JPH05115539A - Highly viscous aromatic - Google Patents

Abstract

PURPOSE:To attain a good appearance and excellent transparency, and uniform the volatilization of a perfume by containing a norbornane polymer, a terpene hydrocarbon solvent and the perfume in a highly viscous aromatic used in automobiles, rooms of general housing, or toilets. CONSTITUTION:A norbornane polymer has a glass transition temperature of 10 deg.C or more, and the number average molecular weight of the polymer is 1,000,000 or more. For a terpene hydrocarbon solvent, a monoterpene having n=2 of terpene hydrocarbons represented by the general formula (C5H8)n is used as the solvent. The norbornane polymer, the terpene hydrocarbon solvent and a perfume are mixed at ordinary temperature, and the resulting mixture is heated followed by cooling, whereby a highly viscous aromatic of a pseudo- gelled transparent fluid is provided. It can be charged in a glass bottle, plastic vessel, a tube vessel or the like because of the pseudo-gelled fluid. Further, the solvent and the perfume are firmly held in the polymer by using the ultra- high molecular polymer, the volatilization of the perfume is suppressed, and a moderate stable aroma can be enjoyed over a long period.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an air freshener used in automobiles, indoors of ordinary houses and toilets.

[0002]

2. Description of the Related Art Conventionally, solid and gel type fragrances have been widely used in automobiles, indoors of general houses and toilets (for example, Japanese Patent Laid-Open No. 62-2243).
No. 53), especially in the case of gelled fragrance, has a problem in that the skin is generated and the fragrance is hard to uniformly volatilize due to the reduction in volatilization, resulting in uneven fragrance. Moreover, a small lump was formed at the center as the fragrance was volatilized, and the appearance was extremely bad.

[0003]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The inventors of the present invention use a transparent highly viscous fluid having a pseudo-gel form obtained by dissolving polynorbornene in a terpene solvent to evaporate the fragrance and to prevent The present invention has been completed by finding that a pseudo gel-like aromatic agent having a good appearance and excellent transparency can be obtained by uniformly lowering the liquid level.

[0004]

Thus, according to the present invention, there is provided a high-viscosity fragrance containing a norbornene-based polymer, a terpene hydrocarbon-based solvent and a fragrance. The glass transition temperature of the norbornene-based polymer in the present invention is 10 ° C or higher, preferably 20 ° C or higher, more preferably 30 ° C to 60 ° C, and the number average molecular weight of the polymer is 1,000,000 or higher. If the glass transition temperature is less than 10 ° C. and the number average molecular weight is less than 1,000,000, the object of the present invention cannot be achieved. The norbornene-based polymer used in the present invention is a ring-opening polymer or copolymer of bicyclo (2.2.1) heptene-2 or its derivative. For example, by polymerizing by a method described in Japanese Patent Publication No. 47-35800. The resulting polymer. The monomer used is bicyclo (2.2.1) heptene-2, methyl-5-bicyclo
(2.2.1) Heptene-2, ethyl-5-bicyclo (2.2.1) Alkyl-5-bicyclo (2.2.1) heptene-2 and other monomers, methoxy-5-bicyclo (2.2.1) ) Heptene-2, ethoxy-5- (2.2.1) heptene-2 and other alkoxy-5-bicyclo (2.2.1) heptene-2 type monomers, cyano-5-bicyclo (2.2.1) heptene-2 , Bicyclo (2.2.1) heptene-2-5-
Examples thereof include carboxylic acid ester-based monomers, bicyclo (2.2.1) heptene-2-5,6 dicarboxylic acid diester-based monomers, and mixtures thereof. A typical polymer is a ring-opening polymer of bicyclo (2.2.1) heptene-2.

The terpene hydrocarbon solvent used in the present invention is preferably a monoterpene of n = 2 in the terpene hydrocarbon represented by the general formula (C5H8) n. As a monoterpene, specifically, α
-Pinene, β-pinene, camphene, parathymene, myrcene, d-limonene and the like. If necessary, a mixed solvent of a terpene hydrocarbon solvent and another aromatic hydrocarbon solvent or an aliphatic hydrocarbon solvent can be used. Aromatic hydrocarbon solvents include isopropylbenzene, n-propylbenzene, 1-methyl-3-ethylbenzene, 1-methyl-4-ethylbenzene, 1,3,5-
Trimethylbenzene, 1-methyl-2-ethylbenzene, t-
Butylbenzene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, etc .; as an aliphatic hydrocarbon solvent
4-methylnonane, 2-methylnonane, 3-methylnonane, n
-Decane, n-undecane, etc. are mentioned. Among these, a solvent having a boiling point of 160 to 200 ° C. is preferable. The concentration of the other aromatic hydrocarbon solvent or aliphatic hydrocarbon solvent in the mixed solvent is preferably within 80% by weight.

Although the fragrance used in the present invention is not particularly limited, it is usually a terpene alcohol, an aliphatic alcohol, an aliphatic ester, an aromatic ester, a terpene ester or an aliphatic ketone. In particular,
As terpene alcohols, linalool, tetrahydrolinalool, dihydromyrcenol, citronellol, geraniol, etc .; as aliphatic alcohols, n
-Hexanol, heptanol, octanol, nonanol, decanol, etc .; Among aliphatic alcohols, those having a phenyl group in the molecule include dimethylbenzylcarbinol, benzyl alcohol, dimethylphenylethyl alcohol, etc .; aliphatic ester Allyl cyclohexyl propionate, allyl hexanoate, cis-3-hexenyl acetate, ethyl 2-methylbutyrate,
Hexyl acetate, ethyl acetoacetate, etc .; Benzyl acetate, cis-3-hexenyl benzoate, dimethylphenylethyl acetate, methyl anthranilate, methyl benzoate, etc. as aromatic ester; Citronellyl acetate, geranyl acetate, isobornyl acetate, etc. as terpene ester; Fat Examples of the group ketone include methylhexenyl ketone and the like. These fragrances can be used in combination of two or more, if necessary.

In addition to the above-mentioned fragrances, linalool oxide, fentyl ethyl ether, rose oxide, 1,4-cineole, methylcedrilone, 2,6-dimethyl-2-heptanol, 4-acetoxy-3-pentyltetrahydrofuran, Isolongifolene ketone, 4-acetoxy-3-amyltetrahydropyran, acetylated cedrene and the like can also be used. The norbornene-based polymer, the terpene hydrocarbon-based solvent, and the fragrance in the high-viscosity fragrance of the present invention are usually blended in proportions of norbornene-based polymer / terpene hydrocarbon-based solvent / perfume = 2 to 35.
/ 98 to 55/1 to 50 (% by weight). By setting the compounding ratio as described above, it is possible to make the viscosity at 23 ° C. measured by the sliding viscosity measurement method be 50,000 cps to 6 million cps. From the viewpoint of workability and economy, norbornene-based polymer / terpene hydrocarbon-based solvent / perfume = 5
25/90 to 60/5 to 15 (% by weight) are preferable,
The viscosity is preferably 100,000 to 3,000,000 cps. The method for preparing the high-viscosity fragrance of the present invention is not particularly limited, but usually, after the components are mixed at room temperature, the mixture is mixed at 80 to 15
By heating to 0 ° C. and then cooling to normal temperature, a uniform highly viscous gel-like transparent fluid high-viscosity fragrance is obtained. As a heating means, any of high-frequency heating, electric heating furnace, heating kneader, etc. can be used. The high-viscosity fragrance of the present invention may contain an appropriate amount of an antioxidant, an ultraviolet absorber, an essential oil, a colorant, etc. within a range that does not impair the effects of the invention. Specific examples of the essential oils include bergamot oil, patchouli oil, petiglen oil, grapefruit oil, lime oil, hyacinth oil, eucalyptus oil, lemon oil, mandarin orange oil and the like. As the colorant, for example, an oily dye is preferable, and specifically, 4,5-dibromo-3,6-fluoranediol, 4,5-diaiodo-3,6-fluoranediol,
3,6-fluoranediol, 2- (2-quinolyl) -1,3-indanediol, 1-methylamino-4-o-tolylaminoanthraquinone, 1-p-phenylazo-phenylazo-2-naphthol, 2, Examples include 4,5,7-tetrabromo-3,6-fluoranediol and 1-phenylazo-2naphthylamine. In addition, if it is oil-soluble, it can be colored in a pale color even if it is slightly dissolved. Further, a water-soluble dye that is soluble in a terpene hydrocarbon solvent can also be used.

[0008]

Since the highly viscous fragrance of the present invention is a pseudo gel-like transparent fluid, it can be filled in fragrance containers such as glass bottles, plastic containers and tube containers. Further, by using an ultra high molecular weight polymer such as norbornene-based polymer as the base material of the fragrance, the solvent and the fragrance are firmly retained in the polymer, the volatilization of the fragrance is suppressed, and a proper and stable fragrance is maintained for a long time. It becomes possible to enjoy.

[0009]

The present invention will be described in more detail with reference to the following examples. (Examples 1 to 5) Norbornene-based polymers, d-limonene, and fragrances were mixed in the mixing ratio shown in Table 1, and 0.1% of 4,5-dibromo-3,6-fluoranediol was added as a coloring agent. A benzyl alcohol solution was mixed in an amount of 0.2% by weight, irradiated with a microwave oven (manufactured by Sanyo Electric Co., Ltd., 500 W) for 5 minutes, heated to a temperature of about 130 ° C., and then air-cooled to remove a high-viscosity aromatic agent. The viscosity was measured. The results are shown in Table 1. Norbornene-based polymer is France ATOCHEM
"No Solex" (Import and sales of Zeon Corporation)
The d-limonene used was manufactured by Takasago International Corporation.
To measure the sliding viscosity of aromatics, use the Roto-Visco rotational viscometer
AAKE, RV-12 M-1500) viscometer was used. The measurement was performed at a cone plate: PK-I 1 °, a rotation speed: 0.1 rpm, and a temperature: 23 ° C. The unit of the mixing ratio of each component in Table 1 is% by weight. Further, the obtained high-viscosity fragrances were all pseudo-gel colored transparent fluids, and the liquid level of the fragrance was uniformly decreased with the evaporation of d-limonene and the fragrance, and no skin was observed. .. As shown in the viscosity measurement results in Table 1, it is found that the fragrance has high viscosity and appropriate fluidity.

[0010]

[Table 1] Linalool was used as the fragrance.

(Aroma Persistence Test) The high-viscosity fragrances obtained in Examples 2 and 4 were selected, and sodium stearate-limonene gel fragrance was used for comparison to maintain the fragrance lasting at room temperature for a long period of time. Tested. The formulation of sodium stearate-limonene gel fragrance is as follows. Sodium stearate 6% by weight d-limonene 66.8 〃 Hexylene glycol 5 〃 Linalool 20 〃 Ion-exchanged water 2 〃 Colorant solution ^{* 1} 0.2 〃 ─────────────── ──────────── 100.0 * 1 Same as Example 2 The following indexes were used for the evaluation of aromaticity. 5 Very strong (aromatic) 4 Very strong 3 Strong 2 Somewhat weak 1 Weak results are shown in Table 2 below.

[0012]

[Table 2] As shown in the results of Table 2, when the high-viscosity fragrance of the present invention is used, the fragrance can be enjoyed for a long period of time.

[0013]

EFFECTS OF THE INVENTION Since the high-viscosity fluid fragrance of the present invention is a pseudo-gel fluid, the liquid level is uniformly reduced by evaporation of the solvent and the surface is kept flat and the appearance is good. Excellent transparency. Perfume volatilization is performed uniformly. It has excellent properties as a fragrance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Sumio Takei, 2-6-1, Marunouchi, Chiyoda-ku, Tokyo Nihon Zeon Co., Ltd. (72) Mitsuru Sano 2-6-1, Marunouchi, Chiyoda-ku, Tokyo Inside Zeon Co., Ltd. (72) Inventor Toshiaki Kobayashi 1-2-1, Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Inside Zeon Corporation R & D Center (72) Inventor Kenji Tsukakoshi 1-2-chome, Kawasaki-ku, Kawasaki-shi, Kanagawa No. 1 in the research and development center of Zeon Corporation

Claims (1)

[Claims] 1. A high-viscosity fragrance containing a norbornene-based polymer, a terpene hydrocarbon-based solvent, and a fragrance.