated carbon to a honeycomb-shaped inorganic base material using an emulsion binder. In these documents, a water-soluble polymer such as acrylamide, methylcellulose, carboxymethylcellulose or the like may be added as a viscosity modifier to a slurry containing an emulsion binder and an adsorbent.

  In Patent Document 6, a conductive fabric is used as a base material, and activated carbon is bonded using an emulsion binder and a cellulose dispersant.

  In Patent Document 7, a porous adsorbent such as activated carbon is bonded to a sheet of fiber material or the like using an emulsion binder and a thickener such as carboxymethylcellulose. Here, it is supposed that the binder and the thickener can be added simultaneously to the activated carbon-containing slurry.

JP 2004-10756 A JP 2001-164032 A JP 2007-330657 A JP 2007-296058 A JP 2005-52785 A Japanese Patent Laid-Open No. 08-260360 JP 2014-133220 A

  Conventional deodorizing materials did not have sufficient deodorizing performance.

  On the other hand, an object of this invention is to provide the manufacturing method of the deodorizing material which can provide easily the deodorizing material which has the outstanding deodorizing performance.

  The inventors of the present invention have found that the deodorizing performance of the conventional deodorizing material is insufficient because the porous adsorbent such as activated carbon clogs the pores of the porous adsorbent, and the porous resin is effective for deodorization. It is considered that the specific surface area of the material is reduced, and the present inventors have intensively studied so that the pores of the porous adsorbent are not blocked by the resin of the binder, it is excellent by a very simple manufacturing method. It has been found that a deodorizing material having high deodorizing performance can be provided.

Specifically, the present inventors have found that the above problems can be solved by the following means.
<< Aspect 1 >>
A method for producing a deodorizing material comprising a breathable substrate, a porous adsorbent, and a binder that binds the porous adsorbent to the breathable substrate, including the following steps:
Adding a water-soluble polymer to the aqueous slurry containing the porous adsorbent;
Mixing an aqueous slurry containing the water-soluble polymer;
Adding the binder to the mixed aqueous slurry; and applying the aqueous slurry containing the binder to the breathable substrate.
<< Aspect 2 >>
The water-soluble polymer is composed of sodium tripolyphosphate, sodium tetraphosphate, sodium hexametaphosphate, polyvinyl alcohol, sodium polyacrylate, polyvinyl pyrrolidone, styrene maleic acid copolymer, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and mixtures thereof. The manufacturing method of the deodorizing material of aspect 1 selected from the group.
<< Aspect 3 >>
The method for producing a deodorizing material according to aspect 2, wherein the water-soluble polymer is hydroxyethyl cellulose.
<< Aspect 4 >>
Any one of aspects 1 to 3, wherein the porous adsorbent is selected from the group consisting of activated carbon, sepiolite, palygorskite, zeolite, activated carbon fiber, activated alumina, sepiolite mixed paper, silica gel, activated clay, permiculite, and diatomaceous earth. The method for producing a deodorizing material according to one item.
<< Aspect 5 >>
Any of aspects 1 to 4 wherein the binder is selected from the group consisting of acrylic resins, acrylic-styrene resins, acrylic-silicon resins, acrylic-urethane resins, vinyl acetate-acrylic resins, polysiloxane-acrylic resins, and butadiene resins. A method for producing the deodorizing material according to claim 1.
<< Aspect 6 >>
The manufacturing method of the deodorizing material as described in any one of aspects 1-5 whose said air permeable base material is a polyurethane foam.
<< Aspect 7 >>
The manufacturing method of the deodorizing material as described in any one of aspects 1-6 in which the said air-permeable base material has several opening part which goes to the other main surface from one main surface.
<< Aspect 8 >>
The deodorizing material obtained by the method as described in any one of aspect 1-6.

  The manufacturing method of the deodorizing material of this invention can provide easily the deodorizing material which has the outstanding deodorizing performance.

It is the schematic of the process of the manufacturing method of the deodorizing material of this invention. It is the schematic of one aspect | mode of the deodorizing material obtained by this invention. It is the schematic of the apparatus for evaluating an aldehyde adsorption | suction performance. It is a figure which shows how the relationship between an activated carbon retention amount and a pressure loss changes with the case where there is an opening part in a deodorizing material, and a case where it does not exist. It is a figure which shows how the relationship between activated carbon retention amount and a deodorizing performance changes with and without the case where an opening part is in a deodorizing material.

<Production method of deodorizing material>
The deodorizing material obtained by the method of the present invention has a breathable substrate, a porous adsorbent, and a binder that binds the porous adsorbent to the breathable substrate. In the method of the present invention, this deodorizing material is produced by going through at least the following steps: a step of adding a water-soluble polymer to a slurry containing a porous adsorbent; and a slurry containing a water-soluble polymer. A step of adding a binder to the mixed slurry; and a step of applying the slurry containing the binder to the breathable substrate. As outlined in FIG. 1, the method of the present invention preferably includes mixing the slurry after adding the binder to the slurry and before applying to the breathable substrate. More preferably, the method of the present invention includes a step of drying the slurry after applying the slurry containing the binder to the substrate.

  As shown in the following examples, the present inventors have found that the deodorizing material thus obtained gives unexpectedly high deodorizing performance. The reason why this deodorizing material has an unexpectedly high deodorizing performance is not limited by theory, but is considered as follows.

  Although the deodorizing material obtained by the conventional manufacturing method has a certain deodorizing performance, the performance is lower than the deodorizing performance expected from the adsorbent alone. This may be due to the fact that the binder resin clogs the pores of the porous adsorbent. However, in the production method of the present invention, by adding the water-soluble polymer to the slurry before adding the binder, the water-soluble polymer functions as a surface protective agent for the porous adsorbent, and the pores formed by the binder are removed. It is thought that occlusion was prevented.

  Conventionally, it has been known to add a water-soluble polymer to a slurry containing a porous adsorbent and a binder when producing a deodorizing material using a breathable substrate. However, the water-soluble polymer used in this case was used as a dispersant for the porous adsorbent in the slurry. In this case, since the addition of the water-soluble polymer to the slurry was performed almost simultaneously with the addition of the binder to the slurry, it is considered that the water-soluble polymer could not function as a surface protective agent for the porous adsorbent. . As shown in the following examples, when the water-soluble polymer is mixed as a surface protective agent for the porous adsorbent before mixing the binder into the slurry, the obtained deodorant is deodorized. The performance was significantly improved.

  In the method of the present invention, this slurry is then mixed to obtain a substantially homogeneous slurry so that the water-soluble polymer is adsorbed on the surface of the porous adsorbent. In this case, the slurry can be stirred and mixed for a sufficient time and force, and depending on the type of the water-soluble polymer and the porous adsorbent, it may be homogenized using a powerful mixer or the like. For example, in the mixing of the water-soluble polymer, after adding the water-soluble polymer to the slurry containing the porous adsorbent, the whole slurry is 5 seconds or longer, 10 seconds or longer, 30 seconds or longer, 1 minute or longer, or 10 minutes or longer. Can be carried out by stirring.

  A binder is added to the slurry thus obtained. Here, the binder is preferably in the form of an emulsion. Preferably, after adding the binder, they are mixed by stirring or the like.

  By applying the slurry thus obtained to the substrate and drying it, the porous adsorbent can be bonded to the substrate via a binder. This application can be carried out, for example, by applying, impregnating, or coating a slurry to the substrate.

(Water-soluble polymer)
The water-soluble polymer used in the production method of the present invention is not particularly limited as long as it is a water-soluble polymer. It is considered that by adding a water-soluble polymer before adding the binder to the slurry in which the porous adsorbent is dispersed, it is adsorbed on the surface of the porous adsorbent. Thereby, the dispersibility of the porous adsorbent in the slurry can be improved, and even when a binder is added to the slurry, the binder can be prevented from entering the pores of the porous adsorbent at least to some extent. it is conceivable that.

  Examples of such water-soluble polymers include synthetic polymer-based water-soluble polymers such as sodium tripolyphosphate, sodium tetraphosphate, sodium hexametaphosphate, polyvinyl alcohol, sodium polyacrylate, polyvinyl pyrrolidone, and styrene maleic acid copolymer. Or cellulose derivative-based water-soluble polymers such as methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, or salts thereof (for example, sodium salts). Among these, hydroxyethyl cellulose and carboxymethyl cellulose are particularly preferable.

  The breathable substrate to which the slurry is applied can be dried for a predetermined time after application. For example, this drying step can be performed at 150 ° C. or lower, 110 ° C. or lower, or 80 ° C. or lower until the slurry dispersion medium is substantially eliminated.

  The amount of the water-soluble polymer added can be, for example, 0.1% by weight or more, 0.5% by weight or more, 1.0% by weight or more, or 2.0% by weight or more with respect to the porous adsorbent. And 30 wt% or less, 20 wt% or less, 15 wt% or less, or 10 wt% or less, but is not limited to this range.

(Porous adsorbent)
The porous adsorbent used for the deodorizing material obtained in the present invention is not particularly limited as long as it has deodorizing performance. The porous adsorbent may be a physical adsorbent, or the physical adsorbent carries a chemical adsorbent, i.e., an adsorbent that adsorbs an adsorbed component by forming a chemical bond with the adsorbed component. May be. While the physical adsorbent has a high adsorption rate, it has the property of easily desorbing the adsorption target, and the chemical adsorbent is difficult to desorb the adsorption target once adsorbed, while the adsorption rate is It has the property of being low.

  As the porous adsorbent that is a physical adsorbent, any adsorbent having a large number of pores can be used, and for example, an inorganic porous adsorbent can also be used.

  Specific examples of the inorganic porous adsorbent include activated carbon, sepiolite, palygorskite, zeolite, activated carbon fiber, activated alumina, sepiolite mixed paper, silica gel, activated clay, permiculite, and diatomaceous earth. Among these porous adsorbents, activated carbon is preferable because it has excellent adsorption performance for various adsorbed components, particularly toluene.

The shape of the inorganic porous adsorbent is not particularly limited as long as the gas to be treated can be contacted. For example, a granular, powdery, or fibrous porous adsorbent can be used. The particle size (median diameter: D ₅₀ ) of the porous adsorbent is preferably small, for example, for slurry formation, and may be, for example, 150 μm or less, 100 μm or less, 50 μm or less, or 25 μm or less. In general, the BET specific surface area of the porous adsorbent is preferably as large as possible, and may be, for example, 400 m ² / g or more, 500 m ² / g or more, or 1000 m ² / g or more.

  As the chemical adsorbent that the porous adsorbent may carry, any chemical adsorbent that can adsorb the adsorbed component by forming a chemical bond with the intended adsorbed component can be used. Moreover, as a chemical adsorbent, one type or a plurality of types can be used.

  For example, when the intended adsorbed component is an aldehyde, one or a plurality of azole compounds and / or hydrazide compounds can be used as the chemical adsorbent. As used herein, an “azole compound” is a five-membered aromatic compound containing at least one heteroatom, wherein at least one of the heteroatoms is a nitrogen atom, particularly aldehydes. Meaning such compounds having the desired adsorption properties. Also, as used herein, “hydrazide compound” means a compound having one or more hydrazide groups, in particular such a compound having desired adsorption properties for aldehydes.

  The azole compound includes diazole, triazole, tetraazole and the like, specifically, 3-methyl-5-pyrazolone, 1,3-dimethyl-5-pyrazolone, 3-methyl-1-phenyl-5-razolone. Pyrazolone compounds such as 3-phenyl-6-pyrazolone and 3-methyl-1- (3-sulfophenyl) -5-pyrazolone; pyrazole, 3-methylpyrazole, 1,4-dimethylpyrazole, 3,5-dimethylzole 3,5-dimethyl-1-phenylpyrazole, 3-aminopyrazole, 5-amino-3-methylpyrazole, 3-methylpyrazole-5-carboxylic acid, 3-methylpyrazole-5-methyl carboxylate, 3-methyl Pyrazoles such as pyrazole-5-carboxylic acid ethyl ester and 3,5-methylpyrazole dicarboxylic acid Compound: 1,2,3-triazole, 1,2,4-triazole, 3-n-butyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 3,5 -Di-n-butyl-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole 3,5-diamino-1,2,4-triazole, 5-amino-3-mercapto-1,2,4-triazole, 3-amino-5-phenyl-1,2,4-triazole, 3,5 -Diphenyl-1,2,4-triazole, 1,2,4-triazol-3-one, urazole (3,5-dioxy-1,2,4-triazole), 1,2,4-triazole-3- Carboxylic acid, 1-hydroxybenzo Triazole compounds such as riazole, 5-hydroxy-7-methyl-1,3,8-triazaindolizine, 1H-benzotriazole, 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole, 2- Amino-5-ethyl-1,3,4-thiadiazole, 5-amino-2-mercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, 5-t-butyl- Examples include thiadiazole compounds such as 2-methylamino-1,3,4-thiadiazole, 2-amino-5-methyl-1,3,4-thiadiazole, and 2-amino-1,3,4-thiadiazole.

  As the azole compound, in particular, 3-aminopyrazole, 5-amino-3-methylpyrazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3,5-diamino- 1,2,4-triazole, 5-amino-3-mercapto-1,2,4-triazole, 3-amino-5-phenyl-1,2,4-triazole 2-amino-5-ethyl-1,3 , 4-thiadiazole, 5-amino-2-mercapto-1,3,4-thiadiazole, 5-t-butyl-2-methylamino-1,3,4-thiadiazole, 2-amino-5-methyl-1, 3,4-thiadiazole and 2-amino-1,3,4-thiadiazole are preferred, and 4-amino-1,2,4-triazole is preferred.

  As the hydrazide compound, a monohydrazide compound, a dihydrazide compound, a trihydrazide compound, preferably a dibasic acid dihydrazide is preferable, and more preferably, adipic acid dihydrazide, sebacic acid dihydrazide, or the like can be used.

  The method for supporting the chemical adsorbent on the porous adsorbent is not particularly limited. For example, after dissolving the chemical adsorbent in water or other solvent, the porous adsorbent is immersed in the obtained chemical solution. Support may be performed.

The loading amount of the chemical adsorbent can be appropriately determined according to the intended type and concentration of the adsorbed component. For example, the loading amount of the chemical adsorbent can be 0.04 μmol to 1 μmol, or 0.06 μmol to 0.8 μmol per 1 m ² of the BET specific surface area of the porous adsorbent. That is, for example, 4 to 100 μmol or 6 to 80 μmol of a chemical adsorbent can be used for 100 g of a porous adsorbent having a BET specific surface area of 1000 m ² / g.

  The deodorizing material obtained by the present invention may hold a porous adsorbent in an arbitrary amount, and particularly may hold a relatively large amount of the porous adsorbent.

Deodorant obtained by the present invention, for example 0.01 g / cm ³ or more, 0.02 g / cm ³ or more, 0.03 g / cm ³ or more, 0.04 g / cm ³ or more, 0.05 g / cm ³ or more, The porous adsorbent may be held in an amount of 0.06 g / cm ³ or more, or 0.07 g / cm ³ or more. The upper limit of the retained amount of the porous adsorbent is not particularly limited as long as the pressure loss of the deodorizing material does not become too high and can be manufactured. For example, the upper limit of the holding amount of the porous adsorbent may be 0.20 g / cm ³ or less, 0.15 g / cm ³ or less, or 0.10 g / cm ³ or less.

As used herein, “the amount of porous adsorbent retained” means the weight (g) of the porous adsorbent supported per 1 cm ^{3 of the} breathable base material. In the case where the porous adsorbent contains a chemical adsorbent, the weight means the total weight including the weight of the chemical adsorbent. This retention amount can be set to a desired value by adjusting the amount of use, concentration, etc. of the slurry containing the porous adsorbent when the porous adsorbent is adhered to the breathable substrate.

  When applied to the breathable substrate, the porous adsorbent may be contained in the slurry by 3 parts by mass, 5 parts by mass, 10 parts by mass, or 20 parts by mass with respect to 100 parts by mass of the dispersion medium. , 60 parts by mass or less, 50 parts by mass or less, or 40 parts by mass or less. The dispersion medium of the slurry containing the porous adsorbent is an aqueous dispersion medium, particularly water.

(binder)
As the binder, an organic binder such as a polymer material capable of binding the porous adsorbent and the breathable substrate can be used.

  Examples of the organic binder include emulsion-based organic binders, and particularly acrylic emulsions such as acrylic resins, acrylic-styrene resins, acrylic-silicon resins, acrylic-urethane resins, vinyl acetate-acrylic resins, and polysiloxane-acrylic resins. , And latex emulsions such as butadiene resins can be used. As the binder, a binder that hardly remains in the pores of the porous adsorbent, for example, an aqueous acrylic resin is preferable.

  The added amount (solid content) of the binder is, for example, 3% by weight or more, 5% by weight or more, 10% by weight or more, or 20% by weight or more, and 200% by weight or less, 150% by weight or less with respect to the porous adsorbent. Although it may be 100% by weight or less, or 60% by weight, it is not limited to this range.

(Breathable substrate)
The breathable substrate for the deodorizing material obtained by the present invention is not particularly limited as long as it has breathability with respect to the gas to be treated. As the air-permeable base material, a material that can penetrate the slurry containing the porous adsorbent into the base material in the production process is preferable. In addition, the breathable base material is relatively rough, so that when the deodorizing material of the present invention is used, the gas to be treated containing the adsorbed component reaches the inside of the breathable base material, and is adsorbed. It is preferred to promote contact between the component and the porous adsorbent on or inside the substrate.

  Specific examples of the breathable substrate include foamed resin, reticulated resin, porous resin film, knitted fabric, woven fabric, non-woven fabric, paper, and inorganic fiber. As the material, synthetic fibers such as polyethylene, polypropylene, polyurethane, nylon, polyester, polyvinyl chloride, polyvinylidene chloride, fluororesin, vinylon, polyacrylic polymer, cellulose acetate, and promix; semi-synthetic fibers; rayon, etc. Regenerated fibers; natural fibers such as cotton, hemp, silk, or inorganic fibers can be used. Further, the breathable substrate may be a woven fabric woven with fine metal wires. In particular, the breathable base material may be foamed polyurethane. The breathable substrate may be in the form of a sheet, for example.

The basis weight of the breathable substrate can be, for example, 50 to 500 g / m ² , 100 to 400 g / m ² , or 150 to 300 g / m ² . As used herein, the term "weight per unit area of the base material" means the weight of the breathable base material per 1 m ^2.

  The thickness of the breathable substrate, that is, the thickness of the deodorizing material may be 0.5 mm or more, 1.0 mm or more, 3.0 mm or more, 5.0 mm or more, or 10 mm or more in consideration of the deodorizing performance. When the thickness is thick, the length of the opening is increased, and the adsorption target object is more likely to come into contact with the adsorbent. Moreover, this thickness may be 200 mm or less, 150 mm or less, 100 mm or less, 50 mm or less, or 30 mm or less, for example.

  The breathable substrate may be provided with an opening. This opening is an opening from one main surface of the substrate to the other main surface, and vents the gas to be processed flowing from the one main surface to the other main surface through the breathable substrate. It may be any opening that reduces the resistance. This opening may or may not penetrate from one main surface to the other main surface. In addition, with respect to the breathable base material, “main surface” means two large surfaces facing each other.

  The shape of the opening is not particularly limited, but may have a cross-sectional shape such as a substantially circular shape, a circular shape, a substantially square shape, a square shape, a substantially rectangular shape, or a rectangular shape. The plurality of openings may be provided in a predetermined arrangement, for example, a 60 ° zigzag type, a square zigzag type, or a series type arrangement. The plurality of openings may be provided in an arrangement that forms a certain pattern, for example, a heart-shaped pattern. Moreover, the direction of the hole of the opening may be perpendicular to the main surface of the breathable substrate or may be an oblique direction.

  The means for forming the opening in the breathable substrate is not particularly limited, and for example, mechanical means, thermal means, and chemical means can be used. Preferably, the opening can be provided by mechanical means in which the opening does not deteriorate thermally or chemically, such as punching or drilling. Here, the term “mechanical” means that the substrate is opened by the shearing force of the tool without substantially melting the substrate. Further, the opening may be formed at the same time as the formation of the air permeable base material, that is, for example, the formwork when forming the air permeable base material may have a shape corresponding to the opening. .

The area per opening on one surface of the breathable substrate is 0.5 mm ² or more, 1.0 mm ² or more, 3.0 mm ² or more, 7.0 mm ² or more, 12 mm ² or more, or 18 mm ² or more. It may be. The area per opening may be 300 mm ² or less, 100 mm ² or less, 50 mm ² or less, 30 mm ² or less, 20 mm ² or less, or 10 mm ² or less. Furthermore, the ratio of the opening area per unit area on one surface of the breathable substrate (surface opening ratio) may be 1% or more, 3% or more, and 5% or more. Further, the surface area ratio may be 50% or less, 40% or less, 30% or less, 20% or less, or 15% or less.

In the breathable base material used in the deodorizing material obtained by the present invention, the presence of the opening portion reduces the pressure loss compared to the case where there is no opening portion. This is particularly useful when the deodorizing material is used in a filter for an air cleaner, for example. Specifically, for example, in a breathable base material containing a porous adsorbent at 0.07 g / cm ³ , the difference between the pressure loss when there are no openings and the pressure loss when there are multiple openings. May be 0.20 mmAq or more, 0.3 mmAq or more, 0.5 mmAq or more, 1.0 mmAq or more, or 2.0 mmAq or more for a wind speed of 0.42 m / s. Further, this difference is 2.5 mmAq or less, 1.5 mmAq or less, 1.2 mmAq or less, 1.0 mmAq or less, 0.8 mmAq or less, or 0.5 mmAq or less with respect to a wind speed of 0.42 m / s. Good. In addition, the air-permeable base material having no aperture is preferably 1.00 mmAq or less and 0.50 mmAq or less with respect to a wind speed of 0.42 m / s in a state where the porous adsorbent is not bonded. Or a pressure loss of 0.3 mmAq or less.

  Here, the pressure loss is as follows. Deodorizing material cut to 50 mmφ is packed in a 50 mmφ column, a differential pressure gauge is set above and below the sheet in the column (inlet and outlet), and the flow rate is 50 L / min (wind velocity conversion 0.424 m / s). Is obtained by measuring the differential pressure between the inlet and the outlet caused by flowing air.

  FIG. 2 shows one embodiment of the deodorizing agent 1 obtained by the present invention. Here, a plurality of openings 3 are provided in the breathable base material 2.

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

≪Experiment A: Examination of order of adding water-soluble polymer and binder to slurry≫
1. Preparation of deodorizing material (Example 1)
To 66.5 parts by mass of pure water, 38 parts by mass of powdered activated carbon (specific surface area 1000 m ² / g, median diameter (D50) 20 μm) was charged as a porous adsorbent. Next, as a water-soluble polymer, 1 part by mass of a hydroxyethyl cellulose (HEC, manufactured by Daicel Finechem, SP600) aqueous solution (2% solids, that is, 50 parts by mass of an aqueous solution) is added to this slurry as a water-soluble polymer. Stir for 30 minutes and mix them thoroughly. Thereafter, 15.9 parts by mass of an anionic acrylic resin emulsion (DIC Boncoat AB-795, solid content 56%) as a binder was added and stirred for 30 minutes to obtain a slurry for supporting 30% solid content. Prepared.

This slurry was impregnated into a foamed polyurethane having a thickness of 5 mm and a density of 22 kg / m ^{3 having} no punching holes (color foam ECS, manufactured by Inoac Co., Ltd.) as a breathable substrate, and dried to obtain an activated carbon weight of 30. A deodorizing material of 0.0 mg / cc was obtained.

(Comparative Example 1)
A deodorizing material of Comparative Example 1 was obtained in the same manner as in Example 1 except that the order of mixing the water-soluble polymer into the slurry and the mixing of the binder were reversed.

(Comparative Example 2)
A deodorizing material of Comparative Example 2 was obtained in the same manner as in Example 1 except that the water-soluble polymer and the binder were simultaneously added to the slurry.

(Comparative Example 3)
The deodorizing material of Comparative Example 3 was obtained in the same manner as in Example 1 except that the water-soluble polymer was not added and the amount of pure water input was 115.5 parts by mass instead.

2. Performance Evaluation Deodorization performance was evaluated as toluene adsorption performance and determined as follows. First, the adsorbent cut to a size of 91 mm × 91 mm × 5.0 mm was placed in a 4 L desiccator, and toluene was injected so that the initial concentration was 10 ppm. Then, the toluene concentration after 30 minutes was measured and the deodorization performance was calculated as follows:
Deodorization performance [%] =
{1- (Adsorbed component concentration after 30 minutes) ÷ (Initial adsorbed component concentration)} × 100

3. Results Table 1 summarizes the characteristics of the deodorizing materials of Example 1 and Comparative Reference Examples 1 to 3 obtained as described above, the outline of the production method, and the deodorizing performance.

  It can be seen that the deodorizing performance is greatly improved only by adding the water-soluble polymer in the order of addition before the binder and mixing. In the deodorizing material of Comparative Example 3 in which the water-soluble polymer was not added, the toluene deodorizing performance was remarkably lowered, and it is considered that the pores of the activated carbon were blocked by the binder component, thereby inhibiting the adsorption of toluene. .

≪Experiment B: Water-soluble polymer, binder, porous adsorbent, and change of type of substrate and examination of variables≫
Deodorizing materials of Examples 2 to 23 were produced in the same manner as in Example 1 except that the water-soluble polymer, the binder, the porous adsorbent, and the substrate were variously changed.

  The performance was evaluated in the same manner as in Experiment A above.

  The results are summarized in Table 2 and Table 3 below.

  From this result, it is understood that the advantageous effects of the present invention can be obtained even when various binders, water-soluble polymers, activated carbon, and base materials are used. In addition, when Examples 8-10 are referred, when water-soluble polymer is extremely few, the effect will remain to a certain level, and it turns out that an effect is suppressed also when there are many water-soluble polymers. Moreover, when Examples 12-15 are referred, it turns out that deodorizing performance improves by increasing the quantity of the slurry applied to a base material. Furthermore, it can be seen that when the specific surface area of the porous adsorbent used is high, the deodorization performance is improved as well.

≪Experiment C: Examination of deodorization performance and pressure loss with and without opening of base material≫
1. Preparation of deodorizing material (Reference Example 1)
A chemical solution was prepared by adding 1 g (0.012 mol) of 4-amino-1,2,4-triazole as a chemical adsorbent to 200 g of water. Into this chemical solution, 100 g of coconut shell activated carbon (specific surface area 1000 m ² / g, median diameter (D50) 25 μm) as a porous adsorbent is added and stirred well. To obtain a porous adsorbent carrying a chemical adsorbent. In the slurry containing the porous adsorbent thus obtained, 131 g of a 2% solution of sodium carboxymethyl cellulose (manufactured by Nacalai Tesque) as a thickener and 74 g of an acrylic emulsion as a binder (bon coat AB-795 made by DIC) with a solid content of 57 %) And stirred for 30 minutes to prepare a slurry for supporting.

Breathable base material as 10mm thick and basis weight 300 g / ^{m 2} of polyurethane foam (Bridgestone Corp., trade name HR-50), the opening 272 at equal intervals punched holes of 3 mm.phi (area of about 7 mm ^2), in which The supporting slurry was coated and dried at 100 ° C. for 5 hours to prepare the deodorizing material of Reference Example 1.

(Reference Example 2)
The hole deodorizing material of Reference Example 2 was prepared in the same manner as Reference Example 1 except that 578 3 mmφ punching holes were formed at equal intervals.

(Reference Example 3)
The deodorizing material of Reference Example 3 was treated in the same manner as Reference Example 1 except that foamed polyurethane (Bridgestone, trade name HR-20) having a thickness of 10 mm and a basis weight of 150 g / m ² was used as the breathable substrate. Produced.

(Reference Example 4)
Reference example except that foamed polyurethane (Bridgestone, trade name HR-20) having a thickness of 10 mm and a basis weight of 150 g / m ² was used as a breathable base material, and the amount of support slurry used was increased. In the same manner as in Example 1, the deodorizing material of Reference Example 4 was produced.

(Reference Example 5)
As a breathable base material, ^two polyurethane foams (Bridgestone Corporation, trade name HR-20) having a thickness of 10 mm and a basis weight of 150 g / m ² are layered, and as a base material having a thickness of 20 mm and a basis weight of 300 g / m ² in effect. A deodorizing material of Reference Example 5 was produced in the same manner as Reference Example 1 except that it was used.

(Reference Example 6)
As a breathable base material, a foamed polyurethane (Bridgestone, trade name HR-20) having a thickness of 10 mm and a basis weight of 150 g / m ² was used as one sheet, and holes of 3 mmφ were equally spaced by a heated metal needle 272. A deodorizing material of Reference Example 6 was produced in the same manner as Reference Example 1 except that the individual pieces were opened.

(Reference Example 7)
As the breathable substrate, a foamed polyurethane (Bridgestone, trade name HR-20) having a thickness of 10 mm and a basis weight of 150 g / m ² was used as one sheet, and 3 mmφ was locally located at the center of the breathable substrate. A deodorizing material of Reference Example 7 was produced in the same manner as Reference Example 1 except that 272 punching holes were formed.

(Reference Example 8)
Use of foamed polyurethane (Bridgestone, trade name HR-20) having a thickness of 10 mm and a basis weight of 150 g / m ² as a breathable base material, and 4-amino-1,2,4-triazole as a chemical adsorbent A deodorizing material of Reference Example 8 was produced in the same manner as Reference Example 1 except that no was used.

(Comparative Reference Example 1)
A deodorizing material of Comparative Reference Example 1 was produced in the same manner as in Reference Example 1 except that no opening was formed.

(Comparative Reference Example 2)
A deodorizing material of Comparative Reference Example 2 was produced in the same manner as in Reference Example 1 except that no opening was formed and the amount of the supporting slurry was reduced.

(Comparative Reference Example 3)
The same as Reference Example 1 except that a foamed polyurethane (Bridgestone, trade name HR-20) having a thickness of 10 mm and a basis weight of 150 g / m ² was used as the breathable base material, and no opening was formed. Thus, a deodorizing material of Comparative Reference Example 3 was produced.

(Comparative Reference Example 4)
The use of foamed polyurethane (Bridgestone, trade name HR-20) having a thickness of 10 mm and a basis weight of 150 g / m ² as the breathable base material, the absence of openings, and the amount of slurry used for supporting A deodorizing material of Comparative Reference Example 4 was produced in the same manner as Reference Example 1 except that the amount was increased.

(Comparative Reference Example 5)
Reference example except that foamed polyurethane (Bridgestone, trade name HR-20) having a thickness of 10 mm and a basis weight of 150 g / m ² was used as a breathable base material, and that activated carbon was not used as a physical adsorbent. In the same manner as in Example 1, a deodorizing material of Comparative Reference Example 5 was produced.

(Comparative Reference Example 6)
Use of foamed polyurethane (Bridgestone, trade name HR-20) having a thickness of 10 mm and a basis weight of 150 g / m ² as a breathable base material, no adsorbent was used, and no opening was formed. A deodorizing material of Comparative Reference Example 6 was produced in the same manner as Reference Example 1 except that.

(Comparative Reference Example 7)
The use of foamed polyurethane (Bridgestone, trade name HR-20) having a thickness of 10 mm and a basis weight of 150 g / m ² as the breathable base material, the absence of openings, and 4- as a chemical adsorbent A deodorizing material of Comparative Reference Example 7 was produced in the same manner as in Reference Example 1 except that amino-1,2,4-triazole was not used.

(Comparative Reference Example 8)
The use of foamed polyurethane (Bridgestone, trade name HR-20) having a thickness of 10 mm and a basis weight of 150 g / m ² as the breathable base material, the absence of openings, and activated carbon as a physical adsorbent A deodorizing material of Comparative Reference Example 8 was produced in the same manner as Reference Example 1 except that it was not used.

2. Performance evaluation The pressure loss was determined as described above.

Deodorization performance was evaluated as aldehyde adsorption performance and determined as follows. Evaluation is performed with the apparatus shown in FIG. 3 according to JEM1467 of the Japan Electrical Manufacturers' Association (Japan Electric Industry Association: JEMA established) and Annex 1 deodorization performance test. Specifically, a gas to be treated containing an adsorbed component is caused to flow from a conduit 6 into a 1 m ³ space where an air purifier 4 using a deodorizing material as a filter and a stirring fan 5 are arranged. The aldehyde concentration in the space before the operation of the cleaner 4 is measured by gas chromatography, and then the aldehyde concentration in the space 30 minutes after the air cleaner 4 is operated, and the deodorizing performance for the aldehyde by the following formula Calculated:
Deodorization performance against aldehyde [%]
= {1- (aldehyde concentration after 30 minutes) ÷ (initial adsorbed component concentration)} × 100

3. Results Table 4 summarizes the characteristics of the deodorizing materials of Reference Examples 1 to 7 and Comparative Reference Examples 1 to 9 obtained as described above, an outline of the production method, and the deodorizing performance.

  FIG. 4 shows the relationship between the amount of activated carbon retained in Reference Examples 3 and 4, and Comparative Reference Examples 2 to 4 and Comparative Reference Example 6, and the pressure loss. When FIG. 4 is seen, when there is no opening part, when activated carbon retention amount is increased, pressure loss will increase drastically, and when it has an opening part, even if activated carbon retention amount is high, it turns out that pressure loss hardly changes. .

  FIG. 5 shows a comparative reference between the amount of activated carbon retained and the deodorizing performance in Reference Examples 3 and 4 and Comparative Reference Examples 2 to 4. Referring to FIG. 5, it can be understood that the deodorization performance is increased by increasing the amount of the activated carbon retained, but the difference in the deodorization performance depends on the presence or absence of the opening. This result can also be confirmed by comparison between Reference Example 1 and Comparative Reference Example 1, and the sheet-like adsorbent has not only the pressure loss significantly reduced but also the deodorization performance. It is high.

  Comparing Reference Example 1 and Reference Example 2, it can be seen that the pressure loss is greatly reduced while maintaining the deodorizing performance equal to or higher due to the high surface area ratio. Furthermore, when Reference Example 1 and Reference Example 4 are compared, by reducing the basis weight of the base material, even if a large amount of adsorbent is contained, pressure loss can be greatly reduced, and deodorization performance is also improved. You can see that

  Comparing Reference Example 4 and Reference Example 5, it can be seen that the deodorizing performance can be improved by increasing the thickness of the sheet-like adsorbent. Further, when Reference Example 4 and Reference Example 6 are compared, it can be seen that the sheet-shaped adsorbent perforated by punching improves the deodorizing performance than the sheet-shaped adsorbent perforated by heating. Furthermore, when Reference Example 4 and Reference Example 8 are compared, it can be seen that the deodorization performance is enhanced by the porous adsorbent carrying the chemical adsorbent.

  Comparing Reference Example 4 and Reference Example 7, they have almost the same performance, and it can be seen that the position of the opening does not have a great influence on the deodorizing performance.

  Comparing Reference Example 8 and Comparative Reference Example 7 both using no chemical adsorbent, the deodorizing performance of Reference Example 8 having a hole in the sheet-like adsorbent remains only slightly higher. This is a different result from the comparison between Reference Examples 1 and 4 and Comparative Reference Examples 1 and 4. In the present invention, the porous adsorbent is loaded with a chemical adsorbent, and the sheet-like adsorbent is used. It can be seen that providing a hole in the material has a synergistic effect.

DESCRIPTION OF SYMBOLS 1 Deodorizing material 2 Breathable base material containing porous adsorbent 3 Multiple openings 4 Air cleaner 5 Stirring fan 6 Gas to be treated

Claims (8)

A method for producing a deodorizing material comprising a breathable substrate, a porous adsorbent, and a binder that binds the porous adsorbent to the breathable substrate, including the following steps:
Adding a water-soluble polymer to the aqueous slurry containing the porous adsorbent;
Mixing an aqueous slurry containing the water-soluble polymer;
Adding the binder to the mixed aqueous slurry; and applying the aqueous slurry containing the binder to the breathable substrate.   If the water-soluble polymer is sodium tripolyphosphate, sodium tetraphosphate, sodium hexametaphosphate, polyvinyl alcohol, sodium polyacrylate, polyvinyl pyrrolidone, styrene maleic acid copolymer, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and mixtures thereof The manufacturing method of the deodorizing material of Claim 1 selected from a group.   The method for producing a deodorizing material according to claim 2, wherein the water-soluble polymer is hydroxyethyl cellulose.   The porous adsorbent is selected from the group consisting of activated carbon, sepiolite, palygorskite, zeolite, activated carbon fiber, activated alumina, sepiolite mixed paper, silica gel, activated clay, permiculite, and diatomaceous earth. A method for producing the deodorizing material according to claim 1.   The binder according to claim 1, wherein the binder is selected from the group consisting of acrylic resins, acrylic-styrene resins, acrylic-silicon resins, acrylic-urethane resins, vinyl acetate-acrylic resins, polysiloxane-acrylic resins, and butadiene resins. The manufacturing method of the deodorizing material as described in any one.   The manufacturing method of the deodorizing material as described in any one of Claims 1-5 whose said air-permeable base material is a polyurethane foam.   The manufacturing method of the deodorizing material as described in any one of Claims 1-6 in which the said air-permeable base material has several opening part which goes to the other main surface from one main surface.   The deodorizing material obtained by the method as described in any one of Claims 1-7.

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