JP2020074849A - Odorant adsorbent - Google Patents

Abstract

To provide an odorant adsorbent that can improve a deodorizing performance even in an environment with insufficient moisture.SOLUTION: An odorant adsorbent has a hydrazine compound, and a divalent metal chloride. Based on the hydrazine compound 100 pts.mass, the content of the divalent metal chloride exceeds 100 pts.mass.SELECTED DRAWING: None

Description

  The present invention relates to an odorant adsorbent.

  In recent years, consumers' needs for deodorization are increasing. Among them, aldehyde compounds such as formaldehyde and acetaldehyde are considered to be causative agents of sick house syndrome, and are difficult to adsorb to general adsorbents (for example, general-purpose activated carbon). It is a substance with a strong demand for odor. As such an adsorbent for odorous substances, for example, a hydrazine compound is known.

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

International Publication No. 2009/122975

  However, there is a case where the deodorizing performance is not exhibited in a scene where adipic acid dihydrazide is used as an adsorbent as a hydrazine compound. Specifically, it has been confirmed that even if adipic acid dihydrazide is dissolved in water and impregnated in glass fiber, and the glass fiber is allowed to stand at room temperature for a certain period of time, the deodorizing performance is not sufficiently exhibited.

  Until now, the cause of this phenomenon has not been accurately grasped, and there have been many cases where hydrazine compounds such as adipic acid dihydrazide cannot be used.

  As a result of intensive investigations into the cause of the above problems, the present inventors have discovered that the activity of the hydrazine compound is significantly reduced when it is dried. For this reason, it has been discovered that the conventional odorant adsorbent cannot properly exhibit the deodorizing performance unless water is present.

  In order to suppress the deterioration of the deodorant performance due to such drying, it is also possible to use a hygroscopic agent together. However, under the circumstances where even the cause of the deterioration of the deodorant performance of the hydrazine compound is not known, an appropriate blending ratio of the hygroscopic agent has not been investigated, and the combined use of the hygroscopic agent does not make the content of the hydrazine compound relatively. The fact is that there has been almost no study on the combined use with a hygroscopic agent because it leads to a decrease in the amount.

  The present invention is intended to solve the above problems, and an object thereof is to provide an odorant adsorbent capable of improving deodorant performance even in an environment where the water content is not sufficient.

  The present inventors have conducted extensive studies to achieve the above object, containing a hydrazine compound and a divalent metal chloride, and by setting the content of the divalent metal chloride in a specific range, It has been found that the above problems can be solved. The present inventors have further researched on the basis of such findings and completed the present invention. That is, the present invention includes the following configurations.

Item 1. A hydrazine compound having a molecular weight of 100 or more and a divalent metal chloride, the molecular weight is 100 parts by mass or more of the hydrazine compound, the content of the divalent metal chloride is greater than 100 parts by mass, Odorant adsorbent.
Item 2. The hydrazine compound having a molecular weight of 100 or more is lauric acid hydrazide, salicylic acid hydrazide, p-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide, 3-hydroxy-2-naphthoic acid hydrazide, benzhydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, amber. Acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, tartaric acid dihydrazide, diglycolide dihydrazide dihydrazide, malic acid dihydrazide dihydrazide Dihydrazide, 2,6-naphthalenedicarboxylic acid dihydrazide, 2.6-naphthoic acid dihydrazide, citric acid trihydrazide, pyromellitic acid trihydrazide, 1,2,4-benzenetricarboxylic acid trihydrazide, nitrilotriacetic acid trihydrazide, 1,3, 5-cyclohexanetricarboxylic acid trihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, benzylhydrazine, phenylhydrazine, 3-amino-5-phenyl-1,2,4-triazole, and Item 8. The odorant adsorbent according to item 1, which is at least one member selected from the group consisting of 4-aminourazole.
Item 3. Item 3. The odorant adsorbent according to Item 1 or 2, wherein the divalent metal chloride is at least one selected from the group consisting of calcium chloride, magnesium chloride and iron chloride.
Item 4. Furthermore, the odorous substance adsorbent according to any one of items 1 to 3, further comprising an inorganic porous material.
Item 5. Item 5. The odorant adsorbent according to Item 4, wherein the inorganic porous material is a compound containing silicon.
Item 6. Item 6. The odorant adsorbent according to Item 4 or 5, wherein the inorganic porous material is silica.
Item 7. Item 7. The odorant adsorbent according to any one of Items 1 to 6, wherein the odorant is at least one selected from the group consisting of aldehyde compounds, ketone compounds and carboxylic acid compounds.
Item 8. Item 8. The odorant adsorbent according to any one of Items 1 to 7, which is used for industrial products in which at least one step in the production process is performed at 130 ° C or higher.
Item 9. A layer containing the odorant adsorbent according to any one of items 1 to 8 is formed on a base material, and the base material has a water content of 5.0 mass evaluated from the weight at 23 ° C and the weight at 60 ° C. An odor substance adsorbing material that is less than or equal to%.
Item 10. Item 10. The odor substance adsorbing material according to Item 9, wherein the base material is a polyethylene terephthalate plate, a glass plate, an aluminum plate or a wallpaper sheet.
Item 11. Item 9. An industrial product containing the odorant adsorbent according to any one of Items 1 to 8 or the odorant adsorbent according to Item 9 or 10.
Item 12. A method for adsorbing an odor substance, comprising a step of bringing the odor substance into contact with the odor substance adsorbent according to any one of Items 1 to 8 or the odor substance adsorbent according to Item 9 or 10.

  The odorant adsorbent of the present invention can sufficiently adsorb odorants even in an environment where the water content is not sufficient, and can exhibit excellent deodorant performance.

  In the present specification, the term “inclusion” is a concept including both “comprise”, “consisting essentially of”, and “consist of”. Further, in the present specification, when the numerical range is indicated by “A to B”, it means A or more and B or less.

  In addition, in the present specification, the “environment with insufficient water content” refers to a daily living space (humidity in air is 5 to 60%) in the absence of a solvent.

1. Odorant Adsorbent The odorant adsorbent of the present invention has a hydrazine compound having a molecular weight of 100 or more, and a divalent metal chloride, and the molecular weight is 100 or more parts by weight of the hydrazine compound, the divalent. The content of metal chloride is greater than 100 parts by mass.

(1-1) Hydrazine Compound The molecular weight of the hydrazine compound is 100 or more, preferably 130 or more, more preferably 150 or more. When the molecular weight of the hydrazine compound is less than 100, the deodorizing performance and the deodorizing rate in an environment where the water content is not sufficient, the heat resistance, the storage stability and the like are poor. Further, the molecular weight of the hydrazine compound is, for example, preferably 500 or less, more preferably 400 or less, and further preferably 300 or less, from the viewpoint of deodorizing performance and deodorizing rate in an environment where the water content is not sufficient.

  As such a hydrazine compound, for example, an acid hydrazide compound, an alkylhydrazine compound, or another hydrazine compound can be used. As the acid hydrazide compound, an acid monohydrazide compound having one hydrazide group in the molecule, an acid dihydrazide compound having two hydrazide groups in the molecule, an acid trihydrazide compound having three hydrazide groups in the molecule, etc. Can be used. Of these, an acid hydrazide compound is preferable, and an acid dihydrazide compound or an acid trihydrazide compound is more preferable, from the viewpoints of deodorizing performance in an environment where the water content is not sufficient, storage stability of the adsorbent, color suppression, and the like.

  As such a hydrazine compound, specifically, as an acid hydrazide compound, lauric acid hydrazide, salicylic acid hydrazide, p-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide, 3-hydroxy-2-naphthoic acid hydrazide, benzhydrazide, shu. Acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, maleic acid dihydrazide, tartaric acid dihydrazide, tartaric acid, tartar dihydrazide, tartar Dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthalene dicarboxylic acid dihydrazide, 2.6-naphthoic acid dihydrazide, citric acid trihydrazide, pyromellitic acid trihydrazide, 1,2,4-benzenetricarboxylic acid trihydrazide, nitrilotria Acetic acid trihydrazide, 1,3,5-cyclohexanetricarboxylic acid trihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide and the like, and the like, as an alkylhydrazine compound, benzylhydrazine, phenylhydrazine, etc. Other examples of the hydrazine compound include 3-amino-5-phenyl-1,2,4-triazole and 4-aminourazole. Among them, the acid hydrazide compound, from the viewpoint of safety, deodorant performance in an environment where the water content is insufficient, deodorization rate in an environment where the water content is not sufficient, color suppression, heat resistance and storage stability are excellent. Preferably, adipic acid dihydrazide, succinic acid dihydrazide, dodecanedioic acid dihydrazide and the like are more preferable. These hydrazine compounds may be used alone or in combination of two or more.

  The content of the hydrazine compound in the odorant adsorbent of the present invention, the deodorant performance in an environment where the water content is not sufficient, the deodorization rate in an environment where the water content is not sufficient, the suppression of coloration, the heat resistance and the storage stability. From the viewpoint of further improving, the total amount of the odorant adsorbent of the present invention is 100% by mass, for example, preferably 0.1% by mass or more, more preferably 1.0% by mass or more, further preferably 3.0% by mass or more, and, for example, 48 mass% or less is preferable, 40 mass% or less is more preferable, 35 mass% or less is further preferable, and 30 mass% or less is particularly preferable.

(1-2) Divalent Metal Chloride The odorant adsorbent of the present invention contains a hydrazine compound as described above, but the presence of water makes it possible to further suppress the dry deactivation of the hydrazine compound and eliminate the deodorant. It is also possible to further improve the performance and the deodorizing rate. However, when an aqueous solvent such as water is used as the solvent of the odorant adsorbent, when heated to a high temperature in at least one step of the manufacturing process, the solvent volatilizes, so that water cannot exist. In order to function as an odorant adsorbent even in an environment in which such water cannot be present or is present in a very small amount even if it can be present, in the present invention, by using a divalent metal chloride as an alternative means, a hydrazine compound of It is possible to effectively suppress dry deactivation and improve the deodorizing performance and the deodorizing rate in an environment where the water content is not sufficient.

  As the divalent metal chloride, a compound having a moisture absorption rate of 50% or more is preferable, a compound having a moisture absorption rate of 100% or more is more preferable, and a compound having a moisture absorption rate of 150% or more is further preferable. Thus, by using a hygroscopic agent having a high hygroscopic rate, it is possible to allow more water to be present in the system even in an environment where the water content is not sufficient, and it is more effective to dry inactivate the hydrazine compound. Therefore, it is possible to further improve the deodorizing performance and the deodorizing speed in an environment where the water content is not sufficient. The upper limit of the moisture absorption rate of the divalent metal chloride is not particularly limited, but is usually 1000%. The hygroscopicity of the divalent metal chloride is measured by allowing the sample to stand in an atmosphere of 25 ° C. and 50% relative humidity until the weight change disappears, and determining the weight change.

  As such a divalent metal chloride, from the viewpoint of the stability of the hydrazine compound, it is preferable to use a substance in which the pH of the aqueous solution after being deliquescent is 9 or less (particularly 0 to 9).

  Examples of such divalent metal chlorides include alkaline earth metal chlorides (calcium chloride, magnesium chloride, etc.), divalent transition metal chlorides (iron chloride, etc.), and the like. Incidentally, these divalent metal chlorides, both anhydrous and hydrates can be used, but highly hygroscopic, from the viewpoint of further improving the deodorant performance and deodorant rate in an environment where the water content is not sufficient. Anhydrous is preferred. These divalent metal chlorides can be used alone or in combination of two or more.

  The content of the divalent metal chloride in the odorant adsorbent of the present invention is more than 100 parts by mass, preferably 120 parts by mass or more, more preferably 150 parts by mass or more, with respect to 100 parts by mass of the hydrazine compound. It is preferably 180 parts by mass or more. When the content of the divalent metal chloride is 100 parts by mass or less, the dry deactivation of the hydrazine compound cannot be suppressed, and the deodorizing performance and the deodorizing rate in an environment where the water content is not sufficient are not sufficient. On the other hand, the upper limit of the content of the divalent metal chloride is not particularly limited, from the viewpoint of more sufficiently enhancing the deodorizing performance and deodorizing rate in an environment where the water content is not sufficient, for example, the hydrazine compound 100 The amount is preferably 2000 parts by mass or less, more preferably 1000 parts by mass or less, still more preferably 500 parts by mass or less, based on the parts by mass.

  The content of the divalent metal chloride in the odorant adsorbent of the present invention is the total amount of the odorant adsorbent from the viewpoint of more sufficiently enhancing the deodorant performance and the deodorant rate in an environment where the water content is not sufficient. As 100 mass%, for example, preferably 0.2 mass% or more, more preferably 1.0 mass% or more, further preferably 3.0 mass% or more, and, for example, 94.0 mass% or less, more preferably 90.0 mass% or less, 85.0. It is more preferably at most% by mass.

  As described above, the present invention can suppress the dry deactivation of the hydrazine compound by the hygroscopicity of the divalent metal chloride, but surprisingly, compared with the hydrazine compound, the content of the divalent metal chloride. By increasing the amount, the deodorizing performance and the deodorizing rate in an environment where the water content is not sufficient can be sufficiently increased. Usually, increasing the content of the divalent metal chloride will reduce the relative content of the hydrazine compound, and it is usually thought that the deodorant performance and deodorant rate will deteriorate, but due to the reduction of the content of the hydrazine compound It means that the effect of improving the deodorant performance and the deodorant rate by suppressing the dry deactivation of the hydrazine compound is equal to or higher than the reduction effect of the deodorant performance and the deodorant rate. In other words, it is not possible to envision increasing the divalent metal chloride content without understanding the mechanism of the activity reduction of the hydrazine compound, which is the deactivation of the hydrazine compound. It is an unexpected result that the deodorizing performance and the deodorizing rate in an environment where the water content is not sufficient can be sufficiently increased by increasing the value.

(1-3) Inorganic porous material The odorant adsorbent of the present invention may contain an inorganic porous material. The inorganic porous material itself does not adsorb odorous substances (has almost no deodorant performance), but when used in combination with the above-mentioned hydrazine compound and divalent metal chloride, it is compared with the case where no inorganic porous material is used. Since the inorganic porous material stores water, the effect of improving the deodorizing performance and the deodorizing rate by the hygroscopic agent can be further enhanced. In addition, the presence of the inorganic porous material increases the contact area with the odorous substance, so that the deodorizing performance can be efficiently exhibited.

  The inorganic porous material is not particularly limited, and examples thereof include compounds containing silicon (silica, activated clay, zeolite, clay, talc, etc.), activated carbon, alumina, ceramics, calcium carbonate and the like. Of these, a compound containing silicon is preferable, and silica is more preferable, from the viewpoint of easily improving the deodorizing performance and the deodorizing rate in an environment where the water content is not sufficient. These inorganic porous materials can be used alone or in combination of two or more.

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

  When a compound containing silicon is used as the inorganic porous material, it may have a substituted or unsubstituted amino group on the surface. Such a material can be obtained by chemically modifying 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. Examples of the silane coupling agent having, a silane coupling agent having a mercapto group, and the like, a compound containing a silicon having a substituted or unsubstituted amino group modified by these silane coupling agents (particularly, these silane coupling agents are It is also possible to employ silica having a substituted or unsubstituted amino group modified therein.

  When the 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 deodorizing performance and the deodorizing rate in an environment where the water content is insufficient are further improved. From the viewpoint of 100 parts by mass of the hydrazine compound, for example, preferably 1 part by mass or more, more preferably 10 parts by mass or more, more preferably 20 parts by mass or more, for example, preferably 20000 parts by mass or less, 5000 The amount is preferably not more than 2000 parts by mass, more preferably not more than 2000 parts by mass.

  When the 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 deodorizing performance and the deodorizing rate in an environment where the water content is insufficient are further improved. From the viewpoint of making the total amount of the odorant adsorbent 100% by mass, for example, preferably 0.1% by mass or more, more preferably 1.0% by mass or more, further preferably 2.0% by mass or more, and, for example, 99.9% by mass or less. It is preferably 99.0% by mass or less, more preferably 95.0% by mass or less.

(1-4) Odorant Adsorbent As described above, the odorant adsorbent of the present invention has a form containing a hydrazine compound, a divalent metal chloride, and, if necessary, an inorganic porous material. In any form, it can be used as it is (in the form of powder solid), or can be dissolved or dispersed in a solvent to give 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. In particular, it is preferably used as a solution or a suspension in consideration of the case of forming on a substrate having a small amount of water described later.

  Examples of the solvent when the odorant 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, n-butanol and the like.

  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, ethylene glycol monomethyl. Examples thereof include ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether.

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

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

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

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

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

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

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

  When the odorant adsorbent of the present invention is 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 in an environment where the water content is not sufficient, the odorant The total amount of the adsorbent is 100 mass%, for example, preferably 30.0 mass% or more, more preferably 50.0 mass% or more, more preferably 70.0 mass% or more, for example, 99.9 mass% or less, preferably 99.0 mass% or less. Is more preferable, and 98.0 mass% or less is further preferable.

  Further, it is also possible to mix and use the above-mentioned respective components and the synthetic resin. Examples of the synthetic resin include polyacrylic resin (acrylic resin, methacrylic resin, etc.), polyvinyl acetate resin (vinyl acetate resin, etc.), polyvinyl chloride resin (vinyl chloride resin, etc.), polyolefin resin (olefin resin). Etc.), ethylene-vinyl acetate copolymer resin (EVA resin), polyurethane resin (urethane resin etc.), polystyrene resin (styrene resin etc.), polyepoxy resin (epoxy resin etc.), silicone resin (silicone resin) Etc.), alkyd resin (alkyd resin etc.), fluorine resin (polytetrafluoroethylene resin etc.), nylon resin, polyester resin (polyester etc .; excluding polyester fiber), polyamide resin (aramid resin etc.), Examples thereof include PET resins (polyethylene terephthalate etc.), ether resins (polyphenylene ether resins etc.), polyamine resins, amino resins (melamine resins, urea resins etc.) and phenol resins. A copolymer resin containing one or more of the above resins can also be employed. It is also possible to employ an emulsion made of the above resin. These synthetic resins may be used alone or in combination of two or more kinds. Of these, polyacrylic resins (acrylic resins, methacrylic resins, etc.) are preferable.

  When a synthetic resin is contained in the odorant adsorbent of the present invention, the content of the synthetic resin is not particularly limited, from the viewpoint of deodorant performance in an environment where the water content is not sufficient, the odorant adsorption of the present invention The total amount of the agent is 100 mass%, for example, preferably 0.1 mass% or more, more preferably 1.0 mass% or more, more preferably 5.0 mass% or more, for example, 99.5 mass% or less, 99.0 mass% or less. It is more preferably 98.0% by mass or less.

  Further, it is also possible to use an inorganic material other than synthetic resin for processed products such as building materials. Examples of such inorganic materials for processed products such as building materials include cement, asphalt, concrete, plaster, mortar, diatomaceous earth, montmorillonite, beidellite, nontronite, saponite, hectorite, kaolinite, and ceramics. These inorganic materials for processed products such as building materials can be used alone or in combination of two or more kinds.

  When an inorganic material for a processed product such as a building material is contained in the odorant adsorbent of the present invention, the content of the inorganic material for a processed product such as a building material is not particularly limited, and the deodorant performance in an environment where the water content is not sufficient From the viewpoint of, the total amount of the odorant adsorbent of the present invention as 100 mass%, for example, preferably 0.1 mass% or more, more preferably 1.0 mass% or more, more preferably 5.0 mass% or more, for example, 99.5 mass% % Or less, preferably 99.0% by mass or less, more preferably 98.0% by mass or less.

  The odorant adsorbent of the present invention can be generally and generally formulated into known additives such as a non-volatile acid, a chelating agent, an antioxidant, a light stabilizer, etc., depending on the purpose, application, etc. 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 used. These non-volatile acids may be used alone or in combination of two or more. By blending such a non-volatile acid, the storage stability of the odorant adsorbent of the present invention can be further improved.

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

  Examples of the chelating agent include ethylenediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, oxalic acid, citric acid and the like, and salts thereof can also be adopted. These chelating agents may be used alone or in combination of two or more. By adding such a chelating agent, the storage stability of the odorant adsorbent of the present invention 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 the odorant adsorbent of the present invention being 100% by mass.

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

  When an antioxidant is used, its content is not particularly limited, and is preferably 1 to 10% by mass with the total amount of the odorant adsorbent of the present invention being 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 may be used alone or in combination of two or more.

  When a light stabilizer is used, its content is not particularly limited, but is preferably 1 to 10 mass% when the total amount of the odorant adsorbent of the present invention is 100 mass%.

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

  Such an odorant adsorbent of the present invention can be used as it is, but can also be formed on a substrate to be used as an odorant adsorbent. The method for forming the odorant adsorbent of the present invention on the substrate is not particularly limited, and a usual method such as a coating method can be adopted. When the coating method is adopted, for example, roller coating, screen coating, doctor blade, spin coating, bar coating and the like can be used.

As for the base material, if the base material has a large amount of water, even in an environment where the water content is not sufficient, it may be possible to suppress the dry deactivation of the hydrazine compound due to the water content in the base material. An excellent deodorizing performance and deodorizing rate may be obtained without using an adsorbent. On the other hand, for a substrate having a low water content, in an environment where the water content is not sufficient, when the odorant adsorbent of the present invention is not used, it is not possible to suppress the dry deactivation of the hydrazine compound, and excellent deodorant performance and No deodorizing rate can be obtained. Thus, in the present invention, when the odorant adsorbent of the present invention is formed on a substrate, excellent deodorizing performance and deodorizing rate are obtained even if the substrate has a small amount of water. It is effective in obtaining points. As such a substrate having a small amount of water, the amount of water evaluated from the weight of the substrate at 23 ° C and the weight of the substrate at 60 ° C is preferably 5.0% by mass or less, and 4.0% by mass or less. It is more preferable that the amount is 3.0% by mass or less. In particular, when the water content is 4.0% by mass or less, the deodorizing performance and the deodorizing rate are inversely improved even though the relative content of the hydrazine compound due to the use of the hygroscopic agent is reduced. It is possible to Further, since the effect of using the odorant adsorbent of the present invention can be expected when the amount of water in the base material is small, the smaller the amount, the better, and the lower limit is 0.0% by mass. The amount of water is the total amount of water contained in the base material itself and the base material weight at 23 ° C. and 50% humidity, and the base material at 60 ° C. has almost no water content. Judge that it is the weight of the base material itself,
(Base material weight at 23 ° C humidity 50% -60 ° C base material weight) / Base material weight at 23 ° C humidity 50% x 100
Calculate by

  Specific examples of the base material having a low water content include a polyethylene terephthalate plate, a glass plate, an aluminum plate, and a wallpaper sheet.

  Further, the odorant adsorbent of the present invention is not only on the substrate, but also as a method of imparting a deodorant function to the object in a form of kneading into the substrate or adding to the material before molding and then molding. Can be used.

  As described above, the odorant adsorbent and odorant adsorbent material of the present invention, even in an environment where the water content is not sufficient, suppresses the dry deactivation of the hydrazine compound, and has excellent deodorant performance and deodorant rate. Therefore, it is effective in that it can be used in applications where the water content is not sufficient, which could not be used due to the dry deactivation of the hydrazine compound in the conventional odorant adsorbents. ..

  Examples of applications used in such an insufficient moisture environment include applications in which at least one step of the manufacturing process is performed at 130 ° C or higher (including the case where all steps are performed at 130 ° C or higher). Be done. This temperature may include both a case where the product temperature reaches 130 ° C. or higher and a case where the ambient temperature (temperature of the dryer or the like) is 130 ° C. or higher. The temperature is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, still more preferably 185 ° C. or higher, particularly preferably 190 ° C. or higher, from the viewpoint of the deodorant performance and deodorant rate of the odorant adsorbent of the present invention. 200 ° C. or higher is particularly preferable. Further, the upper limit of the temperature in the use of the odorant adsorbent of the present invention is not particularly limited, but the temperature not exceeding the boiling point of the hydrazine compound and the use of the odorant adsorbent of the present invention (building materials etc.) It is preferable that the temperature is not higher than the temperature that does not deteriorate the quality. From this point of view, the upper limit of the heating temperature is usually 1000 ° C.

  Examples of applications in which at least one step of such a manufacturing process is performed at 130 ° C or higher (including the case where all steps are performed at 130 ° C or higher) are, for example, building materials (wallpaper, flooring, ceiling material, handrails, etc.), heating Plastics, textile products (kneading type), filters and the like.

(1-5) Odorant The above-mentioned odorant adsorbent of the present invention efficiently and quickly adsorbs odorants (especially aldehyde compounds, ketone compounds, carboxylic acid compounds, etc.) even in an environment where the water content is not sufficient. be able to. The odorant adsorbent of the present invention is effective for the above odorants in combination of one kind or two or more kinds.

  The odorant to be adsorbed by the odorant adsorbent of the present invention is not particularly limited, for example, formaldehyde, acetaldehyde, propionaldehyde, acrolein, n-butyraldehyde, isobutyraldehyde, pentanal, hexanal, heptanal, octanal, Aldehyde odorants (aldehyde compounds) such as nonenal, decanal, 3-methyl-butyraldehyde, crotonaldehyde, 2,4-heptadienal; ketone odorants such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, diacetyl (ketone) Compounds); formic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, 3-methylbutanoic acid, 4-methyloctanoic acid, and other organic acid odorants (carboxylic acid compounds), among others. The odorant adsorbent of the present invention is effective for adsorbing aldehyde compounds, particularly formaldehyde and / or acetaldehyde.

2. Industrial Product Containing Odorant Adsorbent The odorant adsorbent of the present invention can be used by being contained (blended and applied on the surface) in an industrial product. The industrial product includes the present invention (industrial product of the present invention).

  The industrial products refer to industrial products and industrial raw materials that have been widely known. Specifically, building materials (wallpaper, flooring, ceiling materials, handrails, etc.), heating plastics, filters, paints, adhesives, inks, sealing agents, paper products, binders, resin emulsions, pulp, wood materials, wood products. , Plastic products, films, textile products and the like.

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

3. Adsorption method of odor substance using odor substance adsorbent The adsorption method of the odor substance of the present invention, by contacting the odor substance with the odor substance adsorbent of the present invention, even in an environment where the water content is not sufficient, The odorant adsorbent of the invention adsorbs an odorant. Specifically, by contacting an odor substance with an industrial product provided with the odor substance adsorbent of the present invention, to adsorb the odor substance to the odor substance adsorbent of the present invention, even in an environment where the water content is not sufficient You can Examples of applications used in an environment where the water content is not sufficient include applications in which at least one step of the manufacturing process is performed at 130 ° C or higher (including the case where all steps are performed at 130 ° C or higher). According to the adsorption method, the odorant adsorbent of the present invention efficiently and quickly adsorbs the odorant, so that the odorant can be efficiently and quickly removed. For example, when a building material such as a wallpaper provided with the odorant adsorbent of the present invention is installed indoors, the odorous substance contained in the indoor air is brought into contact with the building material such as the wallpaper by natural circulation of indoor air. , Is adsorbed (deodorized).

  Further, a fixed bed, a moving bed, an adsorbing device such as a fluidized bed is an industrial product filled with the odorant adsorbent of the present invention, and the gas containing the odorant is also aerated, whereby the odorant can be efficiently treated. It can be adsorbed and removed well and quickly and over a long period of time.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the embodiments described below. The following reagents were used.
Adipic acid dihydrazide (ADH): manufactured by Tokyo Chemical Industry Co., Ltd. Dodecanedioic acid dihydrazide (DDADH): manufactured by Tokyo Chemical Industry Co., Ltd. Calcium chloride: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Silica: manufactured by Mizusawa Chemical Industry Co., Ltd. Mizukashiru.

Test Example 1: Moisture Content of Base Material The various base materials shown in Table 1 were allowed to stand overnight at 23 ° C. and 50% humidity, and the total weight of the base material itself and the water content in the base material was 23 ° C. Was measured. Next, the various base materials shown in Table 1 were allowed to stand at 60 ° C. for 48 hours, and the weight of the base material itself was measured at 60 ° C. And the following formula:
(Base material weight at 23 ° C humidity 50% -60 ° C base material weight) / Base material weight at 23 ° C humidity 50% x 100
The amount of water in the substrate was calculated by The measurement was performed on two samples each, and the average value was taken as the water content.

As the base material used for the measurement, commercially available products were used for gauze, drawing paper, Chinese plywood, lauan plywood, cedar, urine, cypress, bay pine, thermowood and ACQ, and the following were used.
PET plate: P-1307 manufactured by Kyoei Plastics Co., Ltd.
Glass plate: made by Tayu Kikai Co., Ltd. Aluminum plate: made by Tayu Kikai Co., Ltd. Foamed vinyl chloride: E-7001 white made by Acrysan Day Co., Ltd.

Comparative Example 1: Hydrazine 50: Silica 50: Divalent metal chloride 0 (foamed vinyl chloride)
To 95 parts by mass of an acrylic emulsion (Ultraika 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 2.5 parts by mass of silica were added, It was dissolved in a sonic bath to give an adsorbent (adsorption liquid).

  The obtained adsorbent (adsorption liquid) was applied to foamed vinyl chloride (E-7001 white manufactured by Acrysanday Co., Ltd .; water content: 1.9% by mass) with a bar coater to a thickness of 10 μm, and air-dried at room temperature overnight. Then, by heating in a dryer set at 200 ° C. for 10 minutes, an odorant adsorbent was formed on the foamed vinyl chloride to obtain a deodorant test sample of Comparative Example 1.

Comparative Example 2: Hydrazine 50: Silica 50: Divalent metal chloride 40 (foamed vinyl chloride)
2.5 parts by mass of dodecanedioic acid dihydrazide, 2.5 parts by mass of silica and 2.0 parts by mass of calcium chloride based on 95 parts by mass of an acrylic emulsion (Ultraika C-63 manufactured by Aika Kogyo Co., Ltd .; adjusted to have a solid content of 10% by mass). Part was added and dissolved in an ultrasonic bath to give an adsorbent (adsorption liquid).

  The obtained adsorbent (adsorption liquid) was applied to foamed vinyl chloride (E-7001 white manufactured by Acrysanday Co., Ltd .; water content: 1.9% by mass) with a bar coater to a thickness of 10 μm, and air-dried at room temperature overnight. Then, by heating in a dryer set at 200 ° C. for 10 minutes, an odorant adsorbent was formed on the foamed vinyl chloride to obtain a sample for deodorant test of Comparative Example 2.

Comparative Example 3: Hydrazine 50: Silica 50: Divalent metal chloride 50 (foamed vinyl chloride)
A deodorant test sample of Comparative Example 3 was obtained in the same manner as Comparative Example 2 except that the amount of calcium chloride used was 2.5 parts by mass instead of 2.0 parts by mass.

Example 1: Hydrazine 50: Silica 50: Bivalent metal chloride 100 (foamed vinyl chloride)
A sample for deodorant test of Example 1 was obtained in the same manner as Comparative Example 2 except that the amount of calcium chloride used was 5.0 parts by mass instead of 2.0 parts by mass.

Example 2: Hydrazine 50: Silica 50: Bivalent metal chloride 200 (foamed vinyl chloride)
A deodorant test sample of Example 2 was obtained in the same manner as Comparative Example 2 except that the amount of calcium chloride used was 10.0 parts by mass instead of 2.0 parts by mass.

Example 3: Hydrazine 50: Silica 50: Bivalent metal chloride 400 (foamed vinyl chloride)
A deodorant test sample of Example 3 was obtained in the same manner as Comparative Example 2 except that the amount of calcium chloride used was 20.0 parts by mass instead of 2.0 parts by mass.

Test example 1 (acetaldehyde adsorption performance)
One sample for deodorant test (each cut into 5 cm x 10 cm) obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was placed in a 1 L sampling bag (smart bag PA, manufactured by GL Sciences Inc.), After sealing, air in the sampling bag was removed using a piston. After that, 1 L of acetaldehyde gas adjusted to 14 ppm was injected, and the residual gas concentrations after 1 hour, 3 hours, and 24 hours were evaluated using a detector tube (Gastec Co., Ltd.). The results are shown in Table 2.

Comparative Example 4: Hydrazine 80: Silica 20: Divalent metal chloride 0 (foamed vinyl chloride)
To 95 parts by mass of acrylic emulsion (Ultraika C-63 manufactured by Aika Kogyo Co., Ltd .; adjusted to have a solid content of 10% by mass), 4.0 parts by mass of adipic acid dihydrazide and 1.0 part by mass of silica were added, and ultrasonic waves were applied. It was dissolved in a bath and used as an adsorbent (adsorption liquid).

  The obtained adsorbent (adsorption liquid) was applied to foamed vinyl chloride (E-7001 white manufactured by Acrysanday Co., Ltd .; water content: 1.9% by mass) with a bar coater to a thickness of 10 μm, and air-dried at room temperature overnight. Then, by heating in a dryer set at 200 ° C. for 10 minutes, an odorant adsorbent was formed on the foamed vinyl chloride, and a sample for deodorant test of Comparative Example 4 was obtained.

Comparative Example 5: Hydrazine 80: Silica 20: Divalent metal chloride 40 (foamed vinyl chloride)
With respect to 95 parts by mass of acrylic emulsion (Ultraika C-63 manufactured by Aika Kogyo Co., Ltd .; adjusted to have a solid content of 10% by mass), 4.0 parts by mass of adipic dihydrazide, 1.0 part by mass of silica, and 2.0 parts by mass of calcium chloride. Part was added and dissolved in an ultrasonic bath to obtain an adsorbent (adsorption liquid).

  The obtained adsorbent (adsorption liquid) was applied to foamed vinyl chloride (E-7001 white manufactured by Acrysanday Co., Ltd .; water content: 1.9% by mass) with a bar coater to a thickness of 10 μm, and then overnight at room temperature. It was air-dried and then heated in a dryer set at 200 ° C. for 10 minutes to form an odorant adsorbent on the foamed vinyl chloride, and used as a sample for the deodorant test of Comparative Example 5.

Comparative Example 6: Hydrazine 80: Silica 20: Divalent metal chloride 80 (foamed vinyl chloride)
A deodorant test sample of Comparative Example 6 was obtained in the same manner as Comparative Example 5 except that the amount of calcium chloride used was 4.0 parts by mass instead of 2.0 parts by mass.

Example 4: Hydrazine 80: Silica 20: Divalent metal chloride 160 (foamed vinyl chloride)
A sample for deodorant test of Example 4 was obtained in the same manner as Comparative Example 5 except that the amount of calcium chloride used was 8.0 parts by mass instead of 2.0 parts by mass.

Example 5: Hydrazine 80: Silica 20: Bivalent metal chloride 200 (foamed vinyl chloride)
A deodorant test sample of Example 5 was obtained in the same manner as Comparative Example 5 except that the amount of calcium chloride used was 10.0 parts by mass instead of 2.0 parts by mass.

Example 6: Hydrazine 80: Silica 20: Bivalent metal chloride 400 (foamed vinyl chloride)
A deodorant test sample of Example 6 was obtained in the same manner as Comparative Example 5 except that the amount of calcium chloride used was 20.0 parts by mass instead of 2.0 parts by mass.

Test Example 2 (acetaldehyde adsorption performance)
One sample for deodorant test (each cut to 5 cm x 10 cm) obtained in Examples 4 to 6 and Comparative Examples 4 to 6 was placed in a 1 L sampling bag (smart bag PA, manufactured by GL Sciences Inc.), After sealing, air in the sampling bag was removed using a piston. After that, 1 L of acetaldehyde gas adjusted to 14 ppm was injected, and the residual gas concentrations after 1 hour, 3 hours, and 24 hours were evaluated using a detector tube (Gastec Co., Ltd.). The results are shown in Table 3.

Comparative Example 7: Hydrazine 50: Silica 50: Divalent Metal Chloride 0 (Drawing Paper)
To 95 parts by mass of an acrylic emulsion (Ultraika 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 2.5 parts by mass of silica were added, It was dissolved in a sonic bath to give an adsorbent (adsorption liquid).

  The obtained adsorbent (adsorption liquid) was applied to a drawing paper (commercial product; moisture content 4.6% by mass) using a bar coater to a thickness of 10 μm, air-dried at room temperature overnight, and then dried at 200 ° C. By heating for 10 minutes in the machine, an odorant adsorbent was formed on the drawing paper, and used as a sample for the deodorant test of Comparative Example 7.

Comparative Example 8: Hydrazine 50: Silica 50: Divalent Metal Chloride 40 (Drawing Paper)
2.5 parts by mass of dodecanedioic acid dihydrazide, 2.5 parts by mass of silica and 2.0 parts by mass of calcium chloride based on 95 parts by mass of an acrylic emulsion (Ultraika C-63 manufactured by Aika Kogyo Co., Ltd .; adjusted to have a solid content of 10% by mass). Part was added and dissolved in an ultrasonic bath to obtain an adsorbent (adsorption liquid).

  The obtained adsorbent (adsorption liquid) was applied to a drawing paper (commercial product; moisture content 4.6% by mass) using a bar coater to a thickness of 10 μm, air-dried at room temperature overnight, and then dried at 200 ° C. By heating for 10 minutes in the machine, an odorant adsorbent was formed on the drawing paper, and used as a sample for the deodorant test of Comparative Example 8.

Comparative Example 9: Hydrazine 50: Silica 50: Divalent Metal Chloride 50 (Drawing Paper)
A deodorant test sample of Comparative Example 9 was obtained in the same manner as Comparative Example 8 except that the amount of calcium chloride used was 2.5 parts by mass instead of 2.0 parts by mass.

Example 7: Hydrazine 50: Silica 50: Bivalent Metal Chloride 100 (Drawing Paper)
A sample for deodorant test of Example 7 was obtained in the same manner as Comparative Example 8 except that the amount of calcium chloride used was 5.0 parts by mass instead of 2.0 parts by mass.

Example 8: Hydrazine 50: Silica 50: Bivalent metal chloride 200 (paper)
A deodorant test sample of Example 8 was obtained in the same manner as Comparative Example 8 except that the amount of calcium chloride used was 10.0 parts by mass instead of 2.0 parts by mass.

Example 9: Hydrazine 50: Silica 50: Bivalent metal chloride 400 (drawing paper)
A deodorant test sample of Example 9 was obtained in the same manner as Comparative Example 8 except that the amount of calcium chloride used was 20.0 parts by mass instead of 2.0 parts by mass.

Test example 3 (acetaldehyde adsorption performance)
One sample for deodorant test (each cut into 5 cm x 10 cm) obtained in Examples 7 to 9 and Comparative Examples 7 to 9 was placed in a 1 L sampling bag (smart bag PA, manufactured by GL Sciences Inc.), After sealing, air in the sampling bag was removed using a piston. After that, 1 L of acetaldehyde gas adjusted to 14 ppm was injected, and the residual gas concentrations after 1 hour, 3 hours, and 24 hours were evaluated using a detector tube (Gastec Co., Ltd.). The results are shown in Table 4.

Comparative Example 10: Hydrazine 100: Silica 0: Divalent metal chloride 0 (foamed vinyl chloride)
To 95 parts by mass of an acrylic emulsion (Ultraika C-63 manufactured by Aika Kogyo Co., Ltd .; adjusted to have a solid content of 10% by mass), 5.0 parts by mass of adipic acid dihydrazide was added and dissolved in an ultrasonic bath. , And as an adsorbent (adsorption liquid).

  The obtained adsorbent (adsorption liquid) was applied to foamed vinyl chloride (E-7001 white manufactured by Acrysanday Co., Ltd .; water content: 1.9% by mass) with a bar coater to a thickness of 10 μm, and air-dried at room temperature overnight. Then, by heating in a dryer set at 200 ° C. for 10 minutes, an odorant adsorbent was formed on the foamed vinyl chloride to obtain a sample for deodorant test of Comparative Example 10.

Comparative Example 11: Hydrazine 100: Silica 0: Divalent metal chloride 40 (foamed vinyl chloride)
To 95 parts by mass of acrylic emulsion (Aika Kogyo Co., Ltd., Ultrasol C-63; adjusted to have a solid content of 10% by mass), 5.0 parts by mass of adipic acid dihydrazide and 2.0 parts by mass of calcium chloride were added, It was dissolved in an ultrasonic bath and used as an adsorbent (adsorption liquid).

  The obtained adsorbent (adsorption liquid) was applied to foamed vinyl chloride (E-7001 white manufactured by Acrysanday Co., Ltd .; water content: 1.9% by mass) with a bar coater to a thickness of 10 μm, and then overnight at room temperature. It was air-dried and then heated in a dryer set at 200 ° C. for 10 minutes to form an odorant adsorbent on the foamed vinyl chloride, and used as a sample for the deodorant test of Comparative Example 11.

Comparative Example 12: Hydrazine 100: Silica 0: Bivalent metal chloride 80 (foamed vinyl chloride)
A deodorant test sample of Comparative Example 12 was obtained in the same manner as Comparative Example 11 except that the amount of calcium chloride used was 4.0 parts by mass instead of 2.0 parts by mass.

Example 10: Hydrazine 100: Silica 0: Divalent metal chloride 160 (foamed vinyl chloride)
A sample for deodorant test of Example 10 was obtained in the same manner as Comparative Example 11 except that the amount of calcium chloride used was 8.0 parts by mass instead of 2.0 parts by mass.

Example 11: Hydrazine 100: Silica 0: Bivalent metal chloride 200 (foamed vinyl chloride)
A deodorant test sample of Example 11 was obtained in the same manner as Comparative Example 11 except that the amount of calcium chloride used was 10.0 parts by mass instead of 2.0 parts by mass.

Example 12: Hydrazine 100: Silica 0: Bivalent metal chloride 400 (foamed vinyl chloride)
A deodorant test sample of Example 12 was obtained in the same manner as Comparative Example 11 except that the amount of calcium chloride used was 20.0 parts by mass instead of 2.0 parts by mass.

Example 13: Hydrazine 90: Silica 30: Bivalent metal chloride 180 (foamed vinyl chloride)
4.5 parts by mass of adipic dihydrazide, 9.0 parts by mass of calcium chloride, and 1.5 parts by mass of silica with respect to 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). Part was added and dissolved in an ultrasonic bath to obtain an adsorbent (adsorption liquid).

  The obtained adsorbent (adsorption liquid) was applied to foamed vinyl chloride (E-7001 white manufactured by Acrysanday Co., Ltd .; water content: 1.9% by mass) with a bar coater to a thickness of 10 μm, and then overnight at room temperature. It was air-dried and then heated in a dryer set at 200 ° C. for 10 minutes to form an odorant adsorbent on the foamed vinyl chloride, and used as a sample for the deodorant test of Example 13.

Test Example 4 (acetaldehyde adsorption performance)
One sample for deodorant test obtained in each of Examples 10 to 13 and Comparative Examples 10 to 12 (each cut into 5 cm x 10 cm) was placed in a 1 L sampling bag (smart bag PA, manufactured by GL Sciences Inc.), After sealing, air in the sampling bag was removed using a piston. After that, 1 L of acetaldehyde gas adjusted to 14 ppm was injected, and the residual gas concentrations after 1 hour, 3 hours, and 24 hours were evaluated using a detector tube (Gastec Co., Ltd.). The results are shown in Table 5.

Comparative Example 13: Hydrazine 100: Silica 0: Divalent Metal Chloride 0 (Drawing Paper)
To 95 parts by mass of an acrylic emulsion (Ultraika C-63 manufactured by Aika Kogyo Co., Ltd .; adjusted to have a solid content of 10% by mass), 5.0 parts by mass of adipic acid dihydrazide was added and dissolved in an ultrasonic bath. , And as an adsorbent (adsorption liquid).

  The obtained adsorbent (adsorption liquid) was applied to a drawing paper (commercial product: 4.6% by mass) with a bar coater to a thickness of 10 μm, air-dried at room temperature overnight, and then in a dryer set at 200 ° C. By heating for 10 minutes, an odorant adsorbent was formed on the foamed vinyl chloride and used as a sample for the deodorant test of Comparative Example 13.

Comparative Example 14: Hydrazine 100: Silica 0: Divalent Metal Chloride 40 (Drawing Paper)
To 95 parts by mass of acrylic emulsion (Aika Kogyo Co., Ltd., Ultrasol C-63; adjusted to have a solid content of 10% by mass), 5.0 parts by mass of adipic acid dihydrazide and 2.0 parts by mass of calcium chloride were added, It was dissolved in an ultrasonic bath and used as an adsorbent (adsorption liquid).

  The obtained adsorbent (adsorption liquid) was applied to a drawing paper (commercial product; water content 4.6% by mass) with a bar coater to a thickness of 10 μm, and then air-dried at room temperature overnight, and then set to 200 ° C. By heating in a dryer for 10 minutes, an odorant adsorbent was formed on the expanded vinyl chloride, and used as a sample for the deodorant test of Comparative Example 14.

Comparative Example 15: Hydrazine 100: Silica 0: Divalent Metal Chloride 80 (Drawing Paper)
A deodorant test sample of Comparative Example 15 was obtained in the same manner as Comparative Example 14 except that the amount of calcium chloride used was 4.0 parts by mass instead of 2.0 parts by mass.

Example 14: Hydrazine 100: Silica 0: Divalent Metal Chloride 160 (Drawing Paper)
A deodorant test sample of Example 14 was obtained in the same manner as Comparative Example 14 except that the amount of calcium chloride used was 8.0 parts by mass instead of 2.0 parts by mass.

Example 15: Hydrazine 100: Silica 0: Bivalent metal chloride 200 (Drawing paper)
A deodorant test sample of Example 15 was obtained in the same manner as Comparative Example 14 except that the amount of calcium chloride used was 10.0 parts by mass instead of 2.0 parts by mass.

Example 16: Hydrazine 100: Silica 0: Bivalent metal chloride 400 (drawing paper)
A deodorant test sample of Example 16 was obtained in the same manner as Comparative Example 14 except that the amount of calcium chloride used was 20.0 parts by mass instead of 2.0 parts by mass.

Test Example 5 (acetaldehyde adsorption performance)
One sample for deodorant test obtained in Examples 14 to 16 and Comparative Examples 13 to 15 (each cut into 5 cm x 10 cm) was placed in a 1 L sampling bag (smart bag PA, manufactured by GL Sciences Inc.), After sealing, air in the sampling bag was removed using a piston. After that, 1 L of acetaldehyde gas adjusted to 14 ppm was injected, and the residual gas concentrations after 1 hour, 3 hours, and 24 hours were evaluated using a detector tube (Gastec Co., Ltd.). The results are shown in Table 6.

  As described above, in the case of adding calcium chloride, which is a divalent metal chloride, when the content of calcium chloride is made higher than the content of the hydrazine compound, the relative content of the hydrazine compound by the addition of calcium chloride. Despite the decrease, the deodorant performance and deodorant rate were improved rather than decreased, or at least maintained. In particular, it is a surprising result that the deodorizing performance and the deodorizing rate were remarkably improved when the substrate having a small water content was used. Thus, by increasing the content of calcium chloride, despite the relative content of the hydrazine compound is reduced, it is an unexpected effect that the deodorant performance and deodorant rate is significantly improved. Is. From this fact, the negative effect on the deodorizing performance and the deodorizing rate due to the decrease in the relative content of the hydrazine compound was considered to be due to the loss of the hydrazine compound on drying due to the increase of the divalent metal chloride, calcium chloride. It suggests that the improvement effect by suppressing the activity is equal or higher. In the above examples, as an example, the data in the case of heating at 200 ° C. is shown.However, the inventors of the present invention show that the hydrazine compound is dried and inactivated after standing for several days even at room temperature. It has been found that the deodorizing performance and the deodorizing rate are significantly deteriorated, and since it is possible to suppress this dry deactivation by using a divalent metal chloride, the same result can be obtained even at room temperature. It can be understood.

Claims (12)

A hydrazine compound having a molecular weight of 100 or more and a divalent metal chloride, the molecular weight is 100 parts by mass or more of the hydrazine compound of 100 or more, the content of the divalent metal chloride is greater than 100 parts by mass, Odorant adsorbent. The hydrazine compound having a molecular weight of 100 or more is lauric acid hydrazide, salicylic acid hydrazide, p-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide, 3-hydroxy-2-naphthoic acid hydrazide, benzhydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, amber. Acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, tartaric acid dihydrazide, diglycolide dihydrazide dihydrazide, malic acid dihydrazide dihydrazide Dihydrazide, 2,6-naphthalenedicarboxylic acid dihydrazide, 2.6-naphthoic acid dihydrazide, citric acid trihydrazide, pyromellitic acid trihydrazide, 1,2,4-benzenetricarboxylic acid trihydrazide, nitrilotriacetic acid trihydrazide, 1,3, 5-cyclohexanetricarboxylic acid trihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, benzylhydrazine, phenylhydrazine, 3-amino-5-phenyl-1,2,4-triazole, and The odorant adsorbent according to claim 1, which is at least one selected from the group consisting of 4-aminourazole. The odorant adsorbent according to claim 1 or 2, wherein the divalent metal chloride is at least one selected from the group consisting of calcium chloride, magnesium chloride and iron chloride. The odorant adsorbent according to any one of claims 1 to 3, further comprising an inorganic porous material. The odorant adsorbent according to claim 4, wherein the inorganic porous material is a compound containing silicon. The odorant adsorbent according to claim 4 or 5, wherein the inorganic porous material is silica. The odorant adsorbent according to any one of claims 1 to 6, wherein the odorant is at least one selected from the group consisting of aldehyde compounds, ketone compounds and carboxylic acid compounds. The odorant adsorbent according to any one of claims 1 to 7, which is used for an industrial product in which at least one step of a manufacturing process is performed at 130 ° C or higher. A layer containing the odorant adsorbent according to any one of claims 1 to 8 is formed on a base material, and the base material has a water content of 5.0 evaluated from the weight at 23 ° C and the weight at 60 ° C. An odor substance adsorbing material having a mass% or less. The odor substance adsorbing material according to claim 9, wherein the base material is a polyethylene terephthalate plate, a glass plate, an aluminum plate or a wallpaper sheet. An industrial product comprising the odorant adsorbent according to any one of claims 1 to 8 or the odorant adsorbent according to claim 9 or 10. A method for adsorbing an odor substance, comprising the step of bringing the odor substance into contact with the odor substance adsorbent according to any one of claims 1 to 8 or the odor substance adsorbent material according to claim 9 or 10.