JPS6058153A - Molded aromatic body - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aromatic molded body formed by carrying a fragrance on a honeycomb-shaped activated carbon molded body whose specific surface area and rib thickness are specified, and in particular to a uniform aromatic body when a blended fragrance is used. The present invention relates to an aromatic molded article having good aroma properties and excellent fragrance persistence.

In recent years, the consumption of air fresheners in daily life has increased rapidly, and they have become widespread not only for deodorizing toilets but also for living rooms, cars, public facilities, etc. With the expansion of such fields of application, many proposals have been made not only for the development of perfumes themselves, but also for materials for supporting perfumes. By the way, ordinary fragrances, whether natural or synthetic, contain a wide variety of components, and many of these are susceptible to alterations such as oxidation, decomposition, and isomerization. Moreover, since those with low boiling points among the four components of the blended fragrance composition evaporate early, there is a problem that as the period of use increases, the optimal blending ratio is broken and the fragrance changes significantly. - Solid materials such as paper, carrageenan, and inorganic porous materials (alumina, silica/alumina, and silica gel cores) are commonly used as carriers for fragrances, but they generally have weak support for fragrances.
As mentioned above, there are problems in that the aroma quality is significantly deteriorated due to the early volatilization of low-boiling components and the fragrance is short-lived.

On the other hand, activated alumina, activated silica, and the like have a considerably strong ability to support perfumes, but since they have surface activity, it has been pointed out that the perfumes deteriorate due to their influence.

Against this background, there has been a demand for the development of a carrier that can stably hold unstable blended fragrances for a long period of time and also be able to emit them at a substantially uniform concentration over a long period of time. In response to these demands, JP-A-52-117
A method of supporting a fragrance on granular activated carbon as seen in No. 444, and a method of kneading a fragrance into a resin as shown in JP-A-54-154527 have been proposed. However, these methods have the following problems, and are far from being satisfactory methods. In other words, in the case of a method in which fragrances are supported on granular activated carbon, the activated carbon surface is almost neutral and has low activity toward fragrances, so there is little possibility of oxidation, decomposition, isomerization, etc.;
Specific surface m: so.

~1000 m, /7) may cause considerable deterioration of fragrance. Moreover, since activated carbon has a strong ability to retain fragrance, the supported fragrance is trapped inside without being diffused, and its function as an aromatic agent is significantly reduced. In particular, since the size of general granular activated carbon is about 1 to 6 square meters, there is a problem that the fragrance concentration is distributed within the particles, and the fragrance concentration in the surface layer becomes extremely low.

- In the method of kneading fragrance into resin, 10%
They may be exposed to high temperatures of about 0°C or higher, and depending on the type of fragrance, there is a risk of thermal decomposition, and there is also considerable loss due to evaporation.

The present inventors have focused on these circumstances and have conducted various studies in an attempt to develop a carrier that can uniformly volatilize a blended fragrance at an appropriate rate without altering the quality of the fragrance. The present invention was completed as a result of such research, and its structure consists of forming a carbon material and/or a carbonizable material into a honeycomb shape, and then carbonizing and activating it.
ε; is an aromatic molded body formed by carrying a fragrance on a honeycomb-shaped activated carbon molded body, the honeycomb-shaped activated carbon molded body having a specific feed opening of 400 to 1000 m2/9. The gist is that the thickness of the ribs constituting the honeycomb is 0.1 to 0.50, or in addition to these, the radius of the fine voids that contribute to the specific surface reflection of the molded body is 5 to 15. It is.

The honeycomb-shaped activated carbon molded body used in the present invention is manufactured, for example, by a method as described in Japanese Patent Application Laid-Open No. 57-27180, which was previously proposed by one of the applicants. Then, the result is as follows. That is, as carbonizable materials or carbon materials, for example, phenol resins, furan resins, xylene formaldehyde resins, melamine resins, aniline resins, carbonized coconut husk products, raw ash, coke, etc. are used, and granules of these, After the fibrous material or crushed material is mixed with a suitable fraction of comb (most commonly water) and a binder, it is formed into a honeycomb shape using an extruder with a set of screws or a set of plungers. The binders include MC (methyl cellulose), CMC (carboxymethyl cellulose), starch, CMS (carboxymethyl starch), HE C (hydroxyethyl cellulose),
RPC (hydroxypropyl cellulose), sodium lignosulfonate, calcium lignosulfonate,
Organic binders such as polyvinyl alcohol, polyacrylic esters, and polymethacrylic esters, and inorganic binders exclusively for colloidal silica, colloidal alumina, colloidal titanium, bentonite, and aluminum phosphate can be used.

The honeycomb shaped body thus obtained is dried according to a conventional method and then carbonized in a non-oxidizing atmosphere. The carbonization temperature is preferably 500 to 41.00°C; if it is less than 500°C, carbonization will be insufficient and the supporting capacity will be poor, while if it exceeds 1100°C, the effect of the next activation treatment will not be fully exhibited. Sometimes.

The subsequent activation treatment is performed under an atmosphere of oxidizing gas such as water vapor, carbon dioxide, combustion gas, air, or oxygen.
This is done by heating to 000°C. That is, when the temperature is maintained in the temperature range for a certain period of time, the glassy carbon or amorphous carbon formed in the carbonization process is gradually activated by the atmospheric gas and becomes activated carbon. If the activation progresses too much, the strength of the molded body will drop significantly, so the above holding time for activation is determined by the thickness of the glassy carbon material (n) in the thickness direction of the cells forming the honeycomb shape.
It is preferable to adjust the ratio (A/B) of the thickness (a) of the activated carbon layer to 6) to be 30 times or less.

By the way, in the above-mentioned series of processes of forming, carbonizing, and activating, it is essential to set each process condition so that the specific surface area of the honeycomb-shaped activated carbon formed body finally obtained is 400 to 1000 m''/7. Therefore, setting such a specific surface area is a prerequisite for achieving the purpose of the present invention.That is, Fig. 1 is a graph showing the relationship between the specific surface area of activated carbon and the fragrance storage rate. If the specific surface area is less than 1000 m2/9', the fragrance carrying capacity will be insufficient, and the fragrance will not be able to be carried sufficiently, resulting in insufficient fragrance persistence.On the other hand, if the specific surface area exceeds 1000 m2/9', the fragrance carrying capacity will be strong. If the honeycomb becomes too thick, the ability to diffuse the fragrance will decrease, and if the activity becomes too strong, the isomerization of the fragrance will easily occur.In addition, the thickness of the ribs that make up the honeycomb ensures uniform retention and diffusion of the fragrance, and It is necessary to determine this by taking into account the most dynamic behavior, and it must be adjusted to a range between 0.1 and 0.5.Incidentally, the thickness of the rib must be set to 0.1
It is difficult to manufacture the honeycomb with a thickness of less than mm, and even if it were possible to manufacture the honeycomb, the mechanical strength of the entire honeycomb would be poor and it would easily collapse. On the other hand, if the thickness of the rib exceeds 0.5πm, as pointed out earlier in the explanation of granular activated carbon, the carrying capacity itself will be poor and the concentration of the fragrance will be distributed internally, with some of the fragrance being taken into the interior without being dissipated. It remains as it is.

In the case of conventional granular activated carbon, as mentioned above, 800m2/!
Even with a specific surface area of 1,000 m2/y, the retention force is too strong and the fragrance dissipation ability decreases, whereas with the honeycomb-shaped activated carbon of the present invention, sufficient fragrance dissipation ability can be obtained even with a specific surface area of 1000 m2/y. The reason for this can be considered as follows. In other words, in the case of granular activated carbon, since the particles 0 are large, the supporting force is large in the thickness direction, and when the specific surface area is expanded, the supporting force also increases in the plane, and the problem is that the additive effect of these forces reduces the perfume dispersion ability. Because there is, at most 8
While it was necessary to keep it to around 00 m2/y,
In the honeycomb formed body of the present invention, the thickness of the ribs is 0 as described above.
．． Since it can be made as thin as 1 to 0.5 bait, the holding force in the thickness direction is small, so there is plenty of room for increasing the holding force in the plane.
This is thought to be because even if the specific surface area is considerably expanded, the perfume dispersion ability does not deteriorate. In addition, in the case of granular activated carbon, as mentioned above, the supported part is long when viewed in the D direction, so the particles from which the supported fragrance is released can undergo isomerization in the process of passing through relatively long micropores formed by the activated carbon. However, since the supporting portion of the molded article of the present invention is an extremely thin rib as described above, the possibility that the fragrance is isomerized is also reduced.

In addition, the pore radius of the honeycomb-shaped activated carbon molded body is 5~. 2'
i l-J, y aaf:1. +M At M, #
J-glj, 61 +-4h l #It is extremely preferable because it imparts the following properties to the final product. In other words, after the activation treatment, the molded body is loaded with various fragrances by the method described below and used for the above-mentioned purposes. As shown in the graph showing the relationship between ratios, when a honeycomb-shaped activated carbon body with a pore radius of 5 to 15A is used, the amount of perfume supported increases, the sustained release of the perfume improves, and the fragrance lasts even longer. As the fragrance increases, the adsorption effect of malodorous substances on the activation surface (so to speak, the air-cooled part) after fragrance release improves, and it comes to exhibit an excellent deodorizing function. However, if the pore radius is outside the above range, such deodorizing function will not be fully exhibited.

There are no particular restrictions on the oils and the method of supporting the fragrance on the honeycomb-shaped activated carbon formed body, and any known method may be used to support the fragrance. It is as follows.

As fragrances, natural fragrances, synthetic fragrances, and blended fragrances can be used.Natural fragrances include jaggery, reishin incense, aragonite incense, avinis oil, bergamot oil, boar rose oil, rosewood oil, rosemary oil, and orange. Examples include flower oil, lemon oil, grapefruit oil, cardamom oil, cinnamon oil, cognac oil, honeysuckle oil, spearmint oil, jasmine abunlude, porneocamphor oil, and the like. In addition, synthetic fragrances include limonene,
Hydrocarbons in pinen broom, linalool, ge? Alcohols such as diol, citronellol, menthol, borneol, benzyl alcohol, anis alcohol, β-phenylethyl alcohol, etc. 1.7. t.

Phenols such as alcohol, eugenol, n-butyraldehyde, nonajenal, citralol, citronellal, benzaldehyde, cinnamic aldehyde, heliotropin, aldehydes of vanillin fat, methyl ethyl ketone, methyl nonyl ketone, diacetyl, acetyl propionyl, acetyl butyl, carvone, Mentone,
Ketones such as camphor, acetophenone, p-methylacetophenone, ionone, lactones or oxides such as aminobutyrolactone, ethyl methylphenylglycidate, γ-nonyl lactone, tamarin, cineole, methyl formate, isopropyl formate, linal Formate, ethyl acetate, octyl acetate, pentyl acetate, benzyl acetate, cinnamyl acetate, butyl propionate, isoamyl acetate, isopropyl isobutyrate, allyl isovalerate geraninobecaproate, butyl heptylate, octyl caprylate, heptine Methyl carboxylate, ethyl pelargonate, methyl octylcarboxylate, inacyl caprate, methyl laurate, ethyl myristate, ethyl benzoate, benzyl benzoate, methyl phenylate, butyl phenylate, cinnamyl cinnamate, methyl salicylate, anisic acid Examples include esters such as ethyl, anthranic acid methine ethyl pyrpate, and ethyl α-buty/I/-7′ thylate. Furthermore, examples of mixed fragrances include rose, jasmine, lilac, osmanthus, carnation, and muguet.

There is no need to adopt a particularly special method for supporting these fragrances on the honeycomb-shaped molded body, and any ordinary dipping method, spraying method, dropping method, etc. may be used. However, the key point is that the activated carbon molded body has a specific surface area and rib thickness within a specific range, or by supporting a fragrance on a honeycomb-like material having pores of a specific size, as shown below. An extremely excellent aromatic molded article could be obtained.

[1] The honeycomb-shaped activated carbon molded body has excellent support and sustained release properties for fragrances, and therefore has extremely good fragrance persistence.

[2] Activated carbon is originally a neutral substance and does not easily cause deterioration of fragrances, but by forming it into a honeycomb shape, it is possible to expand the specific surface area without dramatically increasing the activity, so it is more effective than granular activated carbon. The isomer ratio of the fragrance is reliably prevented, and the change over time in the fragrance effect caused by the isomer ratio can be almost completely eliminated.

[8] Fragrances are usually supported as a mixture of many aromatic components, but since these are evenly released from the surface of each rib that makes up the honeycomb-shaped molded body, the properties change over time due to the early release of specific components. It doesn't happen either.

[4] Since the flavor is carried in the thin rib part,
The concentration distribution of the fragrance between the outer layer and the center, as seen in granular activated carbon, is unlikely to occur, and the problem of the fragrance being trapped in the center and unable to dissipate does not occur.

[5] A deodorizing function can also be provided by adjusting the pore radius of the honeycomb-shaped activated carbon molded body to an appropriate range.

Next, experimental examples will be given to further clarify the characteristics of the present invention.

Experimental example [1] Manufacture of honeycomb-shaped activated carbon molded material After uniformly kneading activated carbon raw material powder with appropriate amounts of binder, dispersant, and water, it was formed into a honeycomb shape by extrusion molding with a set of screws, and carbonization and activation treatments were performed. A honeycomb-shaped activated carbon molded body was manufactured. The molding conditions etc. are summarized in Table 1.

Each of the obtained honeycomb-shaped activated carbon molded articles was impregnated with the following fragrance and subjected to an aroma test.

For comparison, granular activated carbon (particle size 8.5-4.
5 mmφ), zeolite particles (particle size 8.5 to 4.5 t
tytrφ), activated alumina particles (particle size 8.5-4.5-
), P paper (thickness: 3 am) was impregnated with the same fragrance and subjected to an aroma test.

[Fragrances used]

■ Aluminum salicylate ■ γ-decalactone ■ Hydroxycitronellal ■ Limonene ■ Linalool ■ Benzyl acetate Each of the flavor mixtures obtained above was hung in a room and left for 3, 10, and 30 days. Add the remaining fragrance to CH2
It was extracted with Cl2, and the residual image of the impregnated base at the beginning of the impregnation was examined by gas chromatography analysis.

It can be seen that the flavor retention effect of the activated carbon shaped body is extremely superior compared to other adsorbent materials.

[Brief explanation of drawings]

Fig. 1 is a graph showing the relationship between the specific surface area of activated carbon and the storage rate, Fig. 2 is a graph showing the relationship between the radius of micropores of activated carbon and the storage rate, and Figs. 3 to 8 are fragrance retention of the molded article of the present invention. It is an experimental graph showing the effect in comparison with that of a known adsorbent. Applicant: Kobe Seisho Co., Ltd. (1 person serving) 18! Company rice cake with l (畔;〉＠) Chiheiba 8 rice cake (can bite Φ) Teitosei correction book (self-motivated) 1. Description of the case 1982 Patent Application No. 167358 2 Name of the invention Aromatic molded article 3 Person making the amendment Relationship to the case Patent applicant 3-18 Wakihama-cho-chome, Chuo-ku, Kobe City (119) Co., Ltd. Kobe Steel Representative: Fuyuhiko Maki (and 1 other person) 4. Agent: Shinny Building, 2-3-7 Dojima, Kita-ku, Osaka 530, “Detailed Description of the Invention” column (1) Specification No. 11 Replace pages ~12 with attached pages 11 and 12. (2) "Aluminum salicylate" in line 9 of page 7517 is corrected to "amyl salicylate-1." Rosewood oil, rosemary oil, orange flower oil, lemon oil, grapefruit oil, cardamom oil, cinnamon oil, cognac oil, hepermint oil, spearmint oil, jasmine absolute 1-1 camphor oil, etc. are praised. . Synthetic fragrances include hydrocarbons such as limonene and pinene, alcohols such as linalool, keraniol, citronellol, menthol, borneol, benzyl alcohol, anise alcohol, and β-phenylethyl alcohol, and phenols such as anethole and eugenol. - Aldehydes such as butyraldehyde, nonajenal, citral, citronellal, benzaldehyde, cinnamic aldehyde, heliotropine, vanillin, ketones such as methyl nonyl ketone, diacetyl, carvone, menthone, camphor, acetophenone, p-methylacetophenone, ionone, Ethylmethylphenylglycitate, γ-nonyllacone, coumarin,
Lactones or oxides such as cineole, methylfur 7
Ohmate, ethyl acetate, octyl acetate,
Pentyl acetate, benzyl acetate, cinnamyl acetate, butyl propionate, inamyl acetate-1, isopropyl inbutyrate, geranyl isovalerate, allyl caproate, octyl cabrylate 1
・Methylheptine carbonate, ethyl benzoate, methyl octyl carbonate, isoamyl caprylate, methyl laurate, ethyl myristate, ethyl benzoate, benzyl 12, methyl benzony 1
-, cinnamyl cinnamate, methyl laurate, ethyl acetate, methyl anthranile-1, ethyl bilbe) s, etc. Furthermore, examples of mixed fragrances include rose, jasmine, lire, osmanthus, carnation, and muguet.

Claims (2)

[Claims] (1) An aromatic molded body obtained by forming a carbon material and/or a carbonizable material into a honeycomb shape, followed by carbonization and activation treatment, and carrying a fragrance on a honeycomb-shaped activated carbon molded body,
The specific surface area of the honeycomb-shaped activated carbon molded body is 400 to 10
00fn/y, and the order of the ribs constituting the honeycomb is 0.1 to 0.5 M. (2) An aromatic molded body obtained by forming a carbon material and/or a carbonizable material into a honeycomb shape, followed by carbonization and activation treatment, and carrying a fragrance on a honeycomb-shaped activated carbon molded body,
The specific surface area of the honeycomb-shaped activated carbon molded body is 400 to 10
00m2/y, the thickness of the ribs constituting the honeycomb is 0.1 to 0.5B, and the radius of the micropores contributing to the specific surface area of the molded body is 5 to 15B. An aromatic molded article.