JPS59186557A - Room aromatic agent - 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 a room air freshener that is installed and used in a living room, a washroom, a passenger car, etc., and more specifically relates to a solid air freshener in which a fragrance is supported on a gel.

Three types of indoor air fresheners are known: solid, liquid, and aerosol. Among these, solid air fresheners can be classified in terms of fragrance carrier: plastic type with plastic as a carrier, and sublimation type with sublimable substance as carrier. It can be roughly divided into gel-type fragrances and gel-type fragrances using a gel-like substance as a carrier. Among these solid fragrances, the plastic type has the disadvantage that it does not necessarily emit enough scent because it is a blend of fragrance into plastic, and the sublimation type has a limitation on the fragrance that can be contained in the sublimable substance. In addition, there is the disadvantage that the speed at which the aroma diffuses cannot be controlled. Under these circumstances, gel-type fragrances are generally preferred as solid fragrances.

By the way, existing gel-type fragrances are made by gelling carrageenan, locust bean gum, cardixymethylcellulose, etc. with inorganic metal salts, etc., and are used as fragrance carriers. For the purpose of improving sustainability or gel stability, efforts have been made to incorporate polyvinyl alcohol, guar gum, gum arabic, agar, sodium alginate, polyvinylpyrrolidone, etc. However, with these conventional gel-type fragrances, the duration of the fragrance is usually limited to 1 to 2 months, which is not always sufficient, and furthermore, the fragrance of the fragrance deteriorates qualitatively when administered orally, leaving room for improvement. ing. In addition, conventional gel-type fragrances tend to freeze in the winter due to their lack of low-temperature stability, and when they freeze, they can even disintegrate due to the generation of xylene.

In order to solve the above-mentioned problems pointed out with conventional gel-type aromatics, the present inventors have conducted extensive research on perfume carriers in particular, and found that chitosan or chitosan derivatives and specific cal-H? It has been found that a gel obtained by reacting with acid anhydride or aldehyde at a predetermined molar ratio has excellent suitability as a fragrance carrier in a gel type fragrance. The present invention is based on this knowledge and provides a new gel-type room air freshener.

That is, the indoor air freshener according to the present invention contains component (c) selected from chitosan and chitosan derivatives, and
The following aliphatic or aromatic carzenic acid anhydride and carbon number 1
0 or less aliphatic or aromatic aldehydes)
It is characterized in that the gel obtained by reacting the component (5) with the component (5) at a ratio of 02 to 8 moles per hexosamil residue in the component is used as a perfume carrier.

In the present invention, chitosan and/or chitosan derivatives can be used as four components for producing the carrier gel. Chitosan is typically obtained by deacetylating chitin collected from the shells of crabs, shrimps, etc. using alkali treatment, but commercially available products can of course also be used. : Ayo Kasei Co., Ltd.)
Chitosan, which is commercially available under the trade name, can be used as component (f) of the present invention. Just to be sure,
In the present invention, the classification index between chitin and chitosan is defined as chitosan if the degree of deacetylation is 60% or more.

When a chitosan derivative is used as the component (d), the chitosan derivative is selected from calzoxy chitosan, alkyl chitosan, glycol chitosan, and glycerin chitosan. Caldoxymethyl chitosan, cardixyethyl chitosan, calzexiprobyl chitosan, etc. can be used as the caldoxychitosan, but among these, the first two are preferred, and as the alkyl chitosan, methyl chitosan, ethyl chitosan, propyl chitosan, etc. can be used. Chitosan and the like can be used, with the first two being preferred. By the way, when the number of carbon atoms in the carboxyalkyl group in carboxychitosan and the alkyl group in alkylchitosan is 4 or more,
This is undesirable because not only the reactivity with component CB) described below decreases, but also the hydrophilicity of the resulting gel decreases, resulting in a decrease in fragrance persistence.

As glycol chitosan, chitosan to which 1 to 24 moles, preferably 1 to 20 moles of ethylene oxide or propylene oxide is added per OH group is used.
A condensate of 1 to 5 moles, preferably 1 to 3 moles of glycerin per H group is used. If a glycol chitosan having an added mole of alkylene oxide of 25 moles or more or a glycerin chitosan having a condensed mole of glycerin of 6 moles or more is used, the resulting gel becomes brittle and its low-temperature stability decreases.

The component (c) which reacts with component (c) to form a gel is an aliphatic or aromatic carminic acid anhydride having 20 or less carbon atoms, preferably 2 to 17 carbon atoms, and an aliphatic or aromatic carminic acid anhydride having 20 or less carbon atoms, preferably 2 to 17 carbon atoms. selected from 2-7 aliphatic or aromatic aldehydes. If a carminic acid anhydride having 21 or more carbon atoms or an aldehyde having 11 or more carbon atoms is used, the reactivity with component (A) will decrease in both cases, and in addition, the hydrophilicity of the resulting gel will decrease. Persistence of fragrance also decreases. Specific examples of carminic anhydride that can be used in the present invention include:
Examples of anhydrides include acetic acid, propionic acid, casillonic acid, lauric acid, myristic acid, palmitic acid, stearic acid, maleic acid, and benzoic acid, and examples of aldehydes include formaldehyde, acetaltehyde,
Examples include cultaraldehyde, benzaldehyde, salicylaldehyde, crotonaldehyde, and acrolein.

The reaction between component (c)) and component [F]) easily proceeds near room temperature, but in the present invention, the reaction between the components (c) and [F]) is carried out based on the amount of the above-mentioned components (per molar equivalent of hexosamil residue in component Ingredients 0.2
The reaction must be carried out in the range of ~8 molar equivalents, preferably 0.3-6 molar equivalents. (2) If the amount of the component is less than 0.2 molar equivalent, the resulting gel will weaken by 1° C. and its low-temperature stability will deteriorate; if it exceeds 8 molar equivalent, the persistence and stability of the aroma will decrease. The reaction between component (A-) and component (■) is usually carried out in the presence of a solvent, and examples of the solvent include organic acids such as lactic acid, formic acid, malic acid, citric acid, tartaric acid, and acetic acid, or sulfuric acid and hydrochloric acid. Aqueous solutions of inorganic acids are commonly used.

= The gel-type indoor air freshener of the present invention is prepared by a method in which (a) and ([3) both components are reacted in the presence of a fragrance, and at this time, a swelling agent, which is commonly used in conventional indoor air fresheners, is added. Surfactants, preservatives, etc. can be present in the reaction system. Fragrance ingredients include geraniol, benzyl acetate, β-phenylethyl alcohol, and lilyaldehyde (or more). mixture of IJ + roll and linalyl alcohol, citral (all citral types), santalol, noξcholy alcohol, cedrenol (all utsudi types), hydroxycitronellol, hydroxycitronellal, ionones, amyl cinnamic aldehyde (The above general-purpose types) can be used in the present invention, and the amount used can be arbitrarily selected within the range of 0.5 to 10 times.

As mentioned above, the gel-type indoor air freshener of the present invention is as described above (
Since the gel-like reaction product of component g) and component Although they exhibit better performance than gel-type fragrances, the reason for their superior effects is not necessarily clear. However, (5
The gel consisting of the reaction product of component ) and component (B) is -
It has a structure in which vesicles with a diameter of 30 to 50 μm and a length of 80 to 150 μm are stacked one on top of the other in a honeycomb shape, and since the fragrance is captured within these vesicles, the fragrance can be maintained for a long time. It is presumed that it is possible to prevent this qualitative deterioration as well. Furthermore, since the honeycomb vesicle structure is mechanically stable, it is considered to have sufficient durability against collapse due to freezing.

Next, the present invention will be explained in more detail with reference to Examples.

Examples 1-9 3 g of propylene glycol, 20.15 g of parahydroxymethylbenzoic acid and 0 g of parahydroxyzorobylbenzoic acid
To 505 g of the mixture was added the amounts of nochitosan, R
EGITEX-NA-500 (trade name, manufactured by Nanyo Kasei Co., Ltd.) was added, and 82.8 g of a 5% aqueous lactic acid solution was further added to obtain a viscous homogeneous solution. After adding 2.5 g of polyoxyethylene sorbitan monopalmitate and 6.5 g of fragrance (floral fragrance) to this solution, a predetermined amount of the aldehyde listed in Table 1 was added, stirred well, and then left at room temperature for 2 hours. A gel-type solid fragrance is obtained. Next, the performance of these fragrances was evaluated by the following method, and the results shown in Table 1 were obtained.

[Performance evaluation of air fresheners]

1. Persistence of fragrance: When a gel-type air freshener is left indoors, it gradually loses weight due to the volatilization of fragrance and water;
If the weight loss is small, it can be considered that the fragrance persistence is good, so a 70 g cylindrical fragrance sample of the initial type flk was placed in an atmosphere with a humidity of 50 °C and a temperature of 20 to 25 °C for 12 hours. Next, an experiment in which the samples were left in an atmosphere with a humidity of 50% and a temperature of 10°C for 12 hours was repeated for 2 months, and the weight of the samples was measured after 2 months, and the fragrance persistence was evaluated based on the weight loss relative to the initial weight using the following criteria. did.

2. Aromatic stability 2 Above 1. The same content of the left experiment as 3.
After the test was continued for several months, the quality of the fragrance evaporated from the air freshener samples was sensory evaluated using the following criteria.

3. Low-temperature stability: A 70 g cylindrical aromatic sample was left in a constant temperature room at -5° C. for 3 months, and the degree of collapse of the sample due to freezing was evaluated using the following criteria.

Examples 10 to 16 Chitosan and REGITEX-NA-50 (trade name, manufactured by Nanyo Kasei Co., Ltd.) in the amounts shown in Table 2 were added to a mixture of 3 g of propylene glycol and 0.1 g of parahydroxymethylbenzoic acid, and % malic acid aqueous solution 87
．． 9 g was added to obtain a viscous homogeneous solution. After adding 0.5 g of polyoxyethylene sorbitan monopalmitate and fragrance (citral fragrance) s, og to this solution, a predetermined amount of carzenic acid anhydride listed in Table 2 was added, stirred well, and then overnight at room temperature. A gel-type solid fragrance was obtained by standing. Also,
For comparison, a mixture of 3 g of propylene glycol and 0.1 g of parahydroxymethylbenzoic acid was mixed with 0.5 g of polyoxyethylene sorbitan monopalmitate, 5.0 g of the above fragrance, and 3.5 g of carrageenan (Example 15) or carpochloride. A gel-type solid fragrance was obtained by adding oxymethylcellulose (Example 16). Next, the performance of each of these fragrances was evaluated using the methods described in Examples 1 to 9, and the results shown in Table 2 were obtained.

Examples 17-26 A predetermined amount of the chitosan derivative shown in Table 3 was added to a mixture of 3 g of propylene glycol and 1 g of parahydroxymethylbenzoic acid θ, and then 87.9 g of a 5% aqueous malic acid solution was added to form a viscous homogeneous solution. It's a good deal. To this solution, add monopalmitic acid polyoxyethylene vine, 0.5 g of bitanium, and fragrance (Utudi fragrance)5. og was added, and acetic anhydride corresponding to 2.0 mol pixels per mol equivalent of hexosamil residue of the chitosan derivative was added, stirred thoroughly, and then left overnight at room temperature to obtain a gel-type solid fragrance. . The performance of these fragrances was then evaluated using the methods described in Examples 1-9. The results are shown in Table 3.

(Margin below)

Claims (1)

[Claims] 1. Chitosan and chitosan derivatives i- (5
) component and (5) component selected from aliphatic or aromatic carminic acid anhydride having 20 or less carbon atoms and aliphatic or aromatic aldehyde having 10 or less carbon atoms; A room air freshener containing a fragrance in a gel obtained by reaction at a ratio of 0.2 to 8 molar equivalents of component (B) per molar equivalent. 2. The indoor air freshener according to claim 1, wherein the chitosan derivative is caloxychitosan, glycol chitosan, glycerido chitosan, or alkyl chitosan. 3. The indoor air freshener according to claim 2, wherein the cal-pre-xychitosan is cal-prexymethyl chitosan, cal-prexyethyl chitosan, or cal-xyzologyl chitosan. 4. The indoor air freshener according to claim 2, wherein the glycol chitosan has 1 to 24 moles of ethylene oxide or propylene oxide added to each OH group of chitosan. 5. The indoor air freshener according to claim 2, wherein the glyceride chitosan is a condensation of 1 to 5 moles of glycerin per mole of OH group of chitosan. 6. The indoor air freshener according to claim 2, wherein the alkyl chitosan is methyl chitosan, ethyl chitosan, or propyl chitosan.