Odor-causing substance adsorbent

Abstract

To provide an odorant adsorbent that has an improved ability to adsorb an aldehyde compound having two or more carbon atoms even during heating at high temperatures, and can suppress its coloration.SOLUTION: An odorant adsorbent adsorbs an aldehyde compound having two or more carbon atoms, the odorant adsorbent containing a polycyclic aromatic hydrazine compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to an odor substance adsorbent. [Background technology]

[0002] In recent years, consumer demand for odor elimination has been increasing. Among these, aldehyde compounds with two or more carbon atoms, such as acetaldehyde, are considered to be causative agents of sick building syndrome. Compared to formaldehyde, they are difficult to adsorb with general-purpose adsorbents (for example, general-purpose activated carbon), making them particularly in high demand for odor elimination. Hydrazine compounds are known as adsorbents for such odor substances.

[0003] Among these, dihydrazide adipic acid, which has relatively high deodorizing performance, is widely used (see, for example, Patent Document 1).

[0004] However, in applications where the manufacturing process involves heating to 130°C or higher, there is a problem in that the deodorizing performance of adipic acid dihydrazide is not fully exhibited. This is thought to be because the heat history causes some kind of change in adipic acid dihydrazide, reducing its deodorizing performance. In other words, adipic acid dihydrazide has insufficient heat resistance as a deodorizer. For example, in the field of plastic mixing, which is seen in the manufacture of building materials, the molding and drying processes of coatings may involve exposure to an environment of 200°C for about 10 minutes, which reduces the deodorizing performance of adipic acid dihydrazide.

[0005] As described in Patent Document 2, the present inventors have found that by using hydrazine compounds with a large molecular weight, such as dodecane dioate dihydrazide, the adsorption performance of aldehyde compounds can be improved even when heated at high temperatures. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2009 / 122975 [Patent Document 2] Japanese Patent Publication No. 2018-187336 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] However, even when using dodecane dioxide dihydrazide, there is still room for improvement in coloration during high-temperature heating.

[0008] Therefore, the objective is to provide an odor substance adsorbent that exhibits excellent adsorption performance of aldehyde compounds with two or more carbon atoms, even when heated at high temperatures, and that can suppress discoloration. [Means for solving the problem]

[0009] The inventors of the present invention conducted extensive research to achieve the above objectives and discovered that, although polycyclic aromatic hydrazine compounds do not exhibit high adsorption performance for aldehyde compounds with two or more carbon atoms at room temperature, they surprisingly exhibit excellent deodorizing performance and can suppress discoloration under heating conditions of 130°C or higher. As a result, they found that under heating conditions where the deodorizing performance of adipic acid dihydrazide decreases, polycyclic aromatic hydrazine compounds exhibit excellent adsorption performance and can also suppress discoloration. Based on these findings, the inventors conducted further research and completed the present invention. That is, the present invention encompasses the following configuration.

[0010] Item 1. An odor substance adsorbent that adsorbs aldehyde compounds having 2 or more carbon atoms, An odor-causing adsorbent containing a polycyclic aromatic hydrazine compound.

[0011] Item 2. The odor substance adsorbent according to Item 1, wherein the polycyclic aromatic hydrazine compound has a planar structure.

[0012] Item 3. The odor substance adsorbent according to item 1 or 2, wherein the polycyclic aromatic hydrazine compound has a total of three or more hydrocarbon rings.

[0013] Item 4. The odorant adsorbent according to any one of Items 1 to 3, wherein the polycyclic aromatic hydrazine compound has a fluorene skeleton.

[0014] Item 5. The polycyclic aromatic hydrazine compound is represented by General Formulas (1) to (4):

[0015] [Chemical Formula]

[0016] [In the formula, R 1a , R 2a , R 1b , R 2b , R 1c , R 2c , R 1d and R 2d are the same or different and represent substituents. R 3 , R 4 , R 6 and R 7 are the same or different and represent divalent hydrocarbon groups. R 5 represents a trivalent hydrocarbon group. m1, n1, m2, n2, m3, n3, m4 and n4 are the same or different and represent integers from 0 to 4.] The odorant adsorbent according to claim 4, which is a polycyclic aromatic hydrazine compound represented by the formula.

[0017] Item 6. The odorant adsorbent according to Item 1 or 2, wherein the polycyclic aromatic hydrazine compound has a naphthalene skeleton.

[0018] Item 7. The odorant adsorbent according to any one of Items 1 to 6, which is used for applications involving heating at 130°C or higher.

[0019] Item 8. The odorant adsorbent according to any one of Items 1 to 7, wherein the median diameter of the polycyclic aromatic hydrazine compound is 0.1 to 500 μm.

[0020] Item 9. A molded product containing the odorant adsorbent according to any one of Items 1 to 8.

[0021] Item 10. A molded article as described in Item 9, which is heated to 130°C or higher during the manufacturing process, or is used after being heated to 130°C or higher.

[0022] Item 11. A method for adsorbing odorous substances, comprising the step of bringing an odorous substance containing an aldehyde compound having 2 or more carbon atoms into contact with an odorous substance adsorbent according to any one of items 1 to 8 or a molded article according to item 9 or 10.

[0023] Item 12. The adsorption method according to Item 11, wherein the contact step is a step of bringing the odor substance and the odor substance adsorbent into contact at a temperature of 130°C or higher. [Effects of the Invention]

[0024] The odor substance adsorbent of the present invention exhibits excellent adsorption performance of aldehyde compounds having 2 or more carbon atoms, even under heating conditions where the adsorption performance of adipic acid dihydrazide decreases, and can suppress discoloration. [Brief explanation of the drawing]

[0025] [Figure 1] The results of odor substance adsorption performance measurements using the odor removal test samples obtained in Example 1 and Comparative Examples 1-3 are shown. For comparison, the results for natural depletion (no additives used) and blank (water used) are also shown. [Figure 2] The results of odor substance adsorption performance measurements using the odor elimination test samples obtained in Example 3 and Comparative Examples 4-6 are shown. For comparison, the results for natural depletion (no additives used) and blank (water used) are also shown. [Figure 3] The results of odor substance adsorption performance measurements using the odor elimination test samples obtained in Example 4 and Comparative Examples 7-9 are shown. For comparison, the results for natural depletion (no additive used) and blank (water used) are also shown. [Modes for carrying out the invention]

[0026] In this specification, "contains" is a concept that encompasses all of the following: "contains," "consist essentially of," and "consist of."

[0027] Furthermore, in this specification, when a numerical range is indicated as "A to B", it means A or greater and B or less.

[0028] 1. Odor-causing substance adsorbent The odor substance adsorbent of the present invention is an odor substance adsorbent that adsorbs aldehyde compounds having 2 or more carbon atoms, and contains a polycyclic aromatic hydrazine compound.

[0029] (1-1) Polycyclic aromatic hydrazine compounds In this invention, the hydrazine compound contains a polycyclic aromatic hydrazine compound.

[0030] Although this polycyclic aromatic hydrazine compound has poor reactivity at room temperature and inferior adsorption performance for aldehyde compounds with two or more carbon atoms, when heated to 130°C or higher, it dramatically improves deodorizing performance and deodorizing speed, unlike conventionally widely used adipic acid dihydrazide. In other words, the odor substance adsorbent of the present invention can be used as a deodorizer suitable for applications where heating to 130°C or higher is required.

[0031] Furthermore, this polycyclic aromatic hydrazine compound does not decompose even when heated to 130°C or above, especially 180°C or above, and can effectively suppress discoloration.

[0032] The polycyclic aromatic hydrazine compound is not particularly limited as long as it is an aromatic hydrazine compound having multiple rings (two or more). However, from the viewpoint of adsorption performance and adsorption rate of aldehyde compounds with two or more carbon atoms when heated to high temperatures of 130°C or higher, and suppression of discoloration, it is preferable that it has a planar structure in which hydrocarbon rings are condensed together.

[0033] Examples of rings (preferably hydrocarbon rings) that polycyclic aromatic hydrazine compounds may possess include alicyclic hydrocarbon rings such as cyclopropane rings, cyclobutane rings, cyclopentane rings, and cyclohexane rings; and aromatic hydrocarbon rings such as benzene rings. Although polycyclic aromatic hydrazine compounds have two or more of these rings, they are aromatic compounds and therefore have at least one aromatic hydrocarbon ring.

[0034] The number of rings (preferably hydrocarbon rings) in this polycyclic aromatic hydrazine compound is not particularly limited, but from the viewpoint of adsorption performance and adsorption rate of aldehyde compounds with 2 or more carbon atoms when heated to high temperatures of 130°C or higher, and suppression of discoloration, it is 2 or more, preferably 3 or more. There is no particular upper limit to the number of rings (preferably hydrocarbon rings) in the polycyclic aromatic hydrazine compound, but it is usually 10.

[0035] The skeletons of these polycyclic aromatic hydrazine compounds include, specifically, fluorene, naphthalene, anthracene, tetracene, chrysene, pyrene, and triphenylene skeletons. From the viewpoint of adsorption performance and adsorption rate of aldehyde compounds with two or more carbon atoms at high temperatures of 130°C or higher, as well as discoloration suppression and economic efficiency, fluorene and naphthalene skeletons are preferred.

[0036] While there are no particular limitations on whether such polycyclic aromatic hydrazine compounds have a fluorene skeleton, for example, general formulas (1) to (4):

[0037] [ka]

[0038] [In the formula, R 1a , R 2a , R 1b , R 2b , R 1c , R 2c , R 1d and R 2d R indicates a substituent that is either the same or different.3 , R 4 , R 6 and R 7 These are identical or different, and represent a divalent hydrocarbon group. 5 represents a trivalent hydrocarbon group. m1, n1, m2, n2, m3, n3, m4, and n4 are the same or different, and represent integers from 0 to 4. Preferably, it is a fluorene-containing hydrazine compound represented by [formula].

[0039] In the above general formulas (1) to (4), substituent R 1a , R 2a , R 1b , R 2b , R 1c , R 2c , R 1d and R 2d Examples of such groups are not particularly limited, but include cyano groups, halogen atoms, carboxyl groups, hydrocarbon groups (alkyl groups, cycloalkyl groups, aryl groups, etc.), and acyl groups.

[0040] Examples of halogen atoms used as substituents include fluorine atoms, chlorine atoms, and bromine atoms.

[0041] Examples of alkyl groups used as substituents include linear or branched alkyl groups having 1 to 12 carbon atoms (particularly 1 to 8, and even more specifically 1 to 4), such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups.

[0042] Alkyl groups may have substituents. Examples of substituents that alkyl groups may have include cyano groups, the halogen atoms mentioned above, carboxyl groups, cycloalkyl groups (described later), aryl groups (described later), and acyl groups (described later). When an alkyl group has substituents, there is no particular limit to the number of substituents, and it can be 1 to 6, or more specifically 1 to 3.

[0043] Examples of cycloalkyl groups used as substituents include cycloalkyl groups having 3 to 10 carbon atoms (particularly 4 to 8 carbon atoms), such as cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl groups.

[0044] Cycloalkyl groups may have substituents. Examples of substituents that cycloalkyl groups may have include cyano groups, the halogen atoms mentioned above, carboxyl groups, the alkyl groups mentioned above, the cycloalkyl groups mentioned above, the aryl groups described later, and the acyl groups described later. When a cycloalkyl group has substituents, there is no particular limit to the number of substituents, and it can be 1 to 6, and especially 1 to 3.

[0045] Examples of aryl groups used as substituents include aryl groups having 6 to 14 carbon atoms (particularly 6 to 12 carbon atoms), such as phenyl, naphthyl, and biphenyl groups.

[0046] The aryl group may also have substituents. Examples of substituents that the aryl group may have include the cyano group, the halogen atom mentioned above, the carboxyl group, the alkyl group mentioned above, the cycloalkyl group mentioned above, the aryl group mentioned above, and the acyl group described later. When the aryl group has substituents, there is no particular limit to the number of substituents, and it can be 1 to 6, and especially 1 to 3.

[0047] Examples of acyl groups as substituents include acyl groups composed of the alkyl group and carbonyl group mentioned above, such as methyl carbonyl group and ethyl carbonyl group, which have 2 to 13 carbon atoms (particularly 2 to 9, and even more so 2 to 5). The substituent R1 is often an alkyl group or similar.

[0048] The acyl group may have substituents. Examples of substituents that the acyl group may have include a cyano group, the halogen atom mentioned above, a carboxyl group, the alkyl group mentioned above, the cycloalkyl group mentioned above, the aryl group mentioned above, and the acyl group mentioned above. When the acyl group has substituents, there is no particular limit to the number of substituents, and it can be 1 to 6, and especially 1 to 3.

[0049] In the above formulas (1) to (4), substituent R 1a , R 2a , R 1b , R 2b , R 1c , R 2c , R 1d and R 2d From the viewpoints of compound stability, ease of synthesis, adsorption performance and adsorption rate of aldehyde compounds with 2 or more carbon atoms when heated to high temperatures of 130°C or higher, and suppression of discoloration, hydrocarbon groups are preferred, and alkyl groups are more preferred.

[0050] Furthermore, if there are multiple coefficients m1, n1, m2, n2, m3, n3, m4 and n4 (integers from 2 to 4), then there are multiple substituents R 1a , R 2a , R 1b , R 2b , R 1c , R 2c , R 1d and R 2d The types may be the same or different. Also, substituents R substituted on different benzene rings may be different. 1a , R 2a , R 1b , R 2b , R 1c , R 2c , R 1d and R 2d The types may be the same or different. Also, substituent R 1a , R 2a , R 1b , R 2b , R 1c , R 2c , R 1d and R 2dThe bonding position (substitution position) is not particularly limited and can be, for example, the 2nd or 7th position of the fluorene ring. From the viewpoint of compound stability, ease of synthesis, adsorption performance and adsorption rate of aldehyde compounds with 2 or more carbon atoms when heated to high temperatures of 130°C or higher, and suppression of discoloration, the coefficients m1, n1, m2, n2, m3, n3, m4, and n4 are all preferably 0 or 1, and more preferably 0. Note that the coefficients m1, n1, m2, n2, m3, n3, m4, and n4 may be the same or different.

[0051] In the above equations (1) to (4), R 3 , R 4 , R 6 and R 7 The divalent hydrocarbon group and R shown by 5 Examples of hydrocarbons corresponding to the trivalent hydrocarbon group shown include aliphatic hydrocarbons such as acyclic aliphatic hydrocarbons (alkanes, alkenes, etc.) and alicyclic hydrocarbons (cycloalkanes, bridged cyclic hydrocarbons, etc.); and aromatic hydrocarbons such as monocyclic arenes and polycyclic arenes.

[0052] R 3 , R 4 , R 6 and R 7 The divalent hydrocarbon group and R shown by 5 Examples of alkanes as acyclic aliphatic hydrocarbons corresponding to the trivalent hydrocarbon group shown include alkanes with 1 to 12 carbon atoms (particularly 1 to 8, and even 1 to 4), such as methane, ethane, propane, butane, isobutane, pentane, isopentane, hexane, heptane, and octane.

[0053] Alkanes may also have substituents. Examples of substituents that alkanes may have include cyano groups, the halogen atoms mentioned above, carboxyl groups, cycloalkyl groups, aryl groups, and acyl groups. When an alkane has substituents, there is no particular limit to the number of substituents, and it can be 1 to 6, and especially 1 to 3.

[0054] R 3 , R 4 , R6 and R 7 and the divalent hydrocarbon group represented by R 5 Examples of the alkene as an acyclic aliphatic hydrocarbon corresponding to the trivalent hydrocarbon group represented by R

[0055] The alkene may have a substituent. Examples of the substituent that the alkene can have include a cyano group, the halogen atom, a carboxy group, the cycloalkyl group, the aryl group, the acyl group, etc. When the alkene has a substituent, the number of substituents is not particularly limited and can be 1 to 6, particularly 1 to 3.

[0056] R 3 、R 4 、R 6 and R 7 and the divalent hydrocarbon group represented by R 5 Examples of the cycloalkane as an alicyclic hydrocarbon corresponding to the trivalent hydrocarbon group represented by R

[0057] The cycloalkane may have a substituent. Examples of the substituent that the alkene can have include a cyano group, the halogen atom, a carboxy group, the alkyl group, the cycloalkyl group, the aryl group, the acyl group, etc. When the alkene has a substituent, the number of substituents is not particularly limited and can be 1 to 6, particularly 1 to 3.

[0058] R 3 、R 4 、R 6 and R 7 and the divalent hydrocarbon group represented by R 5 Examples of the bridged cyclic hydrocarbon as an alicyclic hydrocarbon corresponding to the trivalent hydrocarbon group represented by R

[0059] The bridged cyclic hydrocarbon may also have a substituent. Examples of the substituent that the bridged cyclic hydrocarbon can have include a cyano group, the above-mentioned halogen atom, a carboxy group, the above-mentioned alkyl group, the above-mentioned cycloalkyl group, the above-mentioned aryl group, the above-mentioned acyl group, etc. When the alkene has a substituent, the number of substituents is not particularly limited and can be 1 to 6, particularly 1 to 3.

[0060] R 3 、R 4 、R 6 及びR 7 Examples of the monocyclic arene as the alicyclic hydrocarbon corresponding to the divalent hydrocarbon group represented by and the trivalent hydrocarbon group represented by R 5 include benzene.

[0061] The monocyclic arene may also have a substituent. Examples of the substituent that the monocyclic arene can have include a cyano group, the above-mentioned halogen atom, a carboxy group, the above-mentioned alkyl group, the above-mentioned cycloalkyl group, the above-mentioned aryl group, the above-mentioned acyl group, etc. When the alkene has a substituent, the number of substituents is not particularly limited and can be 1 to 6, particularly 1 to 3.

[0062] R 3 、R 4 、R 6 及びR 7 Examples of the polycyclic arene as the alicyclic hydrocarbon corresponding to the divalent hydrocarbon group represented by and the trivalent hydrocarbon group represented by R 5 include condensed polycyclic arenes such as naphthalene and anthracene.

[0063] The polycyclic arene may also have a substituent. Examples of the substituent that the polycyclic arene can have include a cyano group, the above-mentioned halogen atom, a carboxy group, the above-mentioned alkyl group, the above-mentioned cycloalkyl group, the above-mentioned aryl group, the above-mentioned acyl group, etc. When the alkene has a substituent, the number of substituents is not particularly limited and can be 1 to 6, particularly 1 to 3.

[0064] R that satisfies the above conditions 3 , R 4 , R 6 and R 7 Examples of divalent hydrocarbon groups shown include divalent aliphatic hydrocarbon groups (alkylene groups (or alkylidene groups), arylalkylene groups, cycloalkylene groups, alkylcycloalkylene groups, alkylene-cycloalkylene groups, alkylene-arylene groups, alkylene-arylene-alkylene groups, etc.) and divalent aromatic hydrocarbon groups (arylene groups, alkylarylene groups, etc.).

[0065] Examples of alkylene groups (or alkylidene groups) include linear or branched alkylene groups having 1 to 12 carbon atoms (particularly 1 to 8, and even more so 1 to 4), such as methylene group, ethylene group, ethylidene group, trimethylene group, propylene group, propyridene group, isopropyridene group, tetramethylene group, 2-methylpropane-1,3-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-2-ylidene group, butane-2,3-diyl group, pentamethylene group, pentane-2,3-diyl group, and hexamethylene group.

[0066] Examples of arylalkylene groups include arylalkylene groups consisting of an aryl group having 6 to 12 carbon atoms (particularly 6 to 10), such as a phenylethylene group, and an alkylene group having 1 to 4 carbon atoms (particularly 1 to 2).

[0067] Examples of cycloalkylene groups include cyclobutylene groups, cyclopentylene groups, cyclohexylene groups (such as 1,4-cyclohexylene groups), and cycloheptylene groups, which have 4 to 10 carbon atoms (especially 5 to 8, and even 5 to 6).

[0068] Examples of alkylcycloalkylene groups include alkylcycloalkylene groups consisting of an alkyl group having 1 to 4 carbon atoms, such as a methylcyclohexylene group, and a cycloalkylene group having 4 to 10 carbon atoms.

[0069] Examples of alkylene-cycloalkylene groups include the methylene-cyclohexylene group [-CH2-C6H 10 -](methylene-1,4-cyclohexylene group, etc.), ethylene-cyclohexylene group[-CH2CH2-C6H 10 -](ethylene-1,4-cyclohexylene group, etc.), ethylidene-cyclohexylene group [-CHCH3-C6H 10 Examples include alkylene-cycloalkylene groups, which consist of an alkylene group having 1 to 4 carbon atoms (especially 1 to 2 carbon atoms) and a cycloalkylene group having 4 to 10 carbon atoms (especially 5 to 8 carbon atoms), such as the ethylidene-1,4-cyclohexylene group.

[0070] Examples of alkylene-arylene groups include alkylene-arylene groups consisting of an alkylene group having 1 to 4 carbon atoms, such as a methylene-phenylene group or an ethylene-phenylene group, and an arylene group having 6 to 10 carbon atoms.

[0071] Examples of alkylene-arylene-alkylene groups include alkylene-arylene-alkylene groups consisting of an alkylene group having 1 to 4 carbon atoms, such as a methylene-phenylene-methylene group (xylylene group), an arylene group having 6 to 10 carbon atoms, and an alkylene group having 1 to 4 carbon atoms.

[0072] Examples of arylene groups include phenylene groups and naphthylene groups, which have 6 to 10 carbon atoms.

[0073] Examples of alkylarylene groups include alkylarylene groups consisting of an alkyl group having 1 to 4 carbon atoms, such as a methylphenylene group or a dimethylphenylene group, and an arylene group having 6 to 10 carbon atoms.

[0074] In particular, as divalent hydrocarbon groups, alkylene groups (linear or branched alkylene groups) are preferred from the viewpoint of compound stability, ease of synthesis, adsorption performance and adsorption rate of aldehyde compounds with 2 or more carbon atoms when heated to high temperatures of 130°C or higher, and suppression of discoloration. For example, linear or branched alkylene groups with 1 to 12 carbon atoms (especially 1 to 8, and even more preferably 1 to 4) such as methylene group, ethylene group, trimethylene group, propylene group, 2-ethylethylene group, and 2-methylpropane-1,3-diyl group are preferred.

[0075] Furthermore, as a trivalent hydrocarbon group, in terms of compound stability, ease of synthesis, adsorption performance and adsorption rate of aldehyde compounds with 2 or more carbon atoms at high temperatures of 130°C or higher, and suppression of discoloration, in particular, general formula (5):

[0076] [ka]

[0077] [In the formula, k represents an integer between 0 and 4.] A base represented by is preferred.

[0078] While there are no particular limitations on whether such polycyclic aromatic hydrazine compounds have a naphthalene skeleton, for example, general formulas (6) to (8):

[0079] [ka]

[0080] [In the formula, R 8a , R 9a , R 8b and R 9b R indicates a substituent that is either the same or different. 10 , R 11 and R 12 The same or different elements represent a single bond or a divalent hydrocarbon group. m5, n5, m6, and n6 are the same or different elements and represent integers from 0 to 4. 13 and R 14One of them is a hydrogen atom or an alkoxy group, and the other is

[0081] [ka]

[0082] (In the formula, R 17 (where n represents a divalent hydrocarbon group; n represents 0 or 1.) This indicates the group represented by R. 15 and R 16 One of them is a hydrogen atom or an alkoxy group, and the other is

[0083] [ka]

[0084] (In the formula, R 17 (where n represents the divalent hydrocarbon group described above, and n represents 0 or 1.) This indicates the group represented by [ ]. It is preferable that the compound is a naphthalene-containing hydrazine compound represented by [formula].

[0085] In the above general formulas (6) to (7), substituent R 8a , R 9a , R 8b and R 9b As for the substituent R in the general formulas (1) to (4) described above, 1a , R 2a , R 1b , R 2b , R 1c , R 2c , R 1d and R 2d It can be treated the same way as above.

[0086] In the above general formulas (6) to (7), R 10 , R 11 and R 12 If is a divalent hydrocarbon group, then the R in the general formulas (1) to (4) above is the divalent hydrocarbon group. 3 , R 4 , R 6 and R7 It can be treated the same way as above.

[0087] In the above general formula (8), R 17 The divalent hydrocarbon group shown is R in the general formulas (1) to (4) above. 3 , R 4 , R 6 and R 7 It can be treated the same way as above.

[0088] R 13 , R 14 , R 15 and R 16 When the group is an alkoxy group, examples of alkoxy groups include linear or branched alkoxy groups having 1 to 12 carbon atoms (particularly 1 to 8, and even more specifically 1 to 4), such as methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy groups.

[0089] Alkoxy groups may also have substituents. Examples of substituents that alkoxy groups may have include cyano groups, the halogen atoms mentioned above, carboxyl groups, cycloalkyl groups (described later), aryl groups (described later), and acyl groups (described later). When an alkoxy group has substituents, there is no particular limit to the number of substituents, and it can be 1 to 6, or more specifically, 1 to 3.

[0090] The melting point of the polycyclic aromatic hydrazine compound is not particularly limited, but from the viewpoint of coloration during high-temperature heating, for example, 130°C or higher is preferred, 200°C or higher is more preferred, and 230°C or higher is even more preferred. In terms of the adsorption performance of aldehyde compounds, the melting point of the polycyclic aromatic hydrazine compound does not necessarily have to exceed the aforementioned preferred melting point due to the effect of improved solubility in additives due to heating. There is no particular upper limit to the melting point of the polycyclic aromatic hydrazine compound, but it is usually around 400°C. Furthermore, for example, by using a polycyclic aromatic hydrazine compound with a melting point slightly higher than the temperature at which the industrial product is heated during the manufacturing process or the temperature at which the industrial product is used, some of the compound will melt when heated, reducing the particle size of the odor substance adsorbent of the present invention and increasing its surface area, making it possible to efficiently contact odor substances and thus further improve the deodorizing performance during heating.

[0091] Examples of polycyclic aromatic hydrazine compounds that satisfy the above conditions include, for example, 9,9-bis(hydrazinocarbonylalkyl)fluorenes, 9,9-bis(hydrazinocarbonylcycloalkyl)fluorenes, 9-(hydrazinocarbonyl-hydrazinocarbonylalkyl)fluorenes, 2,6-bis(hydrazinocarbonylalkyl)naphthalenes, and 2-(hydrazinocarbonylalkyl)naphthalenes.

[0092] Examples of 9,9-bis(hydrazinocarbonylalkyl)fluorenes include 9,9-bis(hydrazinocarbonylmethyl)fluorene, 9,9-bis(2-hydrazinocarbonylethyl)fluorene, 9,9-bis(1-hydrazinocarbonylethyl)fluorene, 9,9-bis(1-hydrazinocarbonyl-n-propyl)fluorene, 9,9-bis(2-hydrazinocarbonyl-n-propyl)fluorene, and 9,9- 9,9-bis(hydrazinocarbonyl C)fluorene, such as bis(2-hydrazinocarbonyl-1-methylethyl)fluorene, 9,9-bis(2-hydrazinocarbonyl-1-methyl-n-propyl)fluorene, 9,9-bis(2-hydrazinocarbonyl-n-butyl)fluorene, 9,9-bis(2-hydrazinocarbonyl-1-methyl-n-butyl)fluorene, 9,9-bis(5-hydrazinocarbonyl-n-pentyl)fluorene, etc. 1-6 Examples include alkyl fluorenes.

[0093] Examples of 9,9-bis(hydrazinocarbonylcycloalkyl)fluorenes include 9,9-bis(hydrazinocarbonylcyclohexyl)fluorene and other 9,9-bis(hydrazinocarbonyl C 4-10 Examples include cycloalkyl fluorene.

[0094] Examples of 9-(hydrazinocarbonyl-hydrazinocarbonylalkyl)fluorenes include 9-(1-hydrazinocarbonyl-2-hydrazinocarbonylethyl)fluorene, 9-(2-hydrazinocarbonyl-3-hydrazinocarbonylpropyl)fluorene, and other 9-(hydrazinocarbonyl-hydrazinocarbonyl C 2-6 Alkyl fluorene is an example.

[0095] Examples of 2,6-bis(hydrazinocarbonylalkyl)naphthalenes include 2,6-bis(hydrazinocarbonylmethyl)naphthalene, 2,6-bis(1-hydrazinocarbonylethyl)naphthalene, and 2,6-bis(2-hydrazinocarbonylethyl)naphthalene.

[0096] Examples of 2-(hydrazinocarbonylalkyl)naphthalenes include 2-(hydrazinocarbonylmethyl)naphthalene, 2-(1-hydrazinocarbonylethyl)naphthalene, and 2-(2-hydrazinocarbonylethyl)naphthalene.

[0097] These polycyclic aromatic hydrazine compounds can be used individually or in combination of two or more.

[0098] In particular, polycyclic aromatic hydrazine compounds having a fluorene skeleton or a naphthalene skeleton are preferred from the viewpoint of stability as a compound, ease of synthesis, adsorption performance and adsorption rate of aldehyde compounds having 2 or more carbon atoms when heated at high temperatures of 130°C or higher, and suppression of discoloration, and polycyclic aromatic hydrazine compounds having a fluorene skeleton are more preferred, and fluorene-containing hydrazine compounds represented by general formulas (1) to (4) are even more preferred. Specifically, among these, 9,9-bis(hydrazinocarbonylalkyl)fluorenes are preferred, and 9,9-bis(hydrazinocarbonylC 1-6 Alkyl)fluorene is more preferred, and 9,9-bis(2-hydrazinocarbonylethyl)fluorene, 9,9-bis(1-hydrazinocarbonylethyl)fluorene, 9,9-bis(1-hydrazinocarbonyl-n-propyl)fluorene, 9,9-bis(2-hydrazinocarbonyl-n-propyl)fluorene, etc. are even more preferred.

[0099] These polycyclic aromatic hydrazine compounds can be synthesized by known methods, for example, by the method described in Japanese Patent Publication No. 2019-108311.

[0100] The polycyclic aromatic hydrazine compounds described above may be dissolved in solution, but from the viewpoint of adsorption performance and adsorption rate of aldehyde compounds with 2 or more carbon atoms when heated to high temperatures of 130°C or higher, it is preferable that they remain in a constant shape without dissolving. In this case, for similar reasons, the median diameter of the polycyclic aromatic hydrazine compound is preferably 500 μm or less, more preferably 300 μm or less, even more preferably 150 μm or less, particularly preferably 75 μm or less, and even more preferably 40 μm or less. Also, for similar reasons and from the viewpoint of manufacturing load, the median diameter of the polycyclic aromatic hydrazine compound is preferably 0.1 μm or more, more preferably 0.5 μm or more, even more preferably 1.0 μm or more, particularly preferably 2.0 μm, and even more preferably 4.0 μm or more.

[0101] The content of polycyclic aromatic hydrazine compounds in the odor substance adsorbent of the present invention is not particularly limited. From the viewpoint of adsorption performance and adsorption rate of aldehyde compounds with 2 or more carbon atoms when heated at high temperatures of 130°C or higher, and suppression of discoloration, the content is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and even more preferably 2.0% by mass or more, relative to 100% by mass of the total amount of the odor substance adsorbent. Furthermore, the content of polycyclic aromatic hydrazine compounds in the odor substance adsorbent of the present invention is not particularly limited. From the viewpoint of adsorption performance and adsorption rate of aldehyde compounds with 2 or more carbon atoms when heated at high temperatures of 130°C or higher, and suppression of discoloration, the content is preferably 100% by mass of polycyclic aromatic hydrazine compounds, relative to 100% by mass of the total amount of the odor substance adsorbent, for example, all of it may be polycyclic aromatic hydrazine compounds, or it may be less than 100% by mass for application or economic reasons. When the content of the polycyclic aromatic hydrazine compound is less than 100% by mass, it is preferably 99.9% by mass or less, more preferably 90.0% by mass or less, even more preferably 80.0% by mass or less, and particularly preferably 60.0% by mass or less.

[0102] (1-2) Inorganic porous material The odor substance adsorbent of the present invention may also contain an inorganic porous material.

[0103] Such inorganic porous materials are not particularly limited and include silicon-containing compounds (silica, activated clay, zeolite, clay, talc, etc.), as well as activated carbon, alumina, ceramics, calcium carbonate, etc. Among these, silicon-containing compounds are preferred, and silica is more preferred, from the viewpoint of adsorption performance and adsorption rate of aldehyde compounds with two or more carbon atoms when heated to high temperatures of 130°C or higher, and suppression of discoloration. These inorganic porous materials can be used individually or in combination of two or more types.

[0104] When using silica as such an inorganic porous material, there are no particular restrictions on the type of silica used; wet-process silica (sedimentation silica, gel silica, etc.), dry-process silica, fused silica, etc., can all be used.

[0105] Furthermore, when using silicon-containing compounds as inorganic porous materials, it is possible to have substituted or unsubstituted amino groups on the surface. Such materials can be obtained by chemically modifying them with silane coupling agents having substituted or unsubstituted amino groups. The chemical modification can be carried out according to conventional methods. Examples of silane coupling agents having substituted or unsubstituted amino groups that can be used in this case include silane coupling agents having methacrylic groups, vinyl groups, amino groups, glycidyl groups, and mercapto groups. It is also possible to use silicon-containing compounds (especially silica) modified with the substituted or unsubstituted amino groups of these silane coupling agents.

[0106] When using an inorganic porous material, the content of the inorganic porous material in the odor substance adsorbent of the present invention is not particularly limited. From the viewpoint of adsorption performance and adsorption rate when heated to 130°C or higher, and suppression of discoloration, the content is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and even more preferably 2.0% by mass or more, with the total amount of the odor substance adsorbent being 100% by mass. Similarly, for the same reasons, the content of the inorganic porous material in the odor substance adsorbent of the present invention is not particularly limited. The content is preferably 99.9% by mass or less, more preferably 95.0% by mass or less, and even more preferably 90.0% by mass or less, with the total amount of the odor substance adsorbent being 100% by mass.

[0107] (1-3) Desiccants, superabsorbent polymers, and compounds that can take on a hydrate structure and their hydrates The odor substance adsorbent of the present invention may also use additives such as hygroscopic agents, superabsorbent polymers, compounds that can take on a hydrate structure, or hydrates thereof (hereinafter sometimes referred to as "hygroscopic agents, etc.").

[0108] As a desiccant, compounds with a moisture absorption rate of 50% or more are preferred, compounds with a moisture absorption rate of 100% or more are more preferred, and compounds with a moisture absorption rate of 150% or more are even more preferred, from the viewpoint of adsorption performance and adsorption rate when heated to 130°C or above, as well as suppression of discoloration. There is no particular upper limit to the moisture absorption rate of the desiccant, but it is usually 1000%. The moisture absorption rate of the desiccant is measured by leaving the sample at 25°C and 50% relative humidity until there is no further change in weight, and then determining the change in weight.

[0109] Such desiccant can be used without particular limitations, but from the viewpoint of the stability of polycyclic aromatic hydrazine compounds, it is preferable to use a substance in which the pH of the aqueous solution after deliquescence is 9 or less (especially 0 to 9).

[0110] Examples of such desiccants include calcium chloride, magnesium chloride, sodium carbonate, citric acid, potassium carbonate, phosphorus pentoxide, magnesium perchlorate, manganese sulfate, iron chloride, magnesium sulfate, and sodium sulfate. Both anhydrous and hydrated forms of these desiccants can be used, but anhydrous forms are preferred from the viewpoint of higher hygroscopicity. These desiccants can be used individually or in combination of two or more types.

[0111] However, from the viewpoint of easily suppressing the deterioration of handling properties due to deliquescence, it is preferable that the polycyclic aromatic hydrazine compound does not contain more than 100 parts by mass of divalent metal chlorides such as calcium chloride, magnesium chloride, and iron chloride, and more preferably less than 70 parts by mass. For this reason, the content of the desiccant is preferably 0 to 90 parts by mass, more preferably 0 to 70 parts by mass, per 100 parts by mass of the polycyclic aromatic hydrazine compound, and it is perfectly acceptable for the odor substance adsorbent of the present invention not to contain divalent metal chlorides. In particular, when the polycyclic aromatic hydrazine compound has a naphthalene skeleton, it is especially preferable to adjust the content of the desiccant to be within the above range.

[0112] Superabsorbent polymers can retain moisture by utilizing their moisturizing properties and can be used regardless of their hygroscopicity. Preferably, these superabsorbent polymers are capable of absorbing and retaining 100 times their own weight in moisture (especially 100 to 1000 times). Furthermore, the molecular weight of the superabsorbent polymer is preferably between 1000 and 500000.

[0113] Examples of such superabsorbent polymers include polyacrylates, polysulfonates, polysulfonates, maleate anhydride, polyacrylamide, polyvinyl alcohol, polyethylene oxide, sodium polyacrylate, polyethylene glycol, polyaspartate, polyglutamate, polyalginate, and polysaccharides (derived from starch, cellulose, dextrin, etc.). These superabsorbent polymers can be used individually or in combination of two or more types.

[0114] Compounds that can take on a hydrate structure and their hydrates can retain moisture by utilizing their moisturizing properties and can be used regardless of their hygroscopicity. Preferably, such compounds are those that can take on a structure in which the mass of water of hydration is 50% or more of the weight of the anhydrous structure; more preferably, compounds that can take on a structure in which the mass of water of hydration is 100% or more of the weight of the anhydrous structure; even more preferably, compounds that can take on a structure in which the mass of water of hydration is 150% or more of the weight of the anhydrous structure; and particularly preferably, compounds that can take on a structure in which the mass of water of hydration is 200% or more of the weight of the anhydrous structure. There is no particular upper limit to the mass of water of hydration in the anhydrous structure, but it is usually 1000%.

[0115] Examples of compounds and their hydrates that can adopt such a hydrate structure include sodium sulfate (Na2SO4) and its hydrate (Na2SO4·10H2O, etc.), magnesium sulfate (MgSO4) and its hydrate (MgSO4·10H2O, etc.), aluminum sulfate (Al2(SO4)3) and its hydrate (Al2(SO4)3·16H2O, etc.), sodium acetate (CH3COONa) and its hydrate (CH3COONa·3H2O, etc.), sodium pyrophosphate (Na4P2O7) and its hydrate (Na4P2O7·10H2O, etc.), and carbon Examples include sodium phosphate (Na2CO3) and its hydrate (Na2CO3·10H2O, etc.), potassium carbonate (K2CO3) and its hydrate (K2CO3·10H2O, etc.), sodium tetraborate (Na2B4O7) and its hydrate (Na2B4O7·10H2O, etc.), sodium chromate (Na2CrO4) and its hydrate (Na2CrO4·10H2O, etc.), disodium hydrogen phosphate (Na2HPO4) and its hydrate (Na2HPO4·12H2O, etc.), trisodium phosphate and its hydrate (Na3PO4·12H2O, etc.). These compounds that can take on a hydrate structure and their hydrates can be used individually or in combination of two or more.

[0116] These desiccants, superabsorbent polymers, compounds that can take on a hydrate structure, or their hydrates can be used individually, but multiple types can also be used in combination depending on the purpose. Furthermore, when using the odor substance adsorbent of the present invention for wallpaper applications, it is preferable to use a desiccant from the viewpoint of maintaining aesthetic appeal.

[0117] When using additives such as hygroscopic agents, superabsorbent polymers, compounds that can take on a hydrate structure, or their hydrates, the content of these additives in the odor substance adsorbent of the present invention is not particularly limited. From the viewpoint of adsorption performance and adsorption rate when heated to 130°C or higher, and suppression of discoloration, the content is preferably, for example, 0.1% by mass or more, more preferably 1.0% by mass or more, and even more preferably 2.0% by mass or more, based on 100% by mass of the total amount of the odor substance adsorbent. Similarly, for the same reasons, the content of these additives in the odor substance adsorbent of the present invention is not particularly limited. For example, the content is preferably 95.0% by mass or less, more preferably 90.0% by mass or less, and even more preferably 85.0% by mass or less, based on 100% by mass of the total amount of the odor substance adsorbent.

[0118] Furthermore, when using additives such as hygroscopic agents, superabsorbent polymers, compounds that can take on a hydrate structure, or their hydrates, the amount is not particularly limited. However, from the viewpoint of adsorption performance and adsorption rate when heated to 130°C or higher, and suppression of discoloration, 10 to 1000 parts by mass, more preferably 50 to 1000 parts by mass, and even more preferably 100 to 500 parts by mass are used per 100 parts by mass of the polycyclic aromatic hydrazine compound.

[0119] (1-4) Odor substance adsorbent As described above, the odor substance adsorbent of the present invention can be in the form of a polycyclic aromatic hydrazine compound alone, or a polycyclic aromatic hydrazine compound containing an inorganic porous material, a hygroscopic agent, etc. In any of these forms, it can be used as is (as a powder solid), or it can be dissolved or dispersed in a solvent to form a solution or suspension, which can then be used as an odor substance adsorbent. It can also be further mixed with powder and used as a powder. It can also be used as pellets. In particular, from the viewpoint of adsorption performance and adsorption rate when heated to 130°C or higher, and suppression of discoloration, it is preferable to use it as a suspension without dissolving it in a solvent.

[0120] Examples of solvents used when odor substance adsorbents are in solution or suspension form include water, lower alcohols, polyhydric alcohols, ketones, ethers, esters, aromatic solvents, halogenated hydrocarbon solvents, polar organic solvents, and the like.

[0121] Examples of lower alcohols include alcohols having a linear or branched alkyl group with 1 to 4 carbon atoms. Specifically, these include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and the like.

[0122] 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 (methyl carbitol), and diethylene glycol monoethyl ether.

[0123] Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and propylene carbonate.

[0124] Examples of ethers include dioxane, tetrahydrofuran, and diethyl ether.

[0125] Examples of esters include ethyl acetate, butyl acetate, isobutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, dimethyl adipate, dimethyl glutarate, and dimethyl succinate.

[0126] Examples of aromatic solvents include benzene, toluene, xylene, methylnaphthalene, dimethylnaphthalene, isopropylnaphthalene, diisopropylnaphthalene, ethylbiphenyl, diethylbiphenyl, and solvent naphtha.

[0127] Examples of halogenated hydrocarbon solvents include carbon tetrachloride, chloroform, and methylene chloride.

[0128] Examples of polar organic solvents include dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, and N-methylpyrrolidone.

[0129] Among these, at least one selected from the group consisting of water, lower alcohols, and polyhydric alcohols is preferred from the viewpoint of deodorizing performance, deodorizing speed, and discoloration suppression, with water being more preferred. Furthermore, if polyhydric alcohols are used to more reliably dissolve the polycyclic aromatic hydrazine compound into a solution, it is preferable to use them. These solvents can be used individually or in combination of two or more.

[0130] However, the odor substance adsorbent of the present invention exhibits excellent adsorption performance for aldehyde compounds having 2 or more carbon atoms and can suppress discoloration even under heating conditions where the adsorption performance of adipic acid dihydrazide decreases. The organic solvents used can be either low-boiling point organic solvents (for example, organic solvents with a boiling point of 180°C or less) or high-boiling point organic solvents (for example, organic solvents with a boiling point greater than 180°C), and embodiments that do not use organic solvents can also be adopted. In other words, the odor substance adsorbent of the present invention is effective under heating conditions, but embodiments that do not use the above-mentioned organic solvents, embodiments that use the above-mentioned high-boiling point organic solvents, and embodiments that use low-boiling point solvents without using the above-mentioned high-boiling point organic solvents can also be adopted without any problems.

[0131] When the odor substance adsorbent of the present invention is in the form of a solution or suspension, the solvent content is not particularly limited. However, from the viewpoint of adsorption performance and adsorption rate when heated to 130°C or higher, and suppression of discoloration, the solvent content is preferably 30.0% by mass or more, more preferably 50.0% by mass or more, and even more preferably 70.0% by mass or more, based on 100% by mass of the total amount of the odor substance adsorbent. Similarly, for the same reasons, the solvent content in the odor substance adsorbent of the present invention is not particularly limited. However, the solvent content is preferably 99.9% by mass or less, more preferably 99.0% by mass or less, and even more preferably 98.0% by mass or less, based on 100% by mass of the total amount of the odor substance adsorbent.

[0132] Furthermore, to adjust the average particle size of the polycyclic aromatic hydrazine compound, various mechanochemical treatments such as ball milling, bead milling, rod milling, vibration milling, disc milling, hammer milling, and jet milling may be performed after preparing the solution or suspension. In this case, the conditions for the mechanochemical treatment are not particularly limited and can be carried out according to conventional methods.

[0133] Furthermore, it is possible to use a mixture of each of the above-mentioned components with a synthetic resin. Examples of synthetic resins include polyacrylic resins (acrylic resin, methacrylic resin, etc.), polyvinyl acetate resins (vinyl acetate resin, etc.), polyvinyl chloride resins (vinyl chloride resin, etc.), polyolefin resins (olefin resin, etc.), ethylene-vinyl acetate copolymer resins (EVA resin), polyurethane resins (urethane resin, etc.), polystyrene resins (styrene resin, etc.), polyepoxy resins (epoxy resin, etc.), silicone resins (silicone resin, etc.), alkyd resins (alkyd resin, etc.), fluorine resins (polytetrafluoroethylene resin, etc.), nylon resin, polyester resins (polyester, etc.; excluding polyester fibers), polyamide resins (aramid resin, etc.), PET resins (polyethylene terephthalate, etc.), ether resins (polyphenylene ether resin, etc.), polyamine resins, amino resins (melamine resin, urea resin, etc.), phenolic resins, and the like. Copolymer resins containing one or more of the above-mentioned resins can also be used. Furthermore, emulsions made from the resins described above can also be used. These resins can be used individually or in combination of two or more types. Among these, polyacrylic resins (acrylic resins, methacrylic resins, etc.) are preferred.

[0134] When the odor substance adsorbent of the present invention contains a resin, there are no particular restrictions on the resin content. However, from the viewpoint of adsorption performance and adsorption rate when heated to 130°C or higher, and suppression of discoloration, the resin content is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and even more preferably 5.0% by mass or more, based on 100% by mass of the total amount of the odor substance adsorbent of the present invention. Furthermore, from the viewpoint of economy, workability, etc., the resin content is preferably 95.0% by mass or less, more preferably 90.0% by mass or less, and even more preferably 85.0% by mass or less.

[0135] Furthermore, it is also possible to use inorganic materials other than resins for processed building materials. Examples of such inorganic materials include cement, asphalt, concrete, plaster, mortar, diatomaceous earth, montmorillonite, bydelite, nontronite, saponite, hectorite, kaolinite, and ceramics.

[0136] When an inorganic material is included in the odor substance adsorbent of the present invention, there are no particular restrictions on the amount of the inorganic material. However, from the viewpoint of adsorption performance and adsorption rate when heated to 130°C or higher, and suppression of discoloration, the amount of the inorganic material is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and even more preferably 5.0% by mass or more, based on 100% by mass of the total amount of the odor substance adsorbent of the present invention. Furthermore, from the viewpoint of economy, workability, etc., the amount of the inorganic material is preferably 95.0% by mass or less, more preferably 90.0% by mass or less, and even more preferably 85.0% by mass or less.

[0137] Depending on its purpose and application, the odor substance adsorbent of the present invention may contain various third components widely used in formulation, such as known additives, non-volatile acids, chelating agents, antioxidants, and light stabilizers.

[0138] Preferred non-volatile acids include succinic acid, fumaric acid, maleic acid, and boric acid, and their salts can also be used. These non-volatile acids can be used individually or in combination of two or more. By incorporating such non-volatile acids, the storage stability of the odor substance adsorbent of the present invention can be further improved.

[0139] When using a non-volatile acid, its content is not particularly limited, but it is preferably 1 to 10% by mass, based on 100% by mass of the total amount of the odor substance adsorbent of the present invention.

[0140] Examples of chelating agents include ethylenediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, oxalic acid, and citric acid, and their salts can also be used. These chelating agents can be used individually or in combination of two or more. By incorporating such chelating agents, the storage stability of the odor substance adsorbent of the present invention can be further improved.

[0141] When a chelating agent is used, its content is not particularly limited, but it is preferably 1 to 10% by mass, based on 100% by mass of the total amount of the odor substance adsorbent of the present invention.

[0142] Examples of antioxidants include phenolic antioxidants and amine antioxidants. Specific examples of phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol and 2,2'-methylenebis(4-methyl-6-tert-butylphenol). Specific examples of amine antioxidants include alkyldiphenylamine and N,N'-di-sec-butyl-p-phenylenediamine. These antioxidants can be used individually or in combination of two or more.

[0143] When using antioxidants, their content is not particularly limited, but is preferably 1 to 10% by mass, based on 100% by mass of the total amount of the odor substance adsorbent of the present invention.

[0144] Examples of light stabilizers include hindered amine-based light stabilizers such as bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate. These light stabilizers can be used individually or in combination of two or more.

[0145] When a light stabilizer is used, its content is not particularly limited, but it is preferably 1 to 10% by mass, based on 100% by mass of the total amount of the odor substance adsorbent of the present invention.

[0146] These third components can be used individually, but they can also be used in combination depending on the purpose.

[0147] The odor substance adsorbent of the present invention is intended for use in applications where it is heated to 130°C or higher. Specifically, it is preferable to heat it to 130°C or higher during the manufacturing process or during use. This heating temperature may include both cases where the product temperature reaches 130°C or higher, and cases where the ambient temperature (such as the temperature of a dryer) is 130°C or higher. From the viewpoint of the deodorizing performance, deodorizing speed, and discoloration suppression of the odor substance adsorbent of the present invention, the heating temperature is preferably 180°C or higher, more preferably 200°C or higher, and even more preferably 225°C or higher. Furthermore, there is no particular upper limit to the heating temperature in applications using the odor substance adsorbent of the present invention, but it is preferable that the temperature does not exceed the boiling point of the polycyclic aromatic hydrazine compound and is below a temperature that does not impair the quality of the application in which the odor substance adsorbent of the present invention is used (such as building materials). From this viewpoint, the upper limit of the heating temperature is usually 350°C.

[0148] Examples of applications requiring heating to over 130°C include building materials (wallpaper, flooring, ceiling materials, handrails, etc.), heating plastics, and filters.

[0149] (1-5) Odor substances The odor substance adsorbent of the present invention described above can efficiently and quickly adsorb odor substances (aldehyde compounds with 2 or more carbon atoms) at high temperatures (130°C or higher). Furthermore, the odor substance adsorbent of the present invention is effective against the above odor substances, either individually or in combination of two or more types.

[0150] There are no particular limitations on the odor substances to be adsorbed by the odor substance adsorbent of the present invention, but aldehyde compounds having 2 or more carbon atoms, which are difficult to adsorb with general adsorbents, are preferred.

[0151] The aldehyde compounds having two or more carbon atoms are, for example, aldehyde compounds having two or more carbon atoms (preferably 2 to 10, more preferably 2 to 5), such as acetaldehyde, propionaldehyde, acrolein, n-butyraldehyde, isobutyraldehyde, 3-methyl-n-butyraldehyde, crotonaldehyde, and other aldehyde-based odor substances (aldehyde compounds). Among these, the odor substance adsorbent of the present invention is particularly effective in adsorbing acetaldehyde and / or propionaldehyde.

[0152] 2. Molded articles containing odor substance adsorbents The odor substance adsorbent of the present invention can be used by being included in (blended into) a molded article. Such a molded article encompasses the present invention (a molded article of the present invention).

[0153] The aforementioned molded articles refer to conventionally known molded articles and their raw materials. Specifically, the odor substance adsorbent of the present invention efficiently and quickly adsorbs odor substances containing aldehyde compounds with 2 or more carbon atoms at high temperatures while also suppressing discoloration, and is suitable for textile products (curtains, mats, felt, cushions, chairs, shoe insoles, shoes, clothing, hats, etc.), building materials (wallpaper, flooring, ceiling materials, handrails, etc.), sanitary products (diapers, gauze, masks, napkins, etc.), and pet products (pet sheets, pet toilets, cat litter, pet mats / carpets, pet beds, pet cases). Examples include house paints, straw, deodorizing sprays, pet detergents, pet bowls, grooming supplies, trimming supplies, carrier bags, cat towers, pet toys, aquatic organism water treatment agents, etc.; household goods (toiletries, detergents and finishing agents (fabric softeners), air fresheners, deodorizers (standing, spray, and misting types), household goods, etc.); paints, adhesives, inks, sealants, paper products, binders, resin emulsions, pulp, wood materials, wood products, plastic products, films, filters, etc.

[0154] The content of the odor substance adsorbent of the present invention in the molded article of the present invention is not particularly limited and can be appropriately set depending on the molded article and its intended use.

[0155] 3. Method for adsorbing odor substances using odor substance adsorbents The present invention provides a method for adsorbing odorous substances by bringing an odorous substance containing an aldehyde compound with two or more carbon atoms into contact with the odorous substance adsorbent of the present invention, thereby adsorbing the odorous substance containing the aldehyde compound with two or more carbon atoms onto the odorous substance adsorbent of the present invention. As described above, the odorous substance adsorbent of the present invention exhibits excellent adsorption performance and adsorption rate for aldehyde compounds with two or more carbon atoms, even under conditions of heating to 130°C or higher, and can also suppress discoloration. Therefore, it is preferable to bring an odorous substance containing an aldehyde compound with two or more carbon atoms into contact with the odorous substance adsorbent of the present invention at 130°C or higher. According to the above adsorption method, the odorous substance adsorbent of the present invention can efficiently and quickly adsorb odorous substances containing aldehyde compounds with two or more carbon atoms at high temperatures while also suppressing discoloration. In the adsorption method of the present invention, by bringing the molded article of the present invention containing the odorous substance adsorbent of the present invention into contact with an odorous substance containing an aldehyde compound with two or more carbon atoms, the odorous substance adsorbent and the odorous substance come into contact, and as a result, the odorous substance can be efficiently adsorbed and removed.

[0156] Furthermore, by filling adsorption devices such as fixed beds, movable beds, and fluidized beds with the material and treating them with a gas containing odorous substances including aldehyde compounds with two or more carbon atoms, the odorous substances can be efficiently, quickly, and over a long period of time adsorbed and removed. [Examples]

[0157] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the embodiments shown below. In the examples, the following hydrazine compounds and resin pellets were used. Dihydrazide adipic acid (ADH): Manufactured by Tokyo Chemical Industry Co., Ltd. Dodecane dioxide dihydrazide (DDADH): Manufactured by Tokyo Chemical Industry Co., Ltd. Isophthalate dihydrazide (IDH): Manufactured by Tokyo Chemical Industry Co., Ltd. 9,9-Bis(2-hydrazinocarbonylethyl)fluorene (FDH): Synthesis Example 1 2,6-Bis(hydrazinocarbonyl)naphthalene (NDH): Synthesis Example 2 2-(Hydrazinocarbonyl)naphthalene (2-NH): Manufactured by BLD Pharmatech Ltd. Polyethylene pellets: Novatec LD LF441MD1 manufactured by Mitsubishi Chemical Corporation.

[0158] Synthesis Example 1 9,9-bis(2-hydrazinocarbonylethyl)fluorene (FDH) was prepared as described in Example 1 of Japanese Patent Publication No. 2019-108311.

[0159] Specifically, 9,9-bis(2-methoxycarbonylethyl)fluorene (50.0 g, 0.15 mol) was dissolved in 106 g of isopropyl alcohol (i-PrOH), and hydrazine monohydrate (82.2 g, 1.63 mol) was added dropwise over 30 minutes at room temperature using a dropping funnel. The mixture was then heated to 80°C and stirred for 2 hours. After cooling to room temperature, the precipitated crystals were filtered and dried to obtain the target amount of FDH: 47.2 g (yield 95%).

[0160] 1 H-NMR(300MHz,DMSO-d6):δ=1.20-1.25(m,4H),2.22-2.28(m,4H),3.96(d,J=4.1H z,4H),7.32-7.40(m,4H),7.44-7.50(m,2H),7.80-7.86(m,2H),8.61-8.64(m,2H) Melting point: 239°C.

[0161] Synthesis Example 2 3 g of dimethyl 2,6-naphthalenedicarboxylate and 30 mL of methanol were added to a round-bottom flask, 16 mL of hydrazide hydrate was added, refluxed for 24 hours, cooled to room temperature, allowed to stand for 5 hours, filtered, washed with water, and dried to obtain 2.3 g of 2,6-naphthalenedicarboxyhydrazide (NDH).

[0162] Example 1 To 95.0 parts by mass of polyethylene pellets, 5.0 parts by mass of FDH obtained in Synthesis Example 1 was added as a deodorant, and the mixture was thoroughly mixed using a plastic bag to prepare a premix of deodorant and pellets.

[0163] The resulting premix was kneaded and melted at 230°C for 2 minutes using an extruder (Thermo Fisher Scientific Process 11), and then cut with a pelletizer to prepare polyethylene pellets containing a deodorant.

[0164] The deodorant-containing pellets were weighed to a concentration of 574.1 μmol (1.94 g) of deodorant and placed on an aluminum dish to serve as the sample for the deodorant test in Example 1.

[0165] Example 2 To 95.0 parts by mass of polyethylene pellets, 5.0 parts by mass of NDH obtained in Synthesis Example 2 was added as a deodorant, and the mixture was thoroughly mixed using a plastic bag to prepare a premix of deodorant and pellets.

[0166] The resulting premix was kneaded and melted at 230°C for 2 minutes using an extruder (Thermo Fisher Scientific Process 11), and then cut with a pelletizer to prepare polyethylene pellets containing a deodorant.

[0167] Example 3 The deodorant-containing pellets obtained in Example 1 were weighed to 2 g and placed on an aluminum dish to serve as the sample for the deodorization test in Example 3.

[0168] Example 4 The deodorant-containing pellets obtained in Example 1 were pressed using a press molding machine (manual hydraulic heating press 187E manufactured by Imoto Seisakusho Co., Ltd.) at 200°C under a force of 98kN to obtain a polyethylene sheet containing a deodorant with a thickness of 1.5 mm or 100 μm. One of these sheets was cut to 9.5 cm x 9.5 cm to be used as the sample for the deodorant test in Example 4.

[0169] Comparative Example 1 Deodorant-containing polyethylene pellets were prepared in the same manner as in Example 1, except that ADH was used instead of FDH as the deodorant.

[0170] The obtained deodorant-containing pellets were weighed to a concentration of 574.1 μmol (1.00 g) of deodorant and placed on an aluminum dish to serve as the sample for the deodorant test in Comparative Example 1.

[0171] Comparative Example 2 Deodorant-containing polyethylene pellets were prepared in the same manner as in Example 1, except that DDADH was used instead of FDH as the deodorant.

[0172] The obtained deodorant-containing pellets were weighed to a concentration of 574.1 μmol (1.48 g) of deodorant and placed on an aluminum dish to serve as the sample for the deodorant test in Comparative Example 2.

[0173] Comparative Example 3 Deodorant-containing polyethylene pellets were prepared in the same manner as in Example 1, except that IDH was used instead of FDH as the deodorant.

[0174] The obtained deodorant-containing pellets were weighed to a concentration of 574.1 μmol (1.11 g) of deodorant and placed on an aluminum dish to serve as the sample for the deodorant test in Comparative Example 3.

[0175] Comparative Example 4 The deodorant-containing pellets from Comparative Example 1 were weighed to 2g and placed on an aluminum tray to be used as the sample for the deodorization test in Comparative Example 4.

[0176] Comparative Example 5 The deodorant-containing pellets from Comparative Example 2 were weighed to 2g and placed on an aluminum tray to be used as the sample for the deodorization test in Comparative Example 5.

[0177] Comparative Example 6 The deodorant-containing pellets from Comparative Example 3 were weighed to 2g and placed on an aluminum dish to be used as the sample for the deodorization test in Comparative Example 6.

[0178] Comparative Example 7 Except for using the deodorant-containing pellets from Comparative Example 1 instead of the deodorant-containing pellets obtained in Example 1, a deodorant-containing polyethylene sheet was prepared in the same manner as in Example 4 and used as the sample for the deodorant test in Comparative Example 7.

[0179] Comparative Example 8 Except for using the deodorant-containing pellets from Comparative Example 2 instead of the deodorant-containing pellets obtained in Example 1, a deodorant-containing polyethylene sheet was prepared in the same manner as in Example 4 and used as the sample for the deodorant test in Comparative Example 8.

[0180] Comparative Example 9 Except for using the deodorant-containing pellets from Comparative Example 3 instead of the deodorant-containing pellets obtained in Example 1, a deodorant-containing polyethylene sheet was prepared in the same manner as in Example 4 and used as the sample for the deodorant test in Comparative Example 9.

[0181] Test Example 1 (Color, etc.) The deodorization test samples obtained in Examples 1-2 and Comparative Examples 1-3 were visually inspected for color and other characteristics.

[0182] The results are shown in Tables 1 and 2.

[0183] [Table 1]

[0184] [Table 2]

[0185] Test Example 2 (Odor Substance Adsorption Performance, Part 1) The deodorization test samples obtained in Examples 1, 3, and 4, and Comparative Examples 1 to 9, were placed in 1L sampling bags (Smart Bag PA, manufactured by GL Sciences Co., Ltd.), sealed, and the air inside the sampling bag was removed using a piston. Then, 1L of acetaldehyde gas adjusted to 14 ppm was injected, and the residual gas concentration after 2 hours and 24 hours was measured using a detector tube (Gastec Co., Ltd.).

[0186] The results are shown in Figures 1-3.

[0187] Examples 5-6 1.94 parts by mass of FDH obtained in Synthesis Example 1 and 98.06 parts by mass of water were weighed into a beaker and thoroughly stirred with a stirring rod to suspend the mixture, obtaining an aqueous suspension of FDH. 1 g of this aqueous suspension of FDH was used as the sample for the deodorization test in Example 5. 2 g of the aqueous suspension of FDH was used as the sample for the deodorization test in Example 6. As a result, the number of moles of the deodorant was 57.4 μmol in Example 5 and 114.8 μmol in Example 6. In the obtained aqueous dispersion of FDH, the particle size of FDH was 218 μm at the median diameter and 1337 μm at the maximum particle size.

[0188] Examples 7-8 In Synthesis Example 1, 1.94 parts by mass of FDH and 98.06 parts by mass of methyl carbitol were weighed into a beaker and thoroughly stirred with a stirring rod to completely dissolve them, thereby obtaining a solution of FDH with methyl carbitol. 1 g of this solution of FDH with methyl carbitol was used as the sample for the deodorization test in Example 7. In addition, 2 g of the solution of FDH with methyl carbitol was used as the sample for the deodorization test in Example 8. As a result, the number of moles of the deodorant was 57.4 μmol in Example 7 and 114.8 μmol in Example 8.

[0189] Examples 9-10 95.85% by mass of water, 2.11% by mass of Perex SS-L (manufactured by Kao Corporation), and 2.05% by mass of FDH obtained in Synthesis Example 1 were mixed and bead-milled using a batch-type bead mill (DISPERMAT TML05, manufactured by VMA-GETZMANN) (2000 rpm x 30 minutes) to obtain an aqueous dispersion of FDH. 1 g of this aqueous dispersion of FDH was used as the sample for the deodorization test in Example 9. 2 g of the aqueous dispersion of FDH was used as the sample for the deodorization test in Example 10. As a result, the number of moles of the deodorant was 57.4 μmol in Example 9 and 114.8 μmol in Example 10. In the obtained aqueous dispersion of FDH, the particle size of FDH was 12 μm at the median diameter and 394 μm at the maximum particle size.

[0190] Example 11 1.94 parts by mass of the FDH obtained in Synthesis Example 1, which was ground in a mortar for 10 minutes, and 98.06 parts by mass of water were weighed into a beaker and thoroughly stirred with a stirring rod to suspend the mixture and obtain an aqueous suspension of FDH. 1 g of this aqueous suspension of FDH was used as the sample for the deodorization test in Example 11. As a result, the number of moles of the deodorant was 57.4 μmol. In the obtained aqueous dispersion of FDH, the particle size of FDH was 53 μm at the median diameter and 696 μm at the maximum particle size.

[0191] Example 12 1.94 parts by mass of the FDH obtained in Synthesis Example 1, which was ground in a mortar for 3 minutes, and 98.06 parts by mass of water were weighed into a beaker and thoroughly stirred with a stirring rod to suspend the mixture and obtain an aqueous suspension of FDH. 1 g of this aqueous suspension of FDH was used as the sample for the deodorization test in Example 12. As a result, the number of moles of the deodorant was 57.4 μmol. In the obtained aqueous dispersion of FDH, the particle size of FDH was 112 μm at the median diameter and 913 μm at the maximum particle size.

[0192] Example 13 1.40 parts by mass of NDH obtained in Synthesis Example 2 and 98.60 parts by mass of water were weighed into a beaker and thoroughly stirred with a stirring rod to suspend the mixture, obtaining an aqueous suspension of NDH. 1 g of this aqueous suspension of NDH was used as the sample for the deodorization test in Example 13. As a result, the number of moles of the deodorizer was 57.4 μmol. In the obtained aqueous dispersion of NDH, the particle size of NDH was 85 μm at the median diameter and 852 μm at the maximum particle size.

[0193] Example 14 1.08 parts by mass of 2-NH and 98.92 parts by mass of water were weighed into a beaker and thoroughly stirred with a stirring rod to suspend the mixture, obtaining an aqueous suspension of 2-NH. 1 g of this aqueous suspension of 2-NH was used as the sample for the deodorization test in Example 14. As a result, the number of moles of the deodorant was 57.4 μmol. In the obtained aqueous dispersion of 2-NH, the particle size of 2-NH was 98 μm at the median diameter and 933 μm at the maximum particle size.

[0194] Test Example 3 (Particle Size Measurement) The average particle size of FDH in the deodorization test samples obtained in Examples 5-6 and 9-14 was measured using a laser diffraction / scattering particle size distribution analyzer LA-960V2 manufactured by Horiba, Ltd. The results are shown in Tables 3-4.

[0195] Test Example 4 (Odor Substance Adsorption Performance, Part 2) A predetermined amount (1g or 2g) of the deodorization test sample obtained in Examples 5-14 was dropped onto glass filter paper (5cm x 5cm or 5cm x 10cm) and sealed in a 1L sampling bag (Smart Bag PA AAK-1, manufactured by GL Sciences Co., Ltd.). In Examples 5, 7, 9 and 11-14, 1g of the deodorization test sample was dropped onto 5cm x 5cm glass filter paper, while in Examples 6, 8 and 10, 2g of the deodorization test sample was dropped onto 5cm x 10cm glass filter paper. Acetaldehyde gas at an initial concentration (1000ppm; 44.6μmol) was sealed inside the sampling bag, and the concentration inside the sampling bag was measured over time using gas detection tubes (Gastec Co., Ltd., Acetaldehyde Detection Tubes 92, 92M, 92L). The results are shown in Tables 3-4. For reference, Tables 3-4 also show the results of natural decay.

[0196] [Table 3]

[0197] [Table 4]

[0198] As described above, adipic acid dihydrazide, which has been conventionally used as an odor adsorbent, showed a decrease in deodorizing performance at high temperatures. On the other hand, dodecane dioate dihydrazide showed significantly better deodorizing performance than adipic acid dihydrazide at high temperatures, but it could not suppress discoloration. In contrast, 9,9-bis(2-hydrazinocarbonylethyl)fluorene showed significantly better deodorizing performance than adipic acid dihydrazide at high temperatures, and also suppressed discoloration.

Claims

1. An odor substance adsorbent that adsorbs acetaldehyde, It contains a polycyclic aromatic hydrazine compound, The aforementioned polycyclic aromatic hydrazine compound has the general formula (1): 【Chemistry 1】 [In the formula, R1a and R2a are the same or different and represent substituents. R3 and R4 are the same or different and represent a divalent hydrocarbon group. m1 and n1 are the same or different and represent integers from 0 to 4.] A polycyclic aromatic hydrazine compound represented by [formula], which is an odor substance adsorbent.

2. An odor substance adsorbent according to claim 1, for use in applications where heating is required to 130°C or higher.

3. The odor substance adsorbent according to claim 1 or 2, wherein the median diameter of the polycyclic aromatic hydrazine compound is 0.1 to 500 μm.

4. A molded article containing an odor substance adsorbent according to any one of claims 1 to 3.

5. The molded article according to claim 4, which is heated to 130°C or higher during the manufacturing process, or used after being heated to 130°C or higher.

6. A method for adsorbing an odorous substance, comprising the step of bringing an odorous substance containing acetaldehyde into contact with an odorous substance adsorbent according to any one of claims 1 to 3 or a molded article according to claim 4 or 5.

7. The adsorption method according to claim 6, wherein the contact step is a step of bringing the odor substance and the odor substance adsorbent into contact at a temperature of 130°C or higher.

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