JP6526755B2 - Odorant adsorbent - Google Patents

Description

  The present invention relates to odorant adsorbents.

  In recent years, the need for deodorizing by consumers has increased. Among them, aldehyde compounds such as formaldehyde and acetaldehyde are considered as causative agents of sick house syndrome, and are particularly difficult to adsorb because they are difficult to be adsorbed on general adsorbents (for example, general-purpose activated carbon). It is a substance with high demand for odor. For example, hydrazine compounds are known as adsorbents for such odorous substances.

  Among them, adipic acid dihydrazide having relatively high deodorizing performance is widely used (see, for example, Patent Document 1).

  However, there is a problem that deodorizing performance can not be sufficiently exhibited when using only adipic acid dihydrazide as a hydrazine compound in applications including a process of heating to 130 ° C. or more in the manufacturing process. This is considered to be because when only adipic acid dihydrazide is used as the hydrazine compound, the adipic acid dihydrazide causes some change due to the heat history, and the deodorizing performance is lowered. That is, when only adipic acid dihydrazide is used as the hydrazine compound, the heat resistance as a deodorant is insufficient. For example, in the plastic mixing field seen in the manufacture of building materials, in the forming and drying process of the coating agent, it may be placed under an environment of about 10 minutes at 200 ° C. When only adipic acid dihydrazide is used as a hydrazine compound Deodorizing performance is reduced.

International Publication No. 2009/122975

  As described above, although adipic acid dihydrazide is excellent in deodorizing performance at normal temperature, it can not be said that the heat resistance is sufficient, and the deodorizing performance is deteriorated under heating. Therefore, when using only adipic acid dihydrazide as the hydrazine compound, it is an object of the present invention to provide an odorant adsorbent capable of showing sufficient deodorizing performance even under severe heating such that the deodorizing performance is lowered. Do.

As a result of intensive studies to achieve the above object, the inventors of the present invention have found that hydrazine compounds having a molecular weight of 180 or more do not show any deodorizing performance at normal temperature, but under heating at 130 ° C. or more. It has been surprisingly found that it exhibits excellent deodorizing performance. As a result, it has been found that a hydrazine compound having a molecular weight of 180 or more exhibits excellent deodorizing performance under heating conditions in which the deodorizing performance of adipic acid dihydrazide decreases. The present inventors, when using together a hydrazine compound having a molecular weight of 180 or more and a hydrazine compound having a molecular weight of less than 180, the adsorption performance of the hydrazine compound having a molecular weight of 180 or more alone and the hydrazine compound having a molecular weight of less than 180 While the adsorption performance can be improved more than the adsorption performance assumed from the single adsorption performance, the deodorizing performance under heating conditions has a molecular weight despite the use of the hydrazine compound having a molecular weight of 180 or more being reduced. It has been found that an odorant adsorbent is obtained which is comparable to the case of the hydrazine compound alone in which the is 180 or more. Based on such findings, the present inventors have further studied and completed the present invention. That is, the present invention includes the configurations shown below.
Item 1. The odor substance adsorption agent containing the hydrazine compound whose molecular weight is 180 or more, and used for the use heated to 130 degreeC or more.
Item 2. 2. The odorant adsorbent according to item 1, wherein the hydrazine compound having a molecular weight of 180 or more is at least one selected from the group consisting of sebacic acid dihydrazide, dodecanedioic acid dihydrazide and isophthalic acid dihydrazide.
Item 3. Item 3. The odorant adsorbent according to item 1 or 2, further comprising a hydrazine compound having a molecular weight of less than 180.
Item 4. The odor substance adsorbent according to Item 3, wherein the hydrazine compound having a molecular weight of less than 180 is at least one selected from the group consisting of carbodihydrazide, malonic acid dihydrazide, succinic acid dihydrazide and adipic acid dihydrazide.
Item 5. The odorant adsorbent according to any one of Items 1 to 4, further comprising an inorganic porous material.
Item 6. 6. The odorant adsorbent according to item 5, wherein the inorganic porous material is a compound containing silicon.
Item 7. 7. The odorant adsorbent according to item 5 or 6, wherein the inorganic porous material is silica.
Item 8. Item 8. The composition according to any one of Items 1 to 7, further comprising at least one selected from the group consisting of a hygroscopic agent, a superabsorbent polymer, a compound capable of taking a hydrate structure, and a hydrate thereof. Odorant adsorbent.
Item 9. Item 9. The odorant adsorbent according to any one of Items 1 to 8, wherein the odorant is an aldehyde compound.
Item 10. The industrial product used by heating to 130 degreeC or more in a manufacturing process, or heating to 130 degreeC or more in the manufacturing process including the odor substance adsorption agent of any one of claim 1-9.
Item 11. 10. A building material, a plastic for heating, or a filter (however, except for a filter using polyester fiber), comprising the odorant adsorbent according to any one of Items 1 to 9.
Item 12. Item 10. Use of the odorant adsorbent according to any one of Items 1 to 9 for heating to 130 ° C. or higher.
Item 13. A method for adsorbing an odorous substance, comprising the step of bringing the odorant and the odorant adsorbent according to any one of Items 1 to 9 into contact at 130 ° C. or higher.

  The odorant adsorbent of the present invention can sufficiently adsorb the odorant even under a heating condition in which the deodorizing performance is lowered by adipic acid dihydrazide alone, and can exhibit excellent deodorizing performance.

In Experiment 2, it is a plot which made the DDADH / ADH ratio the horizontal axis and made the residual rate of the odorous substance after 24 hours the vertical axis. For reference, theoretical values of the residual rate calculated from the results of Example 4 and Comparative Example 1 are also shown. In Experiment 3, it is a plot which made the DDADH / ADH ratio the horizontal axis and made the residual ratio of the odorous substance after 24 hours the vertical axis. For reference, theoretical values of the residual rate calculated from the results of Example 6 and Comparative Example 5 are also shown.

  As used herein, “contain” is a concept encompassing any of “comprise”, “consist essentially of”, and “consist of”. Moreover, in this specification, when showing a numerical range by "A-B", A or more and B or less are meant.

1. Odorant Adsorbent The odorant adsorbent of the present invention contains a hydrazine compound having a molecular weight of 180 or more and is used for heating to 130 ° C. or more.

(1-1) Hydrazine Compound Having Molecular Weight of 180 or More In the present invention, a hydrazine compound having a molecular weight of 180 or more is used as the hydrazine compound (hereinafter sometimes referred to as “hydrazine compound (1)”). The molecular weight of this hydrazine compound (1) is 180 or more, preferably 230 or more, and more preferably 250 or more. If the molecular weight of the hydrazine compound (1) is less than 180, although the deodorizing performance at the time of non-heating is excellent, the deodorizing performance at the time of heating is lowered to 130 ° C. or more. In addition, the molecular weight of the hydrazine compound (1) is, for example, preferably 300 or less, more preferably 280 or less, and still more preferably 260 or less, from the viewpoint of adsorption performance and adsorption rate. The hydrazine compound (1) having such a molecular weight of 180 or more is inferior in deodorizing performance and deodorizing speed because its reactivity is poor and almost no odorant can be adsorbed at normal temperature, but when heated to 130 ° C. or more Can dramatically improve the deodorizing performance and the deodorizing speed. That is, the odorant adsorbent of the present invention can be used as a deodorant suitable for applications such as heating to 130 ° C. or higher.

  The melting point of the hydrazine compound (1) is not particularly limited, but, for example, 185 ° C. or higher is preferable, but even if the hydrazine compound does not reach the melting point, it must not necessarily reach the melting point because of its effect of improving the solubility in additives by heating. There is nothing to do. Further, for the same reason, the melting point of the hydrazine compound (1) is preferably 230 ° C. or less, more preferably 220 ° C. or less. In addition, for example, it is dissolved when heated by employing a hydrazine compound (1) having a melting point lower than that of the temperature at which the industrial product to be applied is applied or the temperature at which the industrial product to be applied is used. Since the particle size of the odorant adsorbent of the invention can be reduced to increase the surface area, and the odorant can be efficiently contacted, the deodorizing performance at the time of heating can be further improved. is there.

  As such a hydrazine compound (1), for example, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, isophthalic acid dihydrazide and the like can be mentioned. Among them, dodecanedioic acid dihydrazide, isophthalic acid dihydrazide and the like are preferable, and dodecanedioic acid dihydrazide is more preferable, from the viewpoint of excellent deodorizing performance and deodorizing speed when heated to 130 ° C. or higher. These hydrazine compounds (1) can be used alone or in combination of two or more.

  The content of the hydrazine compound (1) in the odorant adsorbent of the present invention is not particularly limited, and from the viewpoint of further improving the adsorption performance and adsorption rate when heated to 130 ° C. or higher, the total amount of odorant adsorbents For example, 0.1 mass% or more is preferable, 1.0 mass% or more is more preferable, and 2.0 mass% or more is more preferable. Further, the content of the hydrazine compound (1) in the odorant adsorbent of the present invention is not particularly limited, and 100% by mass of the total amount of the odorant adsorbent is, for example, 100% by mass, all hydrazine compounds (1) It may be less than 100% by mass for applications and economic reasons. When content of a hydrazine compound (1) is less than 100 mass%, it can also be 99.9 mass% or less, especially 90.0 mass% or less.

  In the present invention, all of the hydrazine compounds to be used may be hydrazine compounds (1), or may be used in combination with hydrazine compounds having a molecular weight of less than 180 described later. Depending on the measurement conditions, etc., it may be most preferable to use all of the hydrazine compounds used as the hydrazine compound (1), and it may be most preferable to use together with a hydrazine compound having a molecular weight of less than 180 described later. From the viewpoint of further improving the adsorption performance and adsorption rate when heated to 130 ° C. or higher, the hydrazine compound (the total amount of the hydrazine compound (the total amount of the hydrazine compound (1) and the hydrazine compound (2) described below) is 100 mass% For example, 20.0 mass% or more is preferable, as for content of 1), 30.0 mass% or more is more preferable, and 40.0 mass% or more is further more preferable. In addition, the total amount of the hydrazine compound (total amount of the hydrazine compound (1) and the hydrazine compound (2) described later) is 100% by mass, for example, 100% by mass may be entirely the hydrazine compound (1). For economic reasons, it may be less than 100% by mass. When the content of the hydrazine compound (1) is less than 100% by mass, it may be 99.9% by mass or less, particularly 99.0% by mass or less.

(1-2) Hydrazine compound having a molecular weight of less than 180 In the present invention, as a hydrazine compound, a hydrazine compound having a molecular weight of less than 180 besides the above-mentioned hydrazine compound (1) having a molecular weight of 180 or more Compounds (2) can also be used). When the hydrazine compound (2) is used alone, the adsorption performance is significantly deteriorated under heating conditions because of performance degradation due to heat history, but when it is used in combination with hydrazine compound (1), performance due to heat history even under heating conditions Since the decrease can be suppressed, the adsorption performance can be improved more than the adsorption performance assumed from the adsorption performance of the hydrazine compound (1) alone and the adsorption performance of the hydrazine compound (2) alone, and the hydrazine compound (1 Despite the reduction of the amount used, odorant adsorbents having deodorizing performance under heating conditions comparable to those of hydrazine compound (1) alone can be obtained. Hydrazine compound (1) is expensive compared to adipic acid dihydrazide widely used at present, so it is very possible that deodorizing performance and deodorizing speed can be maintained even if the amount of hydrazine compound (1) used is small. It is useful.

  The molecular weight of the hydrazine compound (2) is, for example, preferably 30 or more, more preferably 60 or more, and still more preferably 90 or more from the viewpoint of adsorption performance and adsorption rate. The molecular weight of the hydrazine compound (2) is, for example, preferably 175 or less from the viewpoint of adsorption performance and adsorption rate.

  Examples of such a hydrazine compound (2) include carbodihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide and the like. Among them, adipic acid dihydrazide is preferable from the viewpoint of excellent deodorizing performance and deodorizing speed when heated to 130 ° C. or higher when used in combination with the hydrazine compound (1). These hydrazine compounds (2) can be used alone or in combination of two or more.

  In addition, the total amount of hydrazine compounds (hydrazine compound (1) and hydrazine compound (2) described later, from the viewpoint of further improving the adsorption performance and adsorption rate when heated to 130 ° C. or higher when used in combination with hydrazine compound (1) The content of the hydrazine compound (2) is, for example, preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and still more preferably 20.0% by mass or more. The content of the hydrazine compound (2) is preferably 85.0% by mass or less, and 80.0% by mass or less, based on 100% by mass of the total of the hydrazine compound (1) and the hydrazine compound (2) described later. 70.0 mass% or less is more preferable, 60.0 mass% or less is especially preferable. Among them, when the content of the hydrazine compound (2) is 0.1 to 60.0% by mass, it is possible to further improve the deodorizing performance as compared with the case where the hydrazine compound (2) is not used. Moreover, when content of a hydrazine compound (2) is 0.1-80.0 mass% (especially 20.0-70.0 mass%), it is assumed from the case where a hydrazine compound (1) is independent, and the case where a hydrazine compound (2) is alone. Has superior deodorizing performance as compared to the theoretical value of deodorizing performance.

(1-3) Inorganic Porous Material The odorant adsorbent of the present invention can also contain an inorganic porous material. The inorganic porous material itself does not adsorb any odorant at all (there is almost no deodorizing performance), but when it is used in combination with the above-mentioned hydrazine compound having a molecular weight of 180 or more, 130 compared with the case where the inorganic porous material is not used. It is possible to reduce the amount of use of the hydrazine compound (1) while maintaining the deodorizing performance and the deodorizing speed when heated to a temperature of at least ° C. Therefore, it is possible to obtain excellent deodorizing performance with a smaller amount of hydrazine compound (1). The hydrazine compound (1) used in the present invention is expensive compared to adipic acid dihydrazide widely used at present, so deodorizing performance and deodorizing speed can be achieved even if the amount of the hydrazine compound (1) used is small. Being able to maintain is very useful.

  The inorganic porous material is not particularly limited, and examples thereof include compounds containing silicon (silica, activated clay, zeolite, clay, talc and the like), activated carbon, alumina, ceramic, calcium carbonate and the like. Among them, a compound containing silicon is preferable, and silica is more preferable, from the viewpoint of easily maintaining the deodorizing performance and the deodorizing speed even if the amount of the hydrazine compound (1) used is reduced. These inorganic porous materials can be used alone or in combination of two or more.

  When silica is used as such an inorganic porous material, the type thereof is not particularly limited, and any of wet method silica (precipitation method silica, gel method silica, etc.), dry method silica, fused silica and the like can be adopted.

  In addition, when employ | adopting the compound containing a silicon | silicone as an inorganic porous material, it is also possible to have a substituted or unsubstituted amino group on the surface. Such a material can be obtained by chemical modification with a silane coupling agent having a substituted or unsubstituted amino group. The method of chemical modification can be performed according to a conventional method. As a silane coupling agent having a substituted or non-substituted amino group that can be used at this time, for example, a silane coupling agent having a methacryl group, a silane coupling agent having a vinyl group, a silane coupling agent having an amino group, a glycidyl group These include silane coupling agents having a mercapto group, silane coupling agents having a mercapto group, etc. It is also possible to adopt a compound (especially silica) containing silicon modified with a substituted or non-substituted amino group possessed by these silane coupling agents. It is possible.

  When using an inorganic porous material, the content of the inorganic porous material in the odorant adsorbent of the present invention is not particularly limited, and from the viewpoint of further improving the adsorption performance and adsorption rate when heated to 130 ° C. or higher From the above, the total amount of the odorant adsorbent is 100% by mass, for example, 0.1% by mass or more is preferable, 1.0% by mass or more is more preferable, and 2.0% by mass or more is more preferable. For the same reason, the content of the inorganic porous material in the odorant adsorbent of the present invention is not particularly limited, and the total amount of the odorant adsorbent is 100% by mass, preferably 99.9% by mass or less, for example. 95.0 mass% or less is more preferable, and 90.0 mass% or less is more preferable.

(1-4) Hygroscopic agent, super absorbent polymer, and compound capable of taking a hydrate structure and its hydrate The odorant adsorbent of the present invention is, as described above, a hydrazine compound having a molecular weight of 180 or more, If necessary, it contains a hydrazine compound having a molecular weight of less than 180, an inorganic porous material, etc., but the presence of water causes the drying and deactivation of the hydrazine compound (hydrazine compound (1) and hydrazine compound (2)). It is also possible to further suppress and to improve the deodorizing performance and the deodorizing speed. However, when an aqueous solvent such as water is used as a solvent for the odorant adsorbent, when the solvent is heated at a high temperature during the manufacturing process or use, the solvent is volatilized, and therefore no water can be present. When heating at a high temperature of 130 ° C. or more during the manufacturing process or use as in the present invention, addition of a hygroscopic agent, a super absorbent polymer, a compound capable of taking a hydrate structure or a hydrate thereof or the like as an alternative means By containing water into the system even at high temperature by using a water-proofing agent (hereinafter sometimes referred to as "hygroscopic agent etc."), the drying loss of the hydrazine compound (hydrazine compound (1) and hydrazine compound (2)) It is possible to more effectively suppress the activity and to further improve the deodorizing performance and the deodorizing speed at a high temperature of 130 ° C. or higher.

  As the hygroscopic agent, a compound having a moisture absorption rate of 50% or more is preferable, a compound having a moisture absorption rate of 100% or more is more preferable, and a compound having a moisture absorption rate of 150% or more is more preferable. Thus, by using a hygroscopic agent having a high moisture absorption rate, it is possible to cause more water to be present in the system even at high temperatures of 130 ° C. or higher, and the hydrazine compound (hydrazine compound (1) and hydrazine compound It is possible to more effectively suppress the drying and deactivation of 2)) and to further improve the deodorizing performance and the deodorizing speed at a high temperature of 130 ° C. or higher. The upper limit of the moisture absorption rate of the moisture absorbing agent is not particularly limited, but is usually 1000%. The moisture absorption rate of the moisture absorbent is measured by leaving the sample to stand until the weight change does not occur at 25 ° C. and the relative humidity 50%, and determining the weight change.

  Such a hygroscopic agent can be used without particular limitation, but from the viewpoint of the stability of the hydrazine compound (hydrazine compound (1) and hydrazine compound (2)), the pH of the aqueous solution after showing deliquescence It is preferable to use a substance in which is 9 or less (particularly 0 to 9).

  Examples of such a hygroscopic agent include calcium chloride, magnesium chloride, sodium carbonate, citric acid, potassium carbonate, diphosphorus pentaoxide, magnesium perchlorate, manganese sulfate, iron chloride, magnesium sulfate, sodium sulfate and the like. . As these moisture absorbents, although both anhydrides and hydrates can be used, anhydrides are preferable from the viewpoint of further improving the deodorizing performance and the deodorizing speed at a high temperature of 130 ° C. or higher. These hygroscopic agents can be used alone or in combination of two or more.

  The super absorbent polymer can be made to have water by utilizing its moisturizing ability, and can be used regardless of the moisture absorption rate. It is preferable that the super absorbent polymer be capable of absorbing and retaining water at least 100 times its own weight (in particular, 100 to 1,000 times). The molecular weight of the superabsorbent polymer is preferably 1,000 to 500,000.

  As such a super absorbent polymer, for example, polyacrylate, polysulfonate, polysulfonate, maleate anhydride, polyacrylamide, polyvinyl alcohol, polyethylene oxide, sodium polyacrylate, polyvinyl alcohol, polyethylene glycol And polyaspartate, polyglutamate, polyalginate, polysaccharides (starch-derived, cellulose-derived, dextrin etc.) and the like. These super absorbent polymers can be used alone or in combination of two or more.

  The compound capable of having a hydrate structure and the hydrate thereof can be made to have water by utilizing its moisturizing power, and can be used regardless of the moisture absorption rate. As such a compound, a compound capable of taking a structure in which the mass of water of hydration is 50% or more with respect to the weight of the anhydride structure is preferable, and the mass of water of hydration is 100% with respect to the weight of the anhydride structure. Compounds capable of having the above structure are more preferable, and compounds capable of having a structure in which the mass of water of hydration is 150% or more with respect to the weight of the anhydride structure are more preferable, and hydration with respect to the weight of the anhydride structure is more preferable. Particularly preferred are compounds capable of having a structure in which the mass of water is 200% or more. The upper limit of the mass of water of hydration in the anhydride structure is not particularly limited, but is usually 1000%.

Examples of compounds capable of taking such a hydrate structure and hydrates thereof include sodium sulfate (Na ₂ SO ₄ ) and hydrates thereof (Na ₂ SO ₄ · 10H ₂ O etc.), magnesium sulfate (MgSO ₄ ) ₄ ) and its hydrate (such as MgSO ₄ · ₁₀ H ₂ O), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) and its hydrate (such as Al ₂ (SO ₄ ) ₃ · 16 H ₂ O), sodium acetate (CH ₃ COONa) and its hydrate (such as CH ₃ COONa · 3H ₂ O), sodium pyrophosphate (Na ₄ P ₂ O ₇ ) and its hydrate (such as Na ₄ P ₂ O ₇ · 10H ₂ O) , Sodium carbonate (Na ₂ CO ₃ ) and its hydrate (Na ₂ CO ₃ .10H ₂ O etc.), potassium carbonate (K ₂ CO ₃ ) and its hydrate (K ₂ CO ₃ .10H ₂ O etc.) Sodium tetraborate (Na ₂ B ₄ O ₇ ) and its hydrates (Na ₂ B ₄ O ₇ · ₁₀ H ₂ O etc.), sodium chromate (Na ₂ CrO ₄ ) and its hydrate (Na ₂ CrO ₄₎ · 10H ₂ O, etc.), disodium hydrogen phosphate (Na ₂ HPO ₄₎ and Hydrate _{(Na 2 HPO 4 · 12H 2} O , etc.), etc. trisodium phosphate and hydrates thereof _{(Na 3 PO 4 · 12H 2} O , etc.). The compound which can take these hydrate structure, and its hydrate can also be used independently, and can also be used in combination of 2 or more types.

  These hygroscopic agents, super absorbent polymers, compounds capable of forming a hydrate structure or hydrates thereof can be used alone, but it is also possible to use a plurality of types in combination according to the purpose. In addition, when using the odor substance adsorption agent of this invention for a wallpaper use, it is preferable to use a hygroscopic agent from a viewpoint of maintaining aesthetics.

  When using additives such as a hygroscopic agent, a superabsorbent polymer, a compound capable of taking a hydrate structure or a hydrate thereof, the content of these additives in the odorant adsorbent of the present invention is particularly limited From the viewpoint of further improving the adsorption performance and adsorption rate when heated to 130 ° C. or higher, the total amount of the odorant adsorbent is 100% by mass, preferably 0.1% by mass or more, and more preferably 1.0% by mass or more Preferably, 2.0 mass% or more is more preferable. For the same reason, the content of these additives in the odorant adsorbent of the present invention is not particularly limited, and is preferably 95.0% by mass or less, based on 100% by mass of the odorant adsorbent, 90.0 mass% or less is more preferable, and 85.0 mass% or less is more preferable.

  Moreover, when using additives, such as a hygroscopic agent, a super absorbent polymer, a compound capable of taking a hydrate structure, or a hydrate thereof, the content thereof is not particularly limited, and when heated to 130 ° C. or higher 10 to 1000 parts by mass is preferable with respect to 100 parts by mass of the above hydrazine compound (the total amount of the hydrazine compound (1) and the hydrazine compound (2)) from the viewpoint of further improving the adsorption performance and adsorption rate of A mass part is more preferable, and also 100-500 mass parts are further more preferable.

(1-5) Odorant Adsorbent The odorant adsorbent according to the present invention is, as described above, hydrazineamine (1) alone, hydrazineamine (1) and hydrazine compound (2) in combination, as well as hydrazineamine There is a form in which the compound (hydrazine compound (1) alone or hydrazine compound (1) and hydrazine compound (2)) contains an inorganic porous material, a hygroscopic agent and the like. In any form, it can be used as it is (powdered solid), or it can be dissolved or dispersed in a solvent to form a solution or suspension, which can be used as an odorant adsorbent. Moreover, it can also be mixed with powder and used as a powder. It can also be used as a pellet. However, when the polyester fiber is heated at 130 ° C or higher, the bonds between molecules weaken and a gap is created, and the hydrazine compound is enclosed in it (does not localize in the vicinity of the fiber surface); It is preferable not to use in the form which carry | supported the odorant adsorbent of this invention on the polyester-type fiber from the reason which can not fully exhibit. In particular, from the viewpoint of further suppressing the drying and deactivation of the hydrazine compound (hydrazine compound (1) and hydrazine compound (2)) by the presence of water and further improving the deodorizing performance and the deodorizing speed, It is preferable to use as a turbid solution.

  Examples of the solvent in the case of using the odorant adsorbent as a solution or a suspension include water, lower alcohols, polyhydric alcohols, ketones, ethers, esters, aromatic solvents, halogenated hydrocarbon solvents, polar organic solvents Etc.

  As a lower alcohol, the alcohol which has a C1-C4 linear or branched alkyl group is mentioned, for example. Specifically, methanol, ethanol, n-propanol, isopropanol, n-butanol and the like can be mentioned.

  Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc. may be mentioned.

  Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, propylene carbonate and the like.

  Examples of the ether include dioxane, tetrahydrofuran, diethyl ether and the like.

  Examples of the ester include ethyl acetate, butyl acetate, isobutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, dimethyl adipate, dimethyl glutarate, dimethyl succinate and the like.

  Examples of the aromatic solvents include benzene, toluene, xylene, methyl naphthalene, dimethyl naphthalene, isopropyl naphthalene, diisopropyl naphthalene, ethyl biphenyl, diethyl biphenyl, solvent naphtha and the like.

  Examples of halogenated hydrocarbon solvents include carbon tetrachloride, chloroform, methylene chloride and the like.

  Examples of polar organic solvents include dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, N-methylpyrrolidone and the like.

  Among these, from the viewpoint of further improving the deodorizing performance and the deodorizing speed, at least one selected from the group consisting of water, lower alcohols and polyhydric alcohols is preferable, and water is more preferable. These solvents can be used alone or in combination of two or more.

  When the odorant adsorbent of the present invention is used as a solution or suspension, the content of the solvent is not particularly limited, and from the viewpoint of further improving the adsorption performance and adsorption rate when heated to 130 ° C. or higher, the odorant For example, 30.0 mass% or more is preferable, 50.0 mass% or more is more preferable, and 70.0 mass% or more is further preferable, where the total amount of the adsorbent is 100 mass%. For the same reason, the content of the solvent in the odorant adsorbent of the present invention is not particularly limited, and the total mass of the odorant adsorbent is 100% by mass, for example, preferably 99.9% by mass or less, 99.0% % Or less is more preferable, and 98.0 mass% or less is more preferable.

  Moreover, it is also possible to mix and use each component mentioned above and a synthetic resin. As a synthetic resin, for example, polyacrylic resin (acrylic resin, methacrylic resin etc.), polyvinyl acetate resin (vinyl acetate resin etc.), polyvinyl chloride resin (vinyl chloride resin etc.), polyolefin resin (olefin resin (olefin resin) Etc.), ethylene-vinyl acetate copolymer resin (EVA resin), polyurethane resin (urethane resin etc.), polystyrene resin (styrene resin etc.), polyepoxy resin (epoxy resin etc.), silicone resin (silicone resin) Etc.), alkyd resin (alkyd resin etc.), fluorocarbon resin (polytetrafluoroethylene resin etc.), nylon resin, polyester resin (polyester etc .; excluding polyester fiber), polyamide resin (aramid resin etc.), PET-based resin (polyethylene terephthalate etc.), ether-based resin Niren'eteru resin), a polyamine resin, amino resin (melamine resin, urea resin, etc.), phenolic resins, and the like. Copolymer resins containing one or more of the above resins may also be employed. Moreover, the emulsion which consists of above-described resin is also employable. These resins can be used alone or in combination of two or more. Among them, polyacrylic resins (acrylic resin, methacrylic resin, etc.) are preferable.

  When the odorant adsorbent of the present invention contains a resin, the content of the resin is not particularly limited, and from the viewpoint of deodorizing performance, the total amount of the odorant adsorbent of the present invention is 100% by mass, 0.1%. % By mass or more is preferable, 1.0% by mass or more is more preferable, and 5.0% by mass or more is more preferable. In addition, the content of the resin is preferably 95.0% by mass or less, more preferably 90.0% by mass or less, and still more preferably 85.0% by mass or less, from the viewpoint of economy, workability, and the like.

  Moreover, it is also possible to use an inorganic material for processed products such as building materials other than resin. Examples of such inorganic materials include cement, asphalt, concrete, plaster, mortar, diatomaceous earth, montmorillonite, beidellite, nontronite, saponite, hectorite, kaolinite, ceramic and the like.

  When the odorant adsorbent of the present invention contains an inorganic material, the content of the inorganic material is not particularly limited, and the total amount of the odorant adsorbent of the present invention is 100% by mass from the viewpoint of deodorizing performance. 0.1 mass% or more is preferable, 1.0 mass% or more is more preferable, 5.0 mass% or more is more preferable. In addition, the content of the inorganic material is preferably 95.0% by mass or less, more preferably 90.0% by mass or less, and still more preferably 85.0% by mass or less, from the viewpoint of economy, workability, and the like.

  The odorant adsorbent of the present invention is generally formulated into a wide range of additives such as non-volatile acids, chelating agents, antioxidants, light stabilizers, etc. according to the purpose, use, etc. Can be blended with various third components used in

  Preferred non-volatile acids include succinic acid, fumaric acid, maleic acid, boric acid and the like, and salts thereof may also be employed. These non-volatile acids can be used alone or in combination of two or more. By blending such non-volatile acids, the storage stability of the adsorbent can be further improved.

  When a non-volatile acid is used, its content is not particularly limited, and is preferably 1 to 10% by mass, with the total amount of adsorbent as 100% by mass.

  Examples of the chelating agent include ethylenediaminetetraacetic acid, glycol ether diaminetetraacetic acid, oxalic acid, citric acid and the like, and salts thereof can also be employed. These chelating agents can be used alone or in combination of two or more. By blending such a chelating agent, the storage stability of the adsorbent can be further improved.

  When the chelating agent is used, the content thereof is not particularly limited, and preferably 1 to 10% by mass, with the total amount of the adsorbent as 100% by mass.

  Examples of the antioxidant include phenolic antioxidants, amine antioxidants, and the like. Specific examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-methylphenol and 2,2'-methylenebis (4-methyl-6-tert-butylphenol). Specific examples of the amine antioxidant include alkyl diphenylamine, N, N'-di-sec-butyl-p-phenylenediamine and the like. These antioxidants can be used alone or in combination of two or more.

  When using antioxidant, the content in particular is not restrict | limited, 1-10 mass% is preferable, making the total amount of adsorption agent into 100 mass%.

  Examples of the light stabilizer include hindered amine light stabilizers such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like. These light stabilizers can be used alone or in combination of two or more.

  When the light stabilizer is used, the content thereof is not particularly limited, but preferably 1 to 10% by mass, with the total amount of the adsorbent as 100% by mass.

  These third components can be used alone or in combination according to the purpose.

  Such an odorant adsorbent according to the present invention is used for heating to 130 ° C. or higher. Specifically, it is preferable to use it for heating to 130 ° C. or more in the manufacturing process or heating to 130 ° C. or more at the time of use. The heating temperature may include both when the material temperature reaches 130 ° C. or higher and when the ambient temperature (such as the temperature of the dryer) is 130 ° C. or higher. The heating temperature is preferably 150 ° C. or more, more preferably 180 ° C. or more, still more preferably 185 ° C. or more, particularly preferably 190 ° C. or more, from the viewpoint of deodorizing performance and deodorizing speed of the odorant adsorbent of the present invention. Above 200 ° C. are furthermore particularly preferred. The upper limit of the heating temperature in the use of the odorant adsorbent of the present invention is not particularly limited, but the temperature which does not exceed the boiling point of the hydrazine compound (particularly hydrazine compound (1)) or the odorant adsorbent of the present invention It is preferable to set the temperature not higher than the quality of the use (building materials etc.) for which From such a point of view, the upper limit of the heating temperature is usually 300.degree. In addition, it is possible to improve deodorizing performance especially by adopting for the use heated to the melting point or more of the hydrazine compound (especially hydrazine compound (1)) contained in the odor substance adsorbent of the present invention. .

  As a use which heats to such 130 degreeC or more, a construction material (a wallpaper, a floor material, a ceiling material, a handrail etc.), the plastics for heating, a filter (except the filter using polyester fiber) etc. are mentioned, for example.

(1-6) Odorant The above-mentioned odorant adsorbent of the present invention can efficiently adsorb odorous substances (particularly aldehyde compounds) quickly at high temperatures (130 ° C. or higher). The odorant adsorbent of the present invention is effective for the above odorant in which one or more kinds of them are combined.

  There is no particular limitation on the odorant as a target to be adsorbed by the odorant adsorbent of the present invention, and, for example, formaldehyde, acetaldehyde, propionaldehyde, acrolein, n-butyraldehyde, isobutyraldehyde, 3-methyl-butyraldehyde, croton Aldehyde type odor substances (aldehyde compounds) such as aldehydes; alcohols such as pentanal, hexanal, heptanal, octanal, nonanal, decanal, etc .; formic acid and the like. Among others, the odorant adsorbent of the present invention is particularly effective for adsorbing aldehyde compounds, particularly formaldehyde and / or acetaldehyde.

2. Industrial Products Containing an Odorant Adsorbent The odorant adsorbent of the present invention can be used (blended) in industrial products. The industrial product includes the present invention (the industrial product of the present invention).

  The above-mentioned industrial products refer to industrial products and industrial raw materials widely known conventionally. Specifically, building materials (wall paper, floor materials, ceiling materials, handrails, etc.), plastics for heating, filters (excluding filters using polyester fibers), paints, adhesives, inks, sealants, paper products, binders, resins Emulsions, pulps, wood materials, wood products, plastic products, films, fiber products (excluding polyester fibers) and the like can be mentioned.

  In the industrial product of the present invention, the content of the odorant adsorbent of the present invention is not particularly limited, and can be appropriately set depending on the industrial product and its use.

3. Method for adsorbing odorant using odorant adsorbent The method for adsorbing odorant according to the present invention comprises contacting the odorant with the odorant adsorbent according to the present invention at 130 ° C. or higher to obtain the odorant adsorbent according to the present invention Adsorb odorous substances. According to the above adsorption method, the odorant adsorbent of the present invention adsorbs odorous substances (especially aldehyde compounds) efficiently and quickly at high temperatures, so that the odorous substances (especially aldehyde compounds) are removed efficiently and quickly Can. In the adsorption method of the present invention, the above-mentioned industrial product of the present invention containing the odorant adsorbent of the present invention is brought into contact with an odorant (particularly an aldehyde compound) to obtain an odorant adsorbent and the above odorant (especially aldehyde compound) ), And as a result, the odorous substance can be efficiently adsorbed and removed.

  In addition, the odorant substance can be efficiently and quickly added to an adsorption device such as a fixed bed, moving bed or fluidized bed by aeration treatment of a gas containing an odorant substance (particularly, an aldehyde compound). It can be removed by adsorption over time.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the aspects of the following examples. In addition, the following hydrazides were used.
Adipic acid dihydrazide (ADH): manufactured by Tokyo Chemical Industry Co., Ltd. dodecanedioic acid dihydrazide (DDAH): manufactured by Tokyo Chemical Industry Co., Ltd. isophthalic acid dihydrazide (IDH): manufactured by Tokyo Chemical Industry Co., Ltd.

Comparative example 1: ADH heating 200 ° C.
5 parts by mass of adipic acid dihydrazide is added to 95 parts by mass of an acrylic emulsion (Ultrasol C-63 manufactured by Aika Kogyo Co., Ltd .; adjusted to have a solid content of 10% by mass) and dissolved in an ultrasonic bath , And adsorbent (adsorbent solution).

  The obtained adsorbent (adsorption liquid) was used to make a coating film having a wet film thickness of 10 μm on a drawing sheet using a bar coater. Next, it was air-dried at room temperature to obtain a coating having a dry film thickness of 1 μm. Thereafter, the paper sheet and the coating film were heated for 10 minutes in a dryer set at 200.degree. After heating, the sample was cut to a size of 5 cm × 10 cm to obtain a sample for deodorizing test of Comparative Example 1.

Comparative example 2: DDADH unheated
5 parts by mass of dodecanedioic acid dihydrazide is added to 95 parts by mass of an acrylic emulsion (Ultrasol C-63 manufactured by Aika Kogyo Co., Ltd .; adjusted to have a solid content of 10% by mass) and dissolved in an ultrasonic bath As an adsorbent (adsorbent solution).

  The obtained adsorbent (adsorption liquid) was used to make a coating film having a wet film thickness of 10 μm on a drawing sheet using a bar coater. Next, it was air-dried at room temperature to obtain a coating having a dry film thickness of 1 μm. Then, it cut | judged so that it might be set to 5 cm x 10 cm, and it was set as the sample for the deodorizing test of the comparative example 2.

Example 1: DDADH heating 130 ° C.
The adsorbent (adsorbent solution) and deodorizing test of Example 1 are used in the same manner as Comparative Example 1 except that dodecanedioic acid dihydrazide is used instead of adipic acid dihydrazide, and the heating temperature is 130 ° C. instead of 200 ° C. I got a sample.

Example 2: DDADH heating 150 ° C.
The adsorbent (adsorbent solution) and deodorizing test of Example 2 are used in the same manner as Comparative Example 1 except that dodecanedioic acid dihydrazide is used instead of adipic acid dihydrazide and the heating temperature is set to 150 ° C. instead of 200 ° C. I got a sample.

Example 3: DDADH heating 180 ° C.
The adsorbent (adsorbent solution) and deodorizing test of Example 3 are used in the same manner as Comparative Example 1 except that dodecanedioic acid dihydrazide is used instead of adipic acid dihydrazide, and the heating temperature is set to 180 ° C. instead of 200 ° C. I got a sample.

Example 4: DDADH heating 200 ° C.
The adsorbent (adsorbent solution) and the deodorizing test sample of Example 4 were obtained in the same manner as in Comparative Example 1 except that dodecanedioic acid dihydrazide was used instead of adipic acid dihydrazide.

Example 5: IDH heating 230 ° C.
The adsorbent (adsorbent solution) and the sample for the deodorizing test of Example 5 are similar to Comparative Example 1 except that isophthalic acid dihydrazide is used instead of adipic acid dihydrazide and the heating temperature is set to 230 ° C. instead of 200 ° C. I got

Example 6: DDADH + silica heating 200 ° C.
2.5 parts by mass of dodecanedioic acid dihydrazide and 95 parts by mass of acrylic emulsion (Ultrasol C-63 manufactured by Aika Kogyo Co., Ltd .; adjusted to have a solid content of 10% by mass) and silica (Mizusawa Chemical Industry Co., Ltd.) 2.5 parts by mass of Mizukasil P-758C) was added and dissolved in an ultrasonic bath to obtain an adsorbent (adsorption liquid).

  The obtained adsorbent (adsorption liquid) was used to make a coating film having a wet film thickness of 10 μm on a drawing sheet using a bar coater. Next, it was air-dried at room temperature to obtain a coating having a dry film thickness of 1 μm. Thereafter, the paper sheet and the coating film were heated for 10 minutes in a dryer set at 200.degree. After heating, it was cut to a size of 5 cm × 10 cm to obtain a sample for deodorizing test of Example 6.

Example 7: DDADH + activated carbon heating 200 ° C.
An adsorbent (adsorbent solution) and a deodorizing test sample of Example 7 were obtained in the same manner as in Example 6 except that activated carbon (Hakuho WP-H manufactured by Osaka Gas Chemical Co., Ltd.) was used instead of silica. The

Comparative Example 3: Silica heating 200 ° C.
5 parts by mass of silica (Mizukasil P-758C manufactured by Mizusawa Chemical Industry Co., Ltd.) relative to 95 parts by mass of an acrylic emulsion (Ultrasol C-63 manufactured by Aika Kogyo Co., Ltd .; adjusted to have a solid content of 10% by mass) Parts were added and dissolved in an ultrasonic bath to obtain an adsorbent (adsorption liquid).

  The obtained adsorbent (adsorption liquid) was used to make a coating film having a wet film thickness of 10 μm on a drawing sheet using a bar coater. Next, it was air-dried at room temperature to obtain a coating having a dry film thickness of 1 μm. Thereafter, the paper sheet and the coating film were heated for 10 minutes in a dryer set at 200.degree. After heating, the sample was cut to a size of 5 cm × 10 cm to obtain a sample for deodorizing test of Comparative Example 3.

Comparative Example 4: Activated carbon heating 200 ° C.
An adsorbent (adsorbent solution) and a deodorizing test sample of Comparative Example 4 were obtained in the same manner as in Comparative Example 3 except that activated carbon (Hakuho WP-H manufactured by Osaka Gas Chemical Co., Ltd.) was used instead of silica. The

Example 8: DDADH + silica + calcium chloride heating 200 ° C.
2.5 parts by mass of dodecanedioic acid dihydrazide relative to 95 parts by mass of an acrylic emulsion (Ultrasol C-63 manufactured by Aika Kogyo Co., Ltd .; adjusted to have a solid content of 10% by mass), silica (Mizusawa Chemical Industry Co., Ltd.) 2.5 parts by mass of Mizukasil P-758C) and 5.0 parts by mass of calcium chloride (dihydrate, manufactured by Wako Pure Chemical Industries, Ltd., reagent) are added, dissolved in an ultrasonic bath, and adsorbent (adsorption liquid) And

  The obtained adsorbent (adsorption liquid) was used to make a coating film having a wet film thickness of 10 μm on a drawing sheet using a bar coater. Next, it was air-dried at room temperature to obtain a coating having a dry film thickness of 1 μm. Thereafter, the paper sheet and the coating film were heated for 10 minutes in a dryer set at 200.degree. After heating, it was cut to a size of 5 cm × 10 cm to obtain a sample for deodorizing test of Example 8.

Example 9: DDADH / ADH = 8: 2 heating to 200 ° C.
The adsorption of Example 9 is the same as Comparative Example 1 except that the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide is 8: 2 in mass ratio instead of 5 parts by mass of adipic acid dihydrazide. An agent (adsorption liquid) and a sample for deodorizing test were obtained.

Example 10: DDADH / ADH = 5: 5 heating to 200 ° C.
The adsorption of Example 10 was carried out in the same manner as Comparative Example 1 except that the blending ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 5: 5 in mass ratio instead of 5 parts by mass of adipic acid dihydrazide. An agent (adsorption liquid) and a sample for deodorizing test were obtained.

Example 11: DDADH / ADH = 4: 6 heating at 200 ° C.
The adsorption of Example 11 was the same as Comparative Example 1 except that the mixing ratio of dodecanedioic acid dihydrazide to adipic acid dihydrazide was 4: 6 in mass ratio instead of 5 parts by mass of adipic acid dihydrazide. An agent (adsorption liquid) and a sample for deodorizing test were obtained.

Example 12: DDADH / ADH = 3: 7 heating at 200 ° C.
The adsorption of Example 12 is the same as Comparative Example 1 except that the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide is 3: 7 in mass ratio instead of 5 parts by mass of adipic acid dihydrazide. An agent (adsorption liquid) and a sample for deodorizing test were obtained.

Example 13: DDADH / ADH = 2: 8 heating to 200 ° C.
The adsorption of Example 13 is the same as Comparative Example 1 except that the mixing ratio of dodecanedioic acid dihydrazide to adipic acid dihydrazide is 2: 8 in mass ratio instead of 5 parts by mass of adipic acid dihydrazide. An agent (adsorption liquid) and a sample for deodorizing test were obtained.

Example 14: DDADH / ADH = 9: 1 + silica heating 200 ° C.
The adsorbent of Example 14 was used in the same manner as Example 6, except that the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 9: 1 in mass ratio instead of dodecanedioic acid dihydrazide, An adsorption solution) and a deodorant test sample were obtained.

Example 15: DDADH / ADH = 8: 2+ Silica heating at 200 ° C.
The adsorbent of Example 15 was used in the same manner as Example 6, except that the blending ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 8: 2 in mass ratio instead of dodecanedioic acid dihydrazide. An adsorption solution) and a deodorant test sample were obtained.

Example 16: DDADH / ADH = 6: 4 + silica heating 200 ° C.
The adsorbent of Example 16 was used in the same manner as Example 6, except that the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 6: 4 in mass ratio instead of dodecanedioic acid dihydrazide. An adsorption solution) and a deodorant test sample were obtained.

Example 17: DDADH / ADH = 5: 5 + silica heating at 200 ° C.
The adsorbent of Example 17 was used in the same manner as Example 6, except that the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 5: 5 in mass ratio instead of dodecanedioic acid dihydrazide. An adsorption solution) and a deodorant test sample were obtained.

Example 18: DDADH / ADH = 4: 6 + silica heating at 200 ° C.
The adsorbent of Example 18 was used in the same manner as Example 6, except that the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 4: 6 in mass ratio instead of dodecanedioic acid dihydrazide. An adsorption solution) and a deodorant test sample were obtained.

Example 19: DDADH / ADH = 2: 8 + silica heating 200 ° C.
The adsorbent of Example 19 was used in the same manner as Example 6, except that the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 2: 8 in mass ratio instead of dodecanedioic acid dihydrazide. An adsorption solution) and a deodorant test sample were obtained.

Comparative example 5: ADH + silica heating 200 ° C.
An adsorbent (adsorbent solution) and a deodorizing test sample of Comparative Example 5 were obtained in the same manner as in Example 6 except that adipic acid dihydrazide was used instead of dodecanedioic acid dihydrazide.

Test Example 1 (Acetaldehyde adsorption performance)
One deodorant test sample obtained in each of Examples 1 to 8 and Comparative Examples 1 to 4 is placed in 1 L of Tedlar bag (manufactured by GL Science Inc.), sealed, and then the air in the Tedlar bag is removed using a piston. The Thereafter, 1 L of acetaldehyde gas adjusted to 14 ppm is injected, and the residual gas concentrations after 30 minutes, 1 hour, 1 hour, 3 hours, 24 hours and 48 hours are detected using a detection tube (Gastec Co., Ltd.) evaluated. The results are shown in Tables 1-2.

Test Example 2 (Acetaldehyde adsorption performance)
The deodorizing test was conducted in the same manner as in Test Example 1 above. Specifically, one sample of the deodorizing test obtained in each of Examples 4 and 9 to 13 and Comparative Example 1 is placed in 1 L of Tedlarback (manufactured by GL Sciences, Inc.), sealed, and then Tedlarback using a piston. I pulled out the air inside. Thereafter, 1 L of acetaldehyde gas adjusted to 14 ppm was injected, and the residual gas concentration only after 24 hours was evaluated using a detection tube (manufactured by Gaztec Inc.). The results are shown in Table 3. In addition, the total content of DDADH and ADH is 1 and the content ratio of DDADH (DDADH content / (DDADH content + ADH content)) is on the horizontal axis, and the remaining ratio of odorant after 24 hours (acetaldehyde after 24 hours A plot with concentration / initial acetaldehyde concentration (14 ppm) × 100 (%)) as a vertical axis is shown in FIG. FIG. 1 also shows theoretical values of the residual rate calculated from the results of Example 4 and Comparative Example 1.

Test Example 3 (Acetaldehyde adsorption performance)
The deodorizing test was conducted in the same manner as in Test Example 2 above. Specifically, one sample of the deodorizing test obtained in each of Examples 6 and 14 to 19 and Comparative Example 5 is placed in 1 L of Tedlar Back (manufactured by GL Science, Inc.), sealed, and then Tedlar Back using a piston. I pulled out the air inside. Thereafter, 1 L of acetaldehyde gas adjusted to 14 ppm is injected, and the residual gas concentration is evaluated using a detection tube (Gas Tech Co., Ltd.) at 0.5 hours, 1 hour, 3 hours, 24 hours and 48 hours. did. The results are shown in Table 4. In addition, the total content of DDADH and ADH is 1 and the content ratio of DDADH (DDADH content / (DDADH content + ADH content)) is on the horizontal axis, and the remaining ratio of odorant after 24 hours (acetaldehyde after 24 hours A plot with concentration / initial acetaldehyde concentration (14 ppm) × 100 (%)) as a vertical axis is shown in FIG. FIG. 2 also shows theoretical values of the residual rate calculated from the results of Example 6 and Comparative Example 5.

  As described above, when adipic acid dihydrazide, which has been conventionally used as an odorant adsorbent, when used alone, its deodorizing performance was degraded at high temperatures. On the other hand, although dodecanedioic acid dihydrazide has almost no deodorizing performance at room temperature, it showed significantly better deodorizing performance than adipic acid dihydrazide at high temperature. This result can also be understood with isophthalic acid dihydrazide. In addition, when dodecanedioic acid dihydrazide was mixed with an inorganic porous material such as silica or activated carbon, the deodorizing performance was maintained although the amount of dodecanedioic acid dihydrazide was reduced. In particular, dodecanedioic acid dihydrazide is expensive compared to adipic acid dihydrazide, so it is useful that excellent deodorizing performance can be obtained even if the amount used is small.

  Furthermore, when dodecanedioic acid dihydrazide and adipic acid dihydrazide are mixed, as shown in Table 3, when the content of adipic acid dihydrazide is 60% by mass or less, adipic acid dihydrazide having low performance is used. Despite mixing, the deodorizing performance was improved over dodecanedioic acid dihydrazide alone. In addition, as shown in Tables 3 to 4 and theoretical values in FIGS. 1 and 2, a performance is conceivable in which a straight line is connected between dodecanedioic acid dihydrazide alone and adipic acid dihydrazide alone, The measured data showed that the residual odor rate was significantly smaller than the theoretical value. For this reason, when dodecanedioic acid dihydrazide and adipic acid dihydrazide are mixed, the deodorizing performance is remarkable compared with theoretical values assumed from the case of dodecanedioic acid dihydrazide alone and the case of adipic acid dihydrazide alone. I was able to improve. This synergistic effect is effective in a wide range, but is particularly remarkable when the content of adipic acid dihydrazide is 20 to 70% by mass. From this, when dodecanedioic acid dihydrazide and adipic acid dihydrazide are mixed, it is thought that the drying inactivation of adipic acid dihydrazide was prevented for some reason because of the presence of dodecanedioic acid dihydrazide. Thus, when dodecanedioic acid dihydrazide and adipic acid dihydrazide are mixed, it is also possible to improve or maintain the deodorizing performance while reducing the amount of expensive dodecanedioic acid dihydrazide used.

  Furthermore, in Test Example 3, silica (Comparative Example 3) which hardly exhibits deodorizing performance in single use is further added to DDADH and, if necessary, ADH, and the amount of use of the hydrazine compound is reduced accordingly. . That is, in Table 4 of Test Example 3, compared with Table 3 of Test Example 2, the silica which does not exhibit the deodorizing performance alone even though the amount of the active ingredient (the used amount of the hydrazine compound) is half. Surprisingly, the remaining rate after 24 hours is as good as or more than Table 3 of Test Example 2 by using. From this result, although silica does not exhibit deodorizing performance when used alone, it has a function to improve the deodorizing performance of DDADH which is a hydrazine compound, and it is considered that it plays a role of synergetic effect imparting as a result .

Claims (10)

A building material, heating plastic or filter which contains dodecanedioic acid dihydrazide and adipic acid dihydrazide and is used by heating to 130 ° C. or higher in the production process or heating to 130 ° C. or higher (but using polyester fiber Odorant adsorbents used for filters). The odorant adsorbent according to claim 1, further comprising an inorganic porous material. The odorant adsorbent according to claim 2 , wherein the inorganic porous material is a compound containing silicon. The odorant adsorbent according to claim 2 or 3 , wherein the inorganic porous material is silica. The composition according to any one of claims 1 to 4 , further comprising at least one selected from the group consisting of a hygroscopic agent, a superabsorbent polymer, and a compound capable of having a hydrate structure and a hydrate thereof. Odorant adsorbent. The odorant adsorbent according to any one of claims 1 to 5 , wherein the odorant is an aldehyde compound. A building material, a plastic for heating, or a filter (wherein the odorant adsorbent according to any one of claims 1 to 6 is used by heating to 130 ° C. or higher or 130 ° C. or higher in the production process) , Excluding polyester fiber filters). Use of an odorant adsorbent containing dodecanedioic acid dihydrazide and adipic acid dihydrazide for industrial products to be used by heating to 130 ° C. or higher or 130 ° C. or higher in the production process. A method for adsorbing an odorant, comprising the step of bringing an odorant into contact with an odorant adsorbent containing dodecanedioic acid dihydrazide and adipic acid dihydrazide at 130 ° C. or higher. A method for producing an industrial product, comprising heating at 130 ° C. or higher in the production process using an odorant adsorbent containing dodecanedioic acid dihydrazide and adipic acid dihydrazide.