WO2018203536A1 - Odorant absorbing agent - Google Patents

Abstract

This odorant absorbing agent contains a hydrazine compound having a molecular weight of 180 or more, and is used for application involving heating at 130°C or higher. The odorant absorbing agent can exhibit sufficient deodorizing capability even under severe heating in which the deodorizing capability drops if adipic dihydrazide alone is used.

Description

Odorant adsorbent

The present invention relates to an odorous substance adsorbent.

In recent years, consumer needs for deodorization are increasing. Among them, aldehyde compounds such as formaldehyde and acetaldehyde are considered as causative substances for sick house syndrome, and are particularly difficult to absorb because they are difficult to adsorb on general adsorbents (for example, general-purpose activated carbon). It is a substance with a high demand for odor. As such an adsorbent for odorous substances, for example, hydrazine compounds are known.

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

However, there is a problem that the deodorizing performance cannot be sufficiently exhibited when only adipic acid dihydrazide is used as a hydrazine compound in an application including a step of heating to 130 ° C. or higher in the production process. This is considered to be because when only adipic acid dihydrazide is used as the hydrazine compound, adipic acid dihydrazide undergoes some change due to the thermal history, and the deodorizing performance decreases. 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 field of plastic kneading found in the manufacture of building materials, in the molding and coating agent drying process, it may be placed in an environment of about 10 minutes at 200 ° C. When only adipic acid dihydrazide is used as the hydrazine compound The deodorizing performance is reduced.

International Publication No. 2009/122975

As described above, although adipic acid dihydrazide is excellent in deodorizing performance at room temperature, it cannot be said that the heat resistance is sufficient, and the deodorizing performance deteriorates under heating. For this reason, when only adipic acid dihydrazide is used as a hydrazine compound, an object of the present invention is to provide an odorous substance adsorbent that can exhibit sufficient deodorizing performance even under severe heating such that the deodorizing performance decreases. To do.

As a result of intensive studies to achieve the above object, the present inventors have found that a hydrazine compound having a molecular weight of 180 or more shows no deodorizing performance at room temperature, but is heated at 130 ° C. or higher. It has been surprisingly found that it exhibits excellent deodorizing performance. As a result, it was found that hydrazine compounds having a molecular weight of 180 or more show excellent deodorizing performance under heating conditions in which the deodorizing performance of adipic acid dihydrazide is reduced. When the present inventors combined use of 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 alone having a molecular weight of 180 or more and the hydrazine compound having a molecular weight of less than 180 Adsorption performance can be improved from the adsorption performance assumed from the single adsorption performance, and the deodorization performance under heating conditions is reduced in molecular weight even though the amount of hydrazine compound with a molecular weight of 180 or more is reduced. It was found that an odorant adsorbent that is comparable to the case of a hydrazine compound having an A of 180 or more can be obtained. Based on such knowledge, the present inventors have further studied and completed the present invention. That is, this invention includes the structure shown below.
Item 1. An odorous substance adsorbent containing a hydrazine compound having a molecular weight of 180 or more and used for heating to 130 ° C or higher.
Item 2. Item 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. Item 4. The odorant 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. Item 5. The odorant adsorbent according to any one of Items 1 to 4, further comprising an inorganic porous material.
Item 6. Item 6. The odorant adsorbent according to Item 5, wherein the inorganic porous material is a compound containing silicon.
Item 7. Item 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. Odor substance 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. Item 10. An industrial product comprising the odorant adsorbent according to any one of Items 1 to 9 and being heated to 130 ° C or higher or heated to 130 ° C or higher in the production process.
Item 11. Item 10. A building material, a heating plastic or a filter (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. 10. A method for adsorbing an odor substance, comprising a step of bringing an odor substance into contact with the odor substance adsorbent according to any one of Items 1 to 9 at 130 ° C. or higher.

The odorous substance adsorbent of the present invention can sufficiently adsorb odorous substances and exhibit excellent deodorizing performance even under heating conditions in which the deodorizing performance decreases with adipic acid dihydrazide alone.

In Test Example 2, the DDADH / ADH ratio is plotted on the horizontal axis, and the residual rate of odorous substances after 24 hours is plotted on the vertical axis. For reference, the theoretical value of the residual ratio calculated from the results of Example 4 and Comparative Example 1 is also shown. In Test Example 3, the plot is plotted with the DDADH / ADH ratio on the horizontal axis and the residual rate of odorous substances after 24 hours on the vertical axis. For reference, the theoretical value of the residual ratio calculated from the results of Example 6 and Comparative Example 5 is also shown.

In the present specification, “containing” is a concept including any of “comprise”, “consistently of”, and “consist of”. In this specification, when the numerical range is indicated by “A to B”, it means A or more and B or less.

1. Odor Substance Adsorbent The odor substance 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 a 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 the hydrazine compound (1) is 180 or more, preferably 230 or more, more preferably 250 or more. If the molecular weight of the hydrazine compound (1) is less than 180, the deodorizing performance when not heated is excellent, but the deodorizing performance when heated to 130 ° C or higher is not suitable for heating applications. In addition, the molecular weight of the hydrazine compound (1) is, for example, preferably 300 or less, more preferably 280 or less, and even more preferably 260 or less, from the viewpoint of adsorption performance and adsorption rate. Such a hydrazine compound (1) having a molecular weight of 180 or more is poor in deodorizing performance and deodorizing speed because it has poor reactivity at room temperature and hardly absorbs odorous substances, but when heated to 130 ° C or higher, Can drastically improve the deodorizing performance and deodorizing speed. That is, the odorous substance adsorbing material 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. For example, it is preferably 185 ° C. or higher. However, even if the hydrazine compound does not reach the melting point, it does not necessarily reach the melting point due to the effect of improving the solubility in the additive by heating. There is nothing that doesn't happen. For the same reason, the melting point of the hydrazine compound (1) is preferably 230 ° C. or lower, and more preferably 220 ° C. or lower. Further, for example, by adopting a hydrazine compound (1) having a melting point lower than the temperature heated in the manufacturing process of the industrial product to be applied or the temperature at which the industrial product to be used is used, Since the particle size of the odorous substance adsorbent of the invention can be reduced and the surface area can be increased, and it is possible to efficiently contact the odorous substance, it is possible to further improve the deodorizing performance during heating. is there.

Examples of such hydrazine compound (1) include sebacic acid dihydrazide, dodecanedioic acid dihydrazide, and isophthalic acid dihydrazide. Of these, 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 the odorant adsorbent Is, for example, preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and further preferably 2.0% by mass or more. Further, the content of the hydrazine compound (1) in the odorous substance adsorbent of the present invention is not particularly limited, and the total amount of the odorant adsorbent is 100% by mass, for example, all 100% by mass is the hydrazine compound (1). It may also be less than 100% by mass for use and economic reasons. When the content of the hydrazine compound (1) is less than 100% by mass, it can be 99.9% by mass or less, particularly 90.0% by mass or less.

In the present invention, all of the hydrazine compounds to be used can be the hydrazine compound (1), or can be used in combination with a hydrazine compound having a molecular weight of less than 180, which will be described later. Depending on the measurement conditions and the like, it may be most preferable to use all of the hydrazine compound to be used as the hydrazine compound (1), or it may be most preferable to use in combination with a hydrazine compound having a molecular weight of less than 180, which will be described later. From the viewpoint of further improving the adsorption performance and adsorption rate when heated to 130 ° C. or higher, the hydrazine compound total amount (total amount of hydrazine compound (1) and hydrazine compound (2) described later) is 100% by mass, For example, the content of 1) is preferably 20.0% by mass or more, more preferably 30.0% by mass or more, and further preferably 40.0% by mass or more. Further, assuming that the total amount of hydrazine compound (total amount of hydrazine compound (1) and hydrazine compound (2) described later) is 100% by mass, for example, all 100% by mass may be hydrazine compound (1). For economic reasons, it may be less than 100% by weight. When the content of the hydrazine compound (1) is less than 100% by mass, it can 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 the hydrazine compound, in addition to the hydrazine compound (1) having a molecular weight of 180 or more, a hydrazine compound having a molecular weight of less than 180 (hereinafter referred to as “hydrazine compound”). Compound (2) ”may also be used. When hydrazine compound (2) is used alone, the adsorption performance is remarkably poor due to performance degradation due to thermal history under heating conditions, but when used together with hydrazine compound (1), performance due to thermal history is also observed under heating conditions. Since the decrease can be suppressed, the adsorption performance can be improved from the adsorption performance expected 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 ) Odor substance adsorbent is obtained in the same manner as the hydrazine compound (1) alone, although the deodorizing performance under heating conditions is reduced, even though the amount of use of) is reduced. Since the hydrazine compound (1) is expensive compared to the widely used adipic acid dihydrazide, it is very possible to maintain the deodorizing performance and deodorizing speed even if the amount of the hydrazine compound (1) is reduced. 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 preferably 175 or less, for example, from the viewpoint of adsorption performance and adsorption rate.

Examples of such hydrazine compound (2) include carbodihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide and the like. Of these, 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.

From the viewpoint of further improving the adsorption performance and adsorption rate when heated to 130 ° C or higher when used in combination with the hydrazine compound (1), the total amount of hydrazine compound (hydrazine compound (1) and hydrazine compound (2) described below) The total 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 further preferably 20.0% by mass or more. Further, the total amount of hydrazine compound (the total amount of hydrazine compound (1) and hydrazine compound (2) described later) is 100% by mass, and the content of hydrazine compound (2) is preferably 85.0% by mass or less, and preferably 80.0% by mass or less. More preferably, it is more preferably 70.0% by mass or less, and particularly preferably 60.0% by mass or less. In particular, when the content of the hydrazine compound (2) is 0.1 to 60.0 mass%, it is possible to further improve the deodorizing performance as compared with the case where the hydrazine compound (2) is not used. In addition, when the content of the hydrazine compound (2) is 0.1 to 80.0 mass% (especially 20.0 to 70.0 mass%), it is assumed from the case of the hydrazine compound (1) alone and the case of the hydrazine compound (2) alone. Compared to the theoretical value of deodorizing performance, it has excellent deodorizing performance.

(1-3) Inorganic porous material The odorous material adsorbent of the present invention may contain an inorganic porous material. The inorganic porous material itself does not adsorb odorous substances at all (there is almost no deodorizing performance), but when used in combination with the hydrazine compound having a molecular weight of 180 or more as compared with the case where the inorganic porous material is not used, it is 130. It is possible to reduce the amount of the hydrazine compound (1) used while maintaining the deodorizing performance and the deodorizing speed when heated to more than ° C. For this reason, it is possible to obtain an excellent deodorizing performance with a smaller amount of the hydrazine compound (1). Since the hydrazine compound (1) used in the present invention is expensive compared to the widely used adipic acid dihydrazide, the deodorizing performance and deodorizing speed can be achieved even if the amount of the hydrazine compound (1) is reduced. It is very useful to be able to maintain it.

Such an inorganic porous material is not particularly limited, and examples thereof include activated carbon, alumina, ceramics, calcium carbonate, etc., in addition to silicon-containing compounds (silica, activated clay, zeolite, clay, talc, etc.). Among these, from the viewpoint of easily maintaining the deodorizing performance and the deodorizing speed even if the amount of the hydrazine compound (1) is reduced, a compound containing silicon is preferable, and silica is more preferable. 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 kind 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 silicon 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 chemical modification method can be performed according to a conventional method. Examples of the silane coupling agent having a substituted or unsubstituted amino group that can be used in this case include a silane coupling agent having a methacryl group, a silane coupling agent having a vinyl group, a silane coupling agent having an amino group, and a glycidyl group. A silane coupling agent having a mercapto group, a silane coupling agent having a mercapto group, and the like, and a compound containing silicon modified with a substituted or unsubstituted amino group (especially silica) included in these silane coupling agents may be employed. Is possible.

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

(1-4) Hygroscopic agent, highly water-absorbing polymer, compound capable of taking a hydrate structure and hydrate thereof As described above, the odorant adsorbent of the present invention comprises a hydrazine compound having a molecular weight of 180 or more, It contains hydrazine compounds with a molecular weight of less than 180, inorganic porous materials, etc. as necessary, but by dehydrating the hydrazine compounds (hydrazine compound (1) and hydrazine compound (2)) can be deactivated by drying. It is possible to further suppress and improve the deodorizing performance and the deodorizing speed. However, when an aqueous solvent such as water is used as the solvent for the odorous substance adsorbent, water is not present because the solvent is volatilized when heated at a high temperature during production or use. When heating at a high temperature of 130 ° C. or more during production or use as in the present invention, addition of a hygroscopic agent, a superabsorbent polymer, a compound capable of taking a hydrate structure or a hydrate thereof as an alternative means Loss of drying of the hydrazine compounds (hydrazine compound (1) and hydrazine compound (2)) by using moisture in the system even at high temperatures by using an agent (hereinafter sometimes referred to as “humectant” etc.) It is possible to suppress the activity more effectively and to further improve the deodorizing performance and deodorizing speed at a high temperature of 130 ° C. or higher.

The hygroscopic agent is preferably a compound having a moisture absorption rate of 50% or more, more preferably a compound having a moisture absorption rate of 100% or more, and further preferably a compound having a moisture absorption rate of 150% or more. In this way, by using a hygroscopic agent having a high moisture absorption rate, it is possible to allow more water to be present in the system even at a high temperature of 130 ° C. or higher, and hydrazine compounds (hydrazine compound (1) and hydrazine compound ( It is possible to more effectively suppress the drying deactivation of 2)) and to further improve the deodorizing performance and deodorizing speed at a high temperature of 130 ° C. or higher. The upper limit of the moisture absorption rate of the hygroscopic agent is not particularly limited, but is usually 1000%. The moisture absorption rate of the hygroscopic agent is measured by allowing the sample to stand until there is no weight change at 25 ° C. and 50% relative humidity, and determining the weight change.

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

Examples of such a hygroscopic agent include calcium chloride, magnesium chloride, sodium carbonate, citric acid, potassium carbonate, diphosphorus pentoxide, magnesium perchlorate, manganese sulfate, iron chloride, magnesium sulfate, sodium sulfate and the like. . These hygroscopic agents may be either anhydrides or hydrates, but anhydrides are preferable from the viewpoint of high hygroscopicity and further improving the deodorization performance and deodorization rate at a high temperature of 130 ° C. or higher. These hygroscopic agents can be used alone or in combination of two or more.

Highly water-absorbing polymers can be used regardless of their moisture absorption rate because their moisture retention can be used to allow moisture to exist. This highly water-absorbing polymer is preferably one that can absorb and retain water 100 times or more (particularly 100 to 1,000 times) of its own weight. The molecular weight of the superabsorbent polymer is preferably 1000 to 500000.

Examples of such superabsorbent polymers include polyacrylate, polysulfonate, polysulfonate, maleic anhydride, polyacrylamide, polyvinyl alcohol, polyethylene oxide, sodium polyacrylate, polyvinyl alcohol, polyethylene glycol. , 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.

A compound that can take a hydrate structure and its hydrate can be used regardless of the moisture absorption rate because moisture can be present by utilizing its moisturizing power. As such a compound, a compound capable of taking a structure in which the mass of hydrated water is 50% or more with respect to the weight of the anhydride structure is preferable, and the mass of hydrated water is 100% with respect to the weight of the anhydride structure. More preferred is a compound capable of taking the above structure, more preferred is a compound capable of taking a structure in which the mass of hydrated water is 150% or more based on the weight of the anhydrous structure, and hydration on the weight of the anhydrous structure A compound that can take a structure in which the mass of water is 200% or more is particularly preferred. The upper limit of the mass of hydrated water in the anhydride structure is not particularly limited, but is usually 1000%.

Examples of the compound capable of taking such a hydrate structure and its hydrate include sodium sulfate (Na ₂ SO ₄ ) and its hydrate (Na ₂ SO ₄ .10H ₂ O etc.), magnesium sulfate (MgSO ₄ ) and hydrates thereof (MgSO ₄ · 10H ₂ O, etc.), aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) and hydrates (Al ₂ (SO ₄ ) ₃ · 16H ₂ O, etc.), sodium acetate (CH ₃ COONa) and hydrates thereof (CH ₃ COONa · 3H ₂ O etc.), sodium pyrophosphate (Na ₄ P ₂ O ₇ ) and hydrates thereof (Na ₄ P ₂ O ₇ · 10H ₂ O etc.) , Sodium carbonate (Na ₂ CO ₃ ) and its hydrates (Na ₂ CO ₃ .10H ₂ O etc.), potassium carbonate (K ₂ CO ₃ ) and its hydrates (K ₂ CO ₃ .10H ₂ O etc.) Sodium tetraborate (Na ₂ B ₄ O ₇ ) and hydrates thereof (Na ₂ B ₄ O ₇ · 10H ₂ O, etc.), sodium chromate (Na ₂ CrO ₄ ) and hydrates (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.). These compounds that can take a hydrate structure and hydrates thereof can be used alone or in combination of two or more.

These hygroscopic agents, highly water-absorbing polymers, compounds capable of taking a hydrate structure or hydrates thereof can be used singly, but a plurality of types can be used in combination according to the purpose. In addition, when using the odorous substance adsorption agent of this invention for wallpaper use, it is preferable to use a hygroscopic agent from a viewpoint of maintaining aesthetics.

When using an additive 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, for example, preferably 0.1% by mass or more, more preferably 1.0% by mass or more. Preferably, 2.0% by 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 the total amount of odorant adsorbent is 100% by mass, for example, preferably 95.0% by mass or less, It is more preferably 90.0% by mass or less, and further preferably 85.0% by mass or less.

In addition, when using an additive such as a hygroscopic agent, a superabsorbent polymer, a compound capable of taking a hydrate structure or a hydrate thereof, the content is not particularly limited, and when heated to 130 ° C. or higher From the viewpoint of further improving the adsorption performance and adsorption rate of the hydrazine compound (the total amount of the hydrazine compound (1) and the hydrazine compound (2)) is preferably 10 to 1000 parts by mass, more preferably 50 to 1000 parts per 100 parts by mass. More preferred is part by mass, and still more preferred is 100 to 500 parts by mass.

(1-5) Odorant Adsorbent As described above, the odorant adsorbent of the present invention includes hydrazine compound (1) alone, hydrazine compound (1), and hydrazine compound (2) in combination. 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, or 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. Further, it can be mixed with powder and used as a powder. It can also be used as a pellet. However, when polyester fibers are heated at 130 ° C or higher, the bonds between molecules weaken and gaps are formed, and hydrazine compounds are encapsulated in them (not localized near the fiber surface), so deodorizing performance with hydrazine compounds Is not used in a form in which the odorant adsorbent of the present invention is supported on a polyester fiber. In particular, from the viewpoint of further suppressing the deactivation of the hydrazine compounds (hydrazine compound (1) and hydrazine compound (2)) by the presence of moisture and further improving the deodorization performance and deodorization rate, It is preferable to use it as a turbid liquid.

Examples of the solvent when the odorous substance adsorbent is a solution or suspension include, for example, water, lower alcohols, polyhydric alcohols, ketones, ethers, esters, aromatic solvents, halogenated hydrocarbon solvents, polar organic solvents. Etc.

Examples of the lower alcohol include alcohols having a linear or branched alkyl group having 1 to 4 carbon atoms. Specific examples include methanol, ethanol, n-propanol, isopropanol, and n-butanol.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and ethylene glycol monomethyl. Examples include ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether.

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

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, and dimethyl succinate.

Examples of the aromatic solvent include benzene, toluene, xylene, methylnaphthalene, dimethylnaphthalene, isopropylnaphthalene, diisopropylnaphthalene, ethylbiphenyl, diethylbiphenyl, and solvent naphtha.

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

Examples of the polar organic solvent include dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, N-methylpyrrolidone and the like.

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

It is also possible to use a mixture of the above components and a synthetic resin. Synthetic resins include, for example, polyacrylic resins (acrylic resins, methacrylic resins, etc.), polyvinyl acetate resins (vinyl acetate resins, etc.), polyvinyl chloride resins (vinyl chloride resins, etc.), polyolefin resins (olefin resins) Etc.), ethylene-vinyl acetate copolymer resin (EVA resin), polyurethane resin (urethane resin etc.), polystyrene resin (styrol resin etc.), polyepoxy resin (epoxy resin etc.), silicone resin (silicone resin) ), Alkyd resin (alkyd resin, etc.), fluorine resin (polytetrafluoroethylene resin, etc.), nylon resin, polyester resin (polyester, etc .; excluding polyester fiber), polyamide resin (aramid resin, etc.), PET resin (polyethylene terephthalate, etc.), ether resin (polyolefin) Niren'eteru resin), a polyamine resin, amino resin (melamine resin, urea resin, etc.), phenolic resins, and the like. A copolymer resin containing one or more of the above-described resins can also be employed. Moreover, the emulsion which consists of above-mentioned resin is also employable. These resins can be used alone or in combination of two or more. Of these, polyacrylic resins (acrylic resin, methacrylic resin, etc.) are preferable.

When a resin is contained in the odorant adsorbent of the present invention, 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 further preferably 85.0% by mass or less from the viewpoints of economy, workability, and the like.

It is also possible to use inorganic materials 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, and ceramic.

When an inorganic material is contained in the odorous substance adsorbent of the present invention, the content of the inorganic material is not particularly limited, and from the viewpoint of deodorizing performance, the total amount of the odorous substance 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 inorganic material is preferably 95.0% by mass or less, more preferably 90.0% by mass or less, and further preferably 85.0% by mass or less from the viewpoints of economy, workability, and the like.

The odorous substance adsorbent of the present invention is generally formulated into a wide variety of known additives such as non-volatile acids, chelating agents, antioxidants, light stabilizers, etc., depending on the purpose and application. Various third components used in the above can be blended.

Preferred non-volatile acids include succinic acid, fumaric acid, maleic acid, boric acid and the like, and salts thereof can also be employed. These nonvolatile acids can be used alone or in combination of two or more. By blending such a non-volatile acid, 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 the adsorbent as 100% by mass.

Examples of chelating agents include ethylenediaminetetraacetic acid, glycol etherdiaminetetraacetic 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 a chelating agent 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 antioxidant include a phenol-based antioxidant and an amine-based antioxidant. 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 amine-based antioxidants include alkyldiphenylamine and N, N′-di-sec-butyl-p-phenylenediamine. These antioxidants can be used alone or in combination of two or more.

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

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

When the light stabilizer is used, its content is not particularly limited, but is 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 odorous substance adsorbent of the present invention is used for heating to 130 ° C. or higher. Specifically, it is preferable to use at a temperature of 130 ° C. or higher in the production process or to be heated to 130 ° C. or higher during use. The heating temperature may include both cases where the product temperature reaches 130 ° C. or higher and where the ambient temperature (dryer temperature or the like) is 130 ° C. or higher. The heating temperature is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, further preferably 185 ° C. or higher, particularly preferably 190 ° C. or higher, from the viewpoint of the deodorizing performance and deodorizing speed of the odorant adsorbent of the present invention. More particularly preferred is 200 ° C. or higher. Further, the upper limit of the heating temperature in the application using the odorant adsorbent of the present invention is not particularly limited, but the temperature not exceeding 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 to a temperature that does not impair the quality of the use (building material, etc.) in which is used. From such a viewpoint, the upper limit of the heating temperature is usually 300 ° C. In addition, it is possible to improve the deodorizing performance in particular by adopting it for heating to the melting point of the hydrazine compound (especially hydrazine compound (1)) contained in the odorous substance adsorbent of the present invention. .

Examples of applications for heating to 130 ° C. or higher include building materials (wallpaper, flooring, ceiling materials, handrails, etc.), heating plastics, filters (excluding filters using polyester fibers), and the like.

(1-6) Odor Substance The odor substance adsorbent of the present invention described above can adsorb odor substances (particularly aldehyde compounds) efficiently and quickly at high temperatures (130 ° C. or higher). The odorous substance adsorbent of the present invention is effective for the above odorous substances that are used alone or in combination of two or more.

The odor substance as an object to be adsorbed by the odor substance adsorbent of the present invention is not particularly limited. For example, formaldehyde, acetaldehyde, propionaldehyde, acrolein, n-butyraldehyde, isobutyraldehyde, 3-methyl-butyraldehyde, croton Examples include aldehyde-based odorous substances (aldehyde compounds) such as aldehydes; alcohols such as pentanal, hexanal, heptanal, octanal, nonanal, and decanal; formic acid and the like. Among these, the odorant adsorbent of the present invention is particularly effective for the adsorption of aldehyde compounds, particularly formaldehyde and / or acetaldehyde.

2. Industrial Products Containing Odor Substance Adsorbent The odor substance adsorbent of the present invention can be used by being included (mixed) in industrial products. The industrial product includes the present invention (the industrial product of the present invention).

The industrial product refers to industrial products and industrial raw materials that have been widely known. Specifically, building materials (wallpaper, flooring, ceiling materials, handrails, etc.), plastics for heating, filters (excluding filters using polyester fibers), paints, adhesives, inks, sealing agents, paper products, binders, resins Emulsions, pulp, 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. Odor Substance Adsorption Method Using Odor Substance Adsorbent The odor substance adsorption method of the present invention is the odor substance adsorbent of the present invention by contacting the odor substance with the odor substance adsorbent of the present invention at 130 ° C. or higher. Adsorb odorous substances on the surface. According to the above adsorption method, the odorous substance adsorbent of the present invention efficiently and quickly adsorbs odorous substances (particularly aldehyde compounds) at a high temperature, so that the odorous substances (particularly aldehyde compounds) can be efficiently and quickly removed. Can do. In the adsorption method of the present invention, the above-mentioned industrial product of the present invention containing the odorous substance adsorbent of the present invention is brought into contact with the odorous substance (particularly an aldehyde compound), whereby the odorous substance adsorbent and the odorous substance (particularly the aldehyde compound). As a result, the odorous substance can also be efficiently adsorbed and removed.

In addition, the above-mentioned odorous substances can be efficiently and quickly removed by filling an adsorbing device such as a fixed bed, moving bed, fluidized bed, etc., and venting a gas containing an odorous substance (especially an aldehyde compound). It can be removed by adsorption over time.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the embodiments of the following examples. The following hydrazides were used.
Adipic acid dihydrazide (ADH): Tokyo Chemical Industry Co., Ltd. dodecanedioic acid dihydrazide (DDADH): Tokyo Chemical Industry Co., Ltd. isophthalic acid dihydrazide (IDH): Tokyo Chemical Industry Co., Ltd. product.

Comparative Example 1: ADH heating 200 ° C
Add 95 parts by mass of an acrylic emulsion (Ultrazol C-63 manufactured by Aika Kogyo Co., Ltd .; adjusted to a solid content of 10% by mass) with 5 parts by mass of adipic acid dihydrazide and dissolve in an ultrasonic bath. Adsorbent (adsorbed liquid).

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

Comparative Example 2: To 95 parts by mass of DDADH non-heated acrylic emulsion ( Ultrazol C-63 manufactured by Aika Kogyo Co., Ltd . ; adjusted to have a solid content of 10% by mass), 5 parts by mass of dodecanedioic acid dihydrazide was added. Then, it was dissolved in an ultrasonic bath to obtain an adsorbent (adsorbed liquid).

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

Example 1: DDADH heating 130 ° C
For the adsorbent (adsorbent) and deodorization test of Example 1 as in Comparative Example 1, except that dodecanedioic acid dihydrazide was used instead of adipic acid dihydrazide and the heating temperature was 130 ° C instead of 200 ° C. A sample was obtained.

Example 2: DDADH heating 150 ° C
For the adsorbent (adsorbent) and deodorization test of Example 2 as in Comparative Example 1, except that dodecanedioic acid dihydrazide was used instead of adipic acid dihydrazide and the heating temperature was 150 ° C instead of 200 ° C. A sample was obtained.

Example 3: DDADH heating 180 ° C
For the adsorbent (adsorbent) and deodorant test of Example 3 as in Comparative Example 1, except that dodecanedioic acid dihydrazide is used instead of adipic acid dihydrazide and the heating temperature is 180 ° C instead of 200 ° C. A sample was obtained.

Example 4: DDADH heating 200 ° C
The adsorbent (adsorbed liquid) and the sample for deodorization test 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
Adsorbent (adsorbed liquid) and sample for deodorization test of Example 5 as in Comparative Example 1 except that isophthalic acid dihydrazide was used instead of adipic acid dihydrazide and the heating temperature was changed to 230 ° C instead of 200 ° C. Got.

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

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

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

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

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

Comparative Example 4: Activated carbon heating 200 ° C
Similar to Comparative Example 3, except that activated carbon (Shirakaba WP-H manufactured by Osaka Gas Chemical Co., Ltd.) was used instead of silica, an adsorbent (adsorbent) and a sample for deodorization test of Comparative Example 4 were obtained. It was.

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

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

Example 9: DDADH / ADH = 8: 2 heating 200 ° C.
Instead of 5 parts by mass of adipic acid dihydrazide, the adsorption of Example 9 was performed in the same manner as in Comparative Example 1, except that the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 8: 2 by mass ratio. An agent (adsorbed liquid) and a sample for deodorization test were obtained.

Example 10: DDADH / ADH = 5: 5 heating 200 ° C.
Instead of 5 parts by weight of adipic acid dihydrazide, the adsorption of Example 10 was performed in the same manner as in Comparative Example 1, except that the blending ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 5: 5 by mass ratio. An agent (adsorbed liquid) and a sample for deodorization test were obtained.

Example 11: DDADH / ADH = 4: 6 heating 200 ° C.
Instead of 5 parts by weight of adipic acid dihydrazide, the adsorption of Example 11 was performed in the same manner as in Comparative Example 1, except that the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 4: 6 by mass ratio. An agent (adsorbed liquid) and a sample for deodorization test were obtained.

Example 12: DDADH / ADH = 3: 7 heating 200 ° C.
Instead of 5 parts by weight of adipic acid dihydrazide, the adsorption of Example 12 was performed in the same manner as in Comparative Example 1 except that the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 3: 7 by mass ratio. An agent (adsorbed liquid) and a sample for deodorization test were obtained.

Example 13: DDADH / ADH = 2: 8 heating 200 ° C.
Instead of 5 parts by mass of adipic acid dihydrazide, the adsorption of Example 13 was performed in the same manner as in Comparative Example 1, except that the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 2: 8 by mass ratio. An agent (adsorbed liquid) and a sample for deodorization test were obtained.

Example 14: DDADH / ADH = 9: 1 + silica heating 200 ° C.
Instead of dodecanedioic acid dihydrazide, the adsorbent of Example 14 was used in the same manner as in Example 6 except that the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 9: 1 by mass. Adsorbed liquid) and a sample for deodorization test were obtained.

Example 15: DDADH / ADH = 8: 2+ silica heating 200 ° C.
Instead of dodecanedioic acid dihydrazide, the adsorbent of Example 15 was used in the same manner as in Example 6 except that the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 8: 2 by mass. Adsorbed liquid) and a sample for deodorization test were obtained.

Example 16: DDADH / ADH = 6: 4 + silica heating 200 ° C.
Instead of dodecanedioic acid dihydrazide, the adsorbent of Example 16 was used in the same manner as in Example 6 except that the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 6: 4 by mass. Adsorbed liquid) and a sample for deodorization test were obtained.

Example 17: DDADH / ADH = 5: 5 + silica heating 200 ° C.
Instead of dodecanedioic acid dihydrazide, the adsorbent of Example 17 was the same as in Example 6 except that the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 5: 5 by mass. Adsorbed liquid) and a sample for deodorization test were obtained.

Example 18: DDADH / ADH = 4: 6 + silica heating 200 ° C.
Instead of dodecanedioic acid dihydrazide, the adsorbent of Example 18 was used in the same manner as in Example 6 except that the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 4: 6 by mass. Adsorbed liquid) and a sample for deodorization test were obtained.

Example 19: DDADH / ADH = 2: 8 + silica heating 200 ° C.
The adsorbent of Example 19 was the same as that of Example 6 except that instead of dodecanedioic acid dihydrazide, the mixing ratio of dodecanedioic acid dihydrazide and adipic acid dihydrazide was 2: 8 in terms of mass ratio. Adsorbed liquid) and a sample for deodorization test were obtained.

Comparative Example 5: ADH + silica heating 200 ° C
An adsorbent (adsorbed liquid) and a sample for deodorization test 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 sample for deodorization test obtained in Examples 1 to 8 and Comparative Examples 1 to 4 is placed in a 1 L Tedlar bag (manufactured by GL Sciences), sealed, and then air is removed from the Tedlar bag using a piston. It was. Thereafter, 1 L of acetaldehyde gas adjusted to 14 ppm was injected, and the residual gas concentration after 30 minutes, 1 hour, 3 hours, 24 hours and 48 hours was detected using a detector tube (Gastech Co., Ltd.). evaluated. The results are shown in Tables 1-2.

Test Example 2 (Acetaldehyde adsorption performance)
A deodorization test was performed in the same manner as in Test Example 1 above. Specifically, one sample for deodorization test obtained in Examples 4 and 9 to 13 and Comparative Example 1 was placed in a 1 L Tedlar bag (manufactured by GL Sciences Inc.), sealed, and then Tedlar bag using a piston. The air inside was pulled out. 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 detector tube (Gastech Co., Ltd.). The results are shown in Table 3. Also, with the total amount of DDADH and ADH as 1, the content ratio of DDADH (DDADH content / (DDADH content + ADH content)) on the horizontal axis, the residual rate of odorous substances after 24 hours (acetaldehyde after 24 hours) FIG. 1 shows a plot with the concentration / initial acetaldehyde concentration (14 ppm) × 100 (%)) as the vertical axis. FIG. 1 also shows the theoretical value of the residual ratio calculated from the results of Example 4 and Comparative Example 1.

Test Example 3 (Acetaldehyde adsorption performance)
A deodorization test was conducted in the same manner as in Test Example 2 above. Specifically, one sample for deodorization test obtained in Examples 6 and 14 to 19 and Comparative Example 5 was placed in a 1 L Tedlar bag (manufactured by GL Sciences Inc.), sealed, and then Tedlar bag using a piston. The air inside was pulled out. Then, 1 L of acetaldehyde gas adjusted to 14 ppm was injected, and the residual gas concentration after 0.5 hours, 1 hour, 3 hours, 24 hours and 48 hours was evaluated using a detector tube (Gastech). did. The results are shown in Table 4. Also, with the total amount of DDADH and ADH as 1, the content ratio of DDADH (DDADH content / (DDADH content + ADH content)) on the horizontal axis, the residual rate of odorous substances after 24 hours (acetaldehyde after 24 hours) FIG. 2 shows a plot with the concentration / initial acetaldehyde concentration (14 ppm) × 100 (%)) as the vertical axis. FIG. 2 also shows the theoretical value 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 used as an odorant adsorbent in the past, was used alone, its deodorizing performance decreased at high temperatures. On the other hand, although dodecanedioic acid dihydrazide has almost no deodorizing performance at room temperature, it exhibited a deodorizing performance far superior to adipic acid dihydrazide at high temperatures. 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 could be maintained even though the amount of dodecanedioic acid dihydrazide was reduced. In particular, since dodecanedioic acid dihydrazide is expensive compared to adipic acid dihydrazide, it is useful that excellent deodorizing performance can be obtained even if the amount used is reduced.

Further, 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, low performance adipic acid dihydrazide is used. Despite being mixed, the deodorizing performance was improved as compared with dodecanedioic acid dihydrazide alone. In addition, as shown in the theoretical values in Tables 3 to 4 and FIGS. 1 and 2, it is assumed that the performance of connecting a straight line between the case of dodecanedioic acid dihydrazide alone and the case of adipic acid dihydrazide alone, The measured data showed that the residual rate of odorous substances was significantly smaller than the theoretical value. For this reason, when dodecanedioic acid dihydrazide and adipic acid dihydrazide are mixed, the deodorizing performance is remarkably compared with the theoretical value expected 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 considered that the presence of dodecanedioic acid dihydrazide prevented the dry deactivation of adipic acid dihydrazide for some reason. Thus, when dodecanedioic acid dihydrazide and adipic acid dihydrazide are mixed, it is 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) that hardly exhibits deodorant performance when used alone is added to DDADH and, if necessary, ADH, and the amount of hydrazine compound used is reduced accordingly. . In other words, in Table 4 of Test Example 3, compared with Table 3 of Test Example 2, the silica that does not exhibit deodorizing performance alone even though the amount of active ingredient (the amount of hydrazine compound used) is halved. Surprisingly, the residual rate after 24 hours is the same as or higher than that in Table 3 of Test Example 2. From this result, although silica does not exhibit deodorant performance when used alone, it has a function of improving the deodorization performance of DDADH, which is a hydrazine compound, and as a result, it is considered that it plays a role of synergistic effect. .

Claims (13)

1. An odorous substance adsorbent containing a hydrazine compound having a molecular weight of 180 or more and used for heating to 130 ° C or higher.
2. 2. The odorant adsorbent according to claim 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.
3. The odorant adsorbent according to claim 1 or 2, further comprising a hydrazine compound having a molecular weight of less than 180.
4. The odorant adsorbent according to claim 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.
5. The odorous substance adsorbent according to any one of claims 1 to 4, further comprising an inorganic porous material.
6. The odorous substance adsorbent according to claim 5, wherein the inorganic porous material is a compound containing silicon.
7. The odorous substance adsorbent according to claim 5 or 6, wherein the inorganic porous material is silica.
8. 8. The composition according to claim 1, 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. Odor substance adsorbent.
9. The odorous substance adsorbent according to any one of claims 1 to 8, wherein the odorous substance is an aldehyde compound.
10. An industrial product comprising the odorous substance adsorbent according to any one of claims 1 to 9 and being used by being heated to 130 ° C or higher or heated to 130 ° C or higher in the production process.
11. A building material, a heating plastic or a filter (except for a filter using polyester fiber) containing the odorant adsorbent according to any one of claims 1 to 9.
12. Use of the odorous substance adsorbent according to any one of claims 1 to 9 for heating to 130 ° C or higher.
13. A method for adsorbing an odorous substance, comprising the step of bringing the odorous substance into contact with the odorous substance adsorbent according to any one of claims 1 to 9 at 130 ° C or higher.

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