JP2019205773A - Fragrance generation method using porous coordination polymer, and analysis method of aromatic component generated by fragrance generation method - Google Patents

Abstract

To provide a fragrance generation method for 'reproduction of incense memory' for generating smell stored once by incense, by using an aromatic material having a function capable of adsorbing a natural or artificial aromatic component, and discharging the smell again, repeatedly.SOLUTION: There is provided a fragrance generation method using a porous coordination polymer having a porous skeleton structure. In the fragrance generation method, fragrance is generated from an aromatic material containing the porous coordination polymer and aromatic molecules, by at least any means among ventilation, heating, application of an electric field and a voltage, application of a magnetic field and vibration.SELECTED DRAWING: Figure 2

Description

  The present invention relates to an aroma generating method using a porous coordination polymer and an analysis method of an aroma component generated by the aroma generating method.

  It is said that odors and fragrances can be felt for the first time when vaporized fragrance components are received by the sense of smell. There are various kinds of fragrance materials made of this fragrance component, such as liquid, diluted, gelled, and kneaded into a solid. The vaporization method includes a method of evaporating the surface and a method of vaporizing a solid liquid by heating. However, in general, aromatic molecules are highly volatile and can be evaporated from the surface or vaporized directly from the solid liquid and diffused around the material without causing irritation such as heating. It feels like a fragrance. Therefore, in the case of liquid or gel materials that are prone to vaporization, in order not to feel odors and fragrances, they must be physically sealed or made with other materials and solid molded. I must. As an exception to natural products, agarwood, a kind of incense tree, is known as a substance that does not aroma in a normal state and has a unique aroma when heated. However, agarwood is expensive because it is difficult to produce artificially, and an aroma molecule cannot be artificially selected. If there is an artificial material that can sense the fragrance only after heating like agarwood and can intentionally select the fragrant molecule, it will open up a new fragrance and sensation world.

Chemical Review No. 14 Taste and odor chemistry, Chemical Society of Japan, first edition of 1976, fifth edition of 1985

  Conventional fragrance materials did not have the function of repeatedly adsorbing natural and artificial fragrance components and releasing odor again.

  On the other hand, there has been a need to use fragrance in a form that can be repeatedly removed, for example, as a small, portable or stationary device. However, conventional fragrances, which are difficult to reproduce repeatedly, cannot meet this need. Furthermore, sufficient consideration has been given to a fragrance generation method that can reversibly and stably generate fragrances. The fact is that it is not broken.

  The present invention uses a fragrance material capable of meeting the above-mentioned demands, and generates a fragrance once for “regeneration of recorded incense memory” to generate an odor once stored by incense. It aims at providing the analysis method of an aromatic component.

Specific means for achieving the above object are as follows.
The present invention is a method for generating a fragrance using a porous coordination polymer having a porous skeleton structure, wherein the fragrance material containing the porous coordination polymer and the fragrance molecule is blown, heated, and an electric field. And a method for generating a fragrance by generating a fragrance by at least one of application of a voltage, application of a magnetic field, and vibration. The fragrance generating method preferably includes means for blowing air to the fragrance material among these means.

  Further, in the method for generating a fragrance of the present invention, the porous coordination polymer having the porous skeleton structure includes at least one chemical structure selected from the group consisting of an imidazole skeleton, a phthalic acid skeleton, and a trimesic acid skeleton. It is preferable to have a ligand.

  In the fragrance generating method of the present invention, the porous coordination polymer having the porous skeleton structure preferably contains at least one metal ion selected from the group consisting of Al, Fe, Zn, and Cu. .

  Moreover, it is preferable that the aromatic generating method of this invention uses the aromatic molecule whose molecular weight is 100-300 as said aromatic molecule.

  The fragrance generating method of the present invention can incorporate a solid or liquid fragrance component into a small device in a chemically stable state and generate a favorite fragrance from the small device at any time with the above-described configuration. Can do.

  Furthermore, the present invention provides a method for analyzing a fragrance component, wherein the type of fragrance molecule generated by the fragrance generation method is analyzed by a gas chromatograph or a mass spectrometer. Thereby, the identification of the kind of fragrance component and the degree of deterioration of the fragrance material can be monitored with high accuracy.

  According to the present invention, it is possible to generate a solid or liquid fragrance component incorporated in a small device in a chemically stable state at any place at any time. Therefore, the fragrance generating method of the present invention can be expected to be applied to, for example, a high-performance fragrance device for mobile use.

It is the schematic which shows the method of storing an aromatic component in a porous coordination polymer by ventilation. It is the schematic which shows the test method when sensory evaluation of an odor is performed before and behind ventilation.

  The fragrance generating method of the present invention is performed to generate odor from a fragrance material recorded according to a recording method described later in order to adsorb or occlude a scent (fragrance component). By repeating the recording method of the fragrance component and the generation method of the present invention, the function of “recording and recording” can be given to the device. Hereinafter, a method for generating a fragrance for recording and recording and recording and recording a fragrance will be described.

(Definition and recording method)
Recording incense means storing a scent (fragrance component). The scent occluded by the recording incense can be released at an arbitrary timing. The aromatic component includes natural components such as flowers, plants and body odors, essential oils obtained by concentrating them, artificially synthesized aromatic components, and mixtures thereof.

  As a method of recording incense, a method of bringing a storage material into contact with an aromatic component can be mentioned. The contact method is not particularly limited. For example, 1) a solid storage material and a gaseous fragrance component (including vapor components generated from solids and liquids), 2) a solid storage material and a liquid fragrance component, and 3) a solid storage material. And a method of bringing a solid fragrance component into contact with each other. In order to effectively perform these contacts 1) to 3), the following methods (Method 1) to (Method 3) are particularly preferable.

  That is, a method of contacting a storage material and an aromatic molecule (Method 1), a method of enclosing the storage material and an aromatic molecule in a container (Method 2), a method of enclosing the storage material and an aromatic molecule in a container and blowing air to the container ( There are three methods 3).

  Method 1 includes a method in which aromatic molecules are dropped onto the storage material with a dropper or syringe, a method in which the aromatic material is added to the storage material as fine droplets such as a spray, and a method in which the solution is gently poured as a solution. Among them, the method of dropping with a dropper is preferable.

  Method 2 includes a method of standing at room temperature, a method of heating a container, and a method of heating a fragrance molecule by providing a temperature gradient in the container and cooling a storage material.

  The blower used in Method 3 includes a device having a function of blowing air by a motor such as a dryer and a device that moves manually. The storage material enclosed together with the blower is preferably sandwiched by a breathable filter so as not to scatter.

  In particular, Method 2 and Method 3 can use a sublimable solid aromatic molecule such as camphor or menthol.

(Aroma generation method for recording and reproducing incense)
As described above, the recording and recording of incense is to generate the same odor as once recorded. The target of recording and recording memory includes natural components such as flowers, plants and body odors, essential oils obtained by concentrating them, artificially synthesized fragrance components, and all fragrance components including a mixture thereof. Examples of the fragrance generation method for recording and reproducing the recording incense include air blowing, heating, application of electric field and voltage, magnetic field, vibration (including oscillation) and the like.

  When performing the fragrance generating method of the present invention by the blowing means, for example, after obtaining the fragrance material containing the fragrance component by performing the recording method for effectively contacting the storage material and the fragrance component, the blower or the like A fragrance is generated by blowing air to the fragrance material using the air blowing means. Here, the recording method includes, for example, direct mixing of a storage material and an aromatic component, adsorption or occlusion to the storage material by vapor deposition of the aromatic component, and vapor deposition using a blower to promote the vapor deposition. Etc.

  Moreover, when implementing the fragrance generating method using a heating means, it is practical to provide a temperature adjusting means for adjusting and controlling the temperature while heating the fragrance material to a desired temperature. Although there is no restriction | limiting in particular as heating temperature, 70 degreeC-400 degreeC is good from a viewpoint that it is better not to feel fragrance and odor at room temperature. Preferably it is 80 degreeC-350 degreeC, More preferably, 100 degreeC-300 degreeC is good.

  In the case of means for applying vibration, stimulation can be applied by manually or automatically swinging the storage unit for storing the fragrance material. As another means for applying vibration, an insertion type ultrasonic wave that can be used inside the storage unit, or a stirrer or stirrer having a stirring mechanism may be used.

  In the fragrance generating method of the present invention, air blowing by the air blowing means may be performed together with other means such as the heating means and the vibration means. Thereby, generation | occurrence | production of a fragrance can be performed effectively.

(Porous coordination polymer)
The porous coordination polymer having a porous skeleton structure is a crystalline solid composed of metal ions and organic ligands. It is also called a metal organic structure (MOF: Metal Organic Frameworks) or a porous polymer metal complex (PCP: Porous Coordination Polymers).

  The porous coordination polymer has a three-dimensional skeleton, and three-dimensionally ordered pores and / or hollows that are partitioned by the three-dimensional skeleton.

  The metal ions used are Sc, Ti, V, Cr, Mn, Co, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Ag, Hf, Al, Zn, Fe, Ta, W, Re, Os and It is at least one metal ion selected from the group consisting of Ir.

  The metal ions to be used are particularly preferably ions of Al, Fe, Zn, and Cu. Of these, Zn ions are preferred.

  Examples of the organic ligand coordinated to the metal ion include 1,2,4,5-tetrakis (4-carboxyphenyl) benzene, 1,3,5-tris (4′-carboxy [1,1′- Biphenyl] -4-yl) benzene, 1,3,5-tris (4-carboxyphenyl) benzene, benzene-1,3,5-tricarboxylic acid, 2,5-dihydroxyterephthalic acid, 2,6-naphthylene dicarboxylic acid Acid, 2-hydroxyterephthalic acid, 3,3 ′, 5,5′-tetracarboxydiphenylmethane, 4,4 ′, 4 ″ -S-triazine-2,4,6-triyl-tris (benzyloxy) benzoic acid, 9,10-anthracene dicarboxylic acid, biphenyl-3,3 ', 5,5'-tetracarboxylic acid, biphenyl-3,4', 5-tricarboxylic acid, terephthalic acid (BD ), Trimesic acid (BTC), [1,1 ′: 4 ′, 1 ″] terphenyl-3,3 ′, 5,5′-tetracarboxylic acid, imidazole, 2-methylimidazole, 2,4,6- Examples include tri (4-pyridyl) -1,3,5-triazine (TPT).

  Among the organic ligands listed above, 2-methylimidazole, terephthalic acid, and benzene-1,3,5-tricarboxylic acid are particularly preferable. Thus, as the organic ligand, those containing at least one chemical structure selected from the group consisting of an imidazole skeleton, a phthalic acid skeleton, and a trimesic acid skeleton are preferable. Among these, methylimidazole and benzene-1,3,5-tricarboxylic acid are particularly preferable.

(Aroma component)
An aromatic component is a group of compounds or a mixture of groups that are recognized as odors by acting on olfactory receptors in humans and animals. The threshold concentration perceived as an odor varies depending on the type of aromatic molecule, but is in the range of several ppb to several hundred ppm. There are three forms, solid, liquid, and gas, but can reach a vapor pressure with a concentration above the threshold at room temperature.

  The fragrance component adsorbed on the storage material includes one or both of those obtained naturally and those obtained by synthesis.

  The liquid fragrance molecule may be either water-soluble or oil-soluble. Monoterpene hydrocarbons, monoterpene alcohols, phenols, phenol methyl ethers, sesquiterpene hydrocarbons, sesquiterpene alcohols, ketones, lactones, carboxylic acids, diterpene alcohols, aldehydes, esters, oxides Any one of (Carbides) or a mixture obtained by blending them in a predetermined ratio is included.

  The main aromatic molecules of monoterpene hydrocarbons include pinene, limonene, myrcene, terpinene, terpinolene, δ-3-carene, tricyclene, camphene, sabinene, osymene, cymene, ferrandlene, paracymene, himalcarene, and caralene. The main aromatic molecules of monoterpene alcohols include citronellol, geraniol, terpinene-4-ol, tweenol-4, menthol, isopulegol, linalool, terpineol, nerol, borneol and nerolidol. The main aromatic components of phenols include anethole, carvacrol, eugenol, thymol, paracresol, and moldol. The main aromatic components of phenol methyl ethers include transanethole, safrole, cabicol methyl ether, paracresol methyl ether, isoeugenol methyl ether, eugenol methyl ether.

The main fragrance components of sesquiterpene hydrocarbons include α-gayen, kazinene, camazulene, β-caryophyllene, bisabolene, serinen, β-sesquiferlandolene, kruzenone, saturene, dehydroazurin, germacren D, cobaene, cedrene, fannessen, ginziberene , Tujobsen, Lindesteren, α-patulene, and Brunessen.
The main aromatic components of sesquiterpene alcohols include cedrol, casinol, santalol, globrol, pyridiflorol, nerolidol, patchoulol, redol, catrol, elemol, and spasrelol.

  The main aromatic components of ketones include camphor, acetophenone, jasmon, note caton, binocamphorphone, berbenone, piperiton, menthone, fencon, carvone, pregon, atlanton, pinocarvone and methylisobutyl. The main aromatic components of lactones include coumarin, furocoumarin, jasmine lactone, jasmon and bergapten. The main aromatic components of carboxylic acids are benzoic acid and cinnamic acid. The main aromatic components of diterpene alcohols include sclareol, phytol, and isophytol.

  The main fragrance components of aldehydes include citral, citronellol, myrtenal, acetaldehyde, perylaldehyde, piperonal, vanillin, decanal, nonanal, hexanal, and heptanal. The main aromatic components of esters include terpinyl acetate, linalyl acetate, neryl acetate, eugenol acetate, geranyl acetate, isobutyl angelate, bornyl acetate, myrtenyl acetate, confinyl benzoate, cinnamyl benzoate, methyl benzoate, benzyl benzoate , Geranyl formate, citronellyl formate, methyl angelate, and benzyl acetate. Main aromatic components of oxides (carbides) include caryophyllene oxide, bisabolol oxide, 1,8 cineol, linalool oxide, and rose oxide.

  As the aromatic molecule, any of the above-mentioned compounds can be used, and the molecular weight is not particularly limited, but is a molecule having a size smaller than the pore size of the porous coordination polymer having a porous skeleton structure described later. It is preferable. In addition, it is preferable that the aromatic molecule has a size of a certain size or more so that it is not released spontaneously when it is not subjected to a stimulus such as heating. Specifically, the molecular weight serving as a guide for size is 80 to 1000, preferably 90 to 500. Furthermore, it is preferable to use those in which the molecular weight of the aromatic molecule is included in 100 to 300.

  Among the compounds mentioned above, in particular, limonene, 2-phenylethanol, dodecanal, camphor, geraniol, nerol, citronellol, citral, indole, furfuryl methyl disulfide, notecaton, muscone, linalyl acetate, methyl jasmonate, linalool Or what mixed these in the predetermined ratio is preferable.

Examples of the mixture include aroma oils and essential oils (essential oils).
Aroma oils and essential oils include asafetida, ajowan, anise seed, amylis, angelica seed, angelica root, angel bread seed, innula, imotel (helichrysum), ylang ylang, irisu, winter green,
Winter savory, elemi, oak moss, allspice, onion, opoponax, oregano, orange sweet, orange bitter, carnation, garlic, cananga, kabos, chamomile german, chamomile roman, kaya, cayupte, caramas, calamint, galangal, cardamom , Galvanum, caraway, carrot seed, cinnamon, kuera (ammi), camphor, cumin, clari sage, grapefruit, cloves, black moji, ghetto, koyamaki, costas, copaiba, coriander, cypress, summer savory, sandalwood, cyst rose, perilla , Cedarwood Atlas, Citronella, Cinnamon Cassia, Cinnamon Bark, Cinnamon Leaf, Siberian Fir, Jasmine, Yunipaberi, silver fur, ginger, cedar, star anise, Sudachi, spikenard, spike lavender, Spanish sage,
Spearmint, sage, geranium, celery seed, st john's wort, turmeric, time mastkina, time linalool, tagget, tanasetam, davana, tarragon, tansy, common tangy, tangerine, champaca, tuberose, tea tree, dill, nutmeg, narcis , Niauri Cineol, Neroli, Violet leaf, Pine, Basil linalool, Parsley, Patchouli, Hakka, Vanilla, Balsam fur, Palmarosa, Valerian, Hyssop, Bitter almond, Hinoki, Hiba, Hyacinth, Fennel, Petit Glen, Petit Glen Mandarin , Black spruce, black pepper, frankincense, frangipani, blue cypress, bloom spanish, vetiver, penny Hyal, peppermint, hemlock spruce, bergamot, bergamot mint, benzoin (benzoic acid), horef, myrtle, marjoram sweet, mustard, mastic tree, manuka, mandarin, mimosa, myrrh, melissa (lemon balm), fir, yarrow, yuzu , Eucalyptus globulus, eucalyptus citriodora, eucalyptus radiata, lime, lavinsara, labandin, labradorti, lavensara, lavender, lantana, ritsukubeba, linden, lemon,
Lemongrass, lemon verbena, lemon myrtle, rose absolute, rosewood, rose otto (damask rose), rosemary, rosemary cineole, rosemary velbenone, lotus, laurel, rosalina, lobe and wild thyme are preferred.

  Particularly preferred among the above-mentioned mixtures are grapefruit, peppermint, lavender, tea tree and rosemary.

  Whether or not the aromatic molecules recorded on the porous coordination polymer having the porous skeleton structure described above can be released by the method of generating aroma according to the present invention is analyzed by using a gas chromatograph or a mass spectrometer. You can find out by doing. At the same time, it is possible to analyze the types of generated aromatic molecules. Various aromatic molecules and mixtures are adsorbed to a porous coordination polymer having a porous skeleton structure used in the present invention, and components released while heating are quantitatively or qualitatively analyzed to accurately detect aroma and odor. Can be reproduced.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” is based on mass.

<Incense recording method using porous coordination polymer>
Reference Example 1: Example of direct mixing To 0.475 g of storage material MOF (manufactured by Sigma-Aldrich, trade name: Basolite Z377, product number Aldrich 794325) in 9 mL of sample vial (Laboran screw tube No. 3), After dropping 0.13 g of a mixture of aromatic molecules (Grapefruit Essential Oil, Living Wooden Co., Ltd.), stirring with a spatula for 10 seconds, closing the lid, shaking the entire container, stirring at 35 rpm for 12 hours, The product was obtained. The mass reduction rate was measured with the differential thermal and thermogravimetric simultaneous measurement device using the obtained powdery product. The measurement conditions were a nitrogen gas atmosphere (100 mL / min) and the temperature was increased from room temperature to 400 ° C. at a rate of 10 ° C./min. The mass reduction rate when heated to 400 ° C. was 28%.

  Using other aromatic molecules instead of nerol, after recording incense under the same conditions, the mass loss rate was measured with a differential thermal / thermogravimetric simultaneous measurement device. The results are summarized in Table 1.

  As shown in Table 1, since the mass reduction rate increased compared to the storage material MOF alone, it was confirmed that the aroma component was recorded in the MOF by direct mixing.

Reference Example 2: Example of Vapor Deposition Evaporation 100 mg of MOF (manufactured by Sigma-Aldrich, product name: Basolite Z1200, product number Aldrich 691348) was added to a microtube (manufactured by AZONE Corporation, product number 02046301). After adding 2 mL of aromatic molecules (Nellore, FUJIFILM Wako Pure Chemical Industries, Ltd., 359-20262) to 50 mL of a sample vial (Laboran screw tube No. 7), the microtube containing the MOF is enclosed, and the screw part After Teflon (registered trademark) tape (PTFE) was applied to the lid, the lid was closed and sealed.

  After standing for 15 days in the sealed container of the sample vial, the storage material was taken out from the sealed container, and the mass reduction rate was measured with a differential thermal / thermogravimetric simultaneous measuring device. The measurement conditions were a nitrogen gas atmosphere (100 mL / min) and the temperature was increased from room temperature to 400 ° C. at a rate of 10 ° C./min. The mass reduction rate when heated to 400 ° C. was 4.0%. Here, the product obtained by leaving after standing for 15 days was powdery.

  Other aromatic molecules instead of nerol were recorded under the same conditions, and the mass reduction rate was measured with a differential thermal / thermogravimetric simultaneous measuring device. The results are shown in Table 2. Since the mass reduction rate is increased as compared with the storage material MOF alone, it can be seen that the aromatic molecules were recorded in the storage material by vapor deposition.

Reference Example 3: Example of vapor deposition using a blower The experimental apparatus shown in FIG. 1 was set up, and a recording method by vapor deposition using a blower was studied. As shown in FIG. 1, a storage material MOF (Sigma-Aldrich, product name: Basolite Z377, product number: Aldrich 794325) 20 mg is sandwiched between two filters made of gauze, and a blower (CAPTAIN STAG OUTDOOR GEAR: battery type) M-7580) was fixed to the air blowing port with a rubber band. To an aluminum container (diameter 5 cm, height 1 cm), 2.0 g of a mixture of aromatic molecules (Grapefruit Essential Oil, Living Wooden Co., Ltd.) was added. The air blower and the aluminum container were put in a polybag (500 mL) and sealed, and then the air blower was turned on to blow air for 1 hour.
Thereafter, the storage material was taken out, and the mass reduction rate was measured with a differential heat / thermogravimetric simultaneous measurement device. The measurement conditions were a nitrogen gas atmosphere (100 mL / min) and the temperature was increased from room temperature to 400 ° C. at a rate of 10 ° C./min. The mass reduction rate when heated to 400 ° C. was 19%.

<Aroma generation method using porous coordination polymer>
Example 1 Example of Fragrance Generation Using a Blower This example will be described below by dividing it into a process [Process 1] in which the recording method is performed and a process [Process 2] in which the fragrance generation method is performed.

[Process 1]: Incense recording of essential oil into storage material MOF Storage material MOF (Sigma-Aldrich, product name: Basolite Z377, product number Aldrich 794325) in 9 mL of sample vial (Laboran screw tube No. 3) ) Add 0.13 g (total weight ratio) of a mixture of fragrance molecules (Grapefruit Essential Oil, Living Wooden Co., Ltd.) to 0.475 g, stir with a spatula for 10 seconds, close the lid, and shake the entire container And stirred at 35 rpm for 12 hours.

[Process 2]: Generation of fragrance from storage material MOF Storage material MOF (produced by Sigma-Aldrich) in which grapefruit essential oil was adsorbed between two filters made of gauze in [Process 1] according to the test contents shown in FIG. The product name: Basolite Z377, product number Aldrich 794325) was sandwiched between 20 mg, and was fixed to the air blowing port of a blower (CAPTAIN STAG OUTDOOR GEAR: battery type M-7580) with a rubber band.

  Next, as shown in FIG. 2, the blower (motor) was turned on, and air was blown at a wind speed of 0.5 m / s for 1 hour. Sensory evaluation performed the smell before and behind ventilation by the detection method by a nose. As a result, under conditions without air blowing, no fragrance could be detected even when the nose was brought close to 5 cm from the storage material MOF. On the other hand, when the nose was brought close to 5 cm from the storage material MOF under the condition with air blowing, the aroma of grapefruit was detected by sensory evaluation.

  Furthermore, the storage material 1 hour after the start of blowing was taken out, and the mass reduction rate was measured with a differential heat / thermogravimetric simultaneous measurement device. The measurement conditions were a temperature increase from room temperature to 400 ° C. at a rate of 10 ° C./min in a nitrogen atmosphere (100 mL / min). As a result, the mass reduction rate when heated to 400 ° C. was 24% with respect to the initial storage material MOF on which the grapefruit essential oil was adsorbed.

  As a control experiment, the mass reduction rate of the unblasted storage material MOF obtained in step 1 was also measured using a differential heat / thermogravimetric simultaneous measurement device. The measurement conditions were a nitrogen atmosphere (100 mL / min) and the temperature was increased from room temperature to 400 ° C. at a rate of 10 ° C./min. The mass reduction rate when heated to 400 ° C. was 21%. When comparing the rate of decrease in the storage amount of the fragrance component (grapefruit essential oil), the effectiveness of the generation of fragrance by blowing was confirmed because the ratio before and after sending was 3% greater than the control case.

  Thus, it can be seen that the fragrance component adsorbed or occluded in the storage material MOF has a slight change in the amount of the fragrance component after one hour of blowing, and can withstand repeated use. Further, when the adsorbed amount or occluded amount of the fragrance component decreases, the fragrance component can be replenished by the recording method as described in Reference Examples 1 to 3 above. Furthermore, by repeating the fragrance generating method of the present invention, it becomes possible to store and reproduce the incense in a device or the like.

<Aroma component analysis method>
Example 2: Analysis Example of Fragrance Component Into a smart bag containing 4 L of dry nitrogen, 2 μL of lavender French essential oil (Living Wooden Co., Ltd.) was added to fill the smart bag. Next, 0.04 L of the full gas in the bag was sampled and added to another smart bag containing 4 L of dry nitrogen gas to be diluted and filled. 25 mg of Besolite Z377 as a porous coordination polymer was weighed in a glass tube, and 0.2 L of this dilution gas was collected in the Besolite Z377 to prepare a sample.

  After the Basolite Z377 thus recorded was heated at 300 ° C. for 2 hours, the vaporized lavender essential oil was adsorbed by air blowing, and then the vaporized components were analyzed by gas chromatography. For gas chromatography, TDU type, gas chromatograph: Agilent 7890, mass spectrometer: 5975C MSD, column: DB-WAX (60 m, diameter 0.25 mm, film thickness 0.25 μm), carrier gas: helium (2.45 mL / min) and the oven temperature (holding time): 40 ° C. (3 min) −5 ° C./min−250° C. (5 min).

  As a reference, gas chromatographic analysis was performed in the same manner as described above using Tenax TA, which is generally used as a collection filler for heat desorption in odor analysis, instead of Besolite Z377. By comparing the analysis result of this example with Tenax TA, it can be confirmed whether the aroma of lavender French essential oil is reliably reproduced in Besolite Z377. The analysis results are shown in Table 3.

  From the results of gas chromatographic analysis shown in Table 3, it was found that Besolite Z377 can reliably reproduce the fragrance of the essential oil in the same manner as Tenax TA of the reference example, although there are some differences in the desorption component and its ratio. Furthermore, it was confirmed that 20 or more kinds of molecules corresponding to 80% of the molecules detected with the essential oil can be adsorbed and desorbed reversibly.

  As described above, the fragrance generating method of the present invention makes it possible to generate a solid, liquid fragrance component incorporated in a small device in a chemically stable state at any place at any time. For example, it can be expected to be applied to a high-performance fragrance device for mobile use.

Claims (6)

  A fragrance generation method using a porous coordination polymer having a porous skeleton structure, wherein the fragrance material containing the porous coordination polymer and the fragrance molecule is used to apply air, heat, electric field and voltage. A method of generating a fragrance by at least one of application of a magnetic field and vibration.   The fragrance generating method according to claim 1, wherein the fragrance generating method is a method having means for blowing air to the fragrance material.   The porous coordination polymer having the porous skeleton structure has a ligand containing at least one chemical structure selected from the group consisting of an imidazole skeleton, a phthalic acid skeleton, and a trimesic acid skeleton. The fragrance generation method as described in any one of -2.   The porous coordination polymer which has the said porous frame | skeleton structure contains at least 1 or more types of metal ion chosen from the group which consists of Al, Fe, Zn, and Cu as described in any one of Claims 1-3. Aroma generation method.   The aroma generating method according to any one of claims 1 to 4, wherein an aromatic molecule having a molecular weight of 100 to 300 is used as the aromatic molecule.   A method for analyzing a fragrance component, wherein the type of fragrance molecule generated by the fragrance generation method according to any one of claims 1 to 5 is analyzed by a gas chromatograph or a mass spectrometer.