JPH03294219A - Persistent aromatic agent - Google Patents

Abstract

PURPOSE:To obtain a persistent aromatic agent capable of stably keeping a perfumery component and emitting balanced perfume at a moderate rate over a long period by adding a perfume as an active component to a photo- degradation polymer. CONSTITUTION:A perfume (e.g. musk, orange oil, lemon oil, peppermint oil, limonene, pinene and camphene) is included in a photodegradation polymer (especially preferably an ethylene-carbon monoxide copolymer or a polyethylene incorporated with a photodegradation accelerator). The photo-degradation polymer such as a photo-degradation ethylene-carbon monoxide copolymer can be produced by copolymerizing ethylene and CO at 230 deg.C under a pressure of about 2,000atm.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a persistent fragrance containing a photodegradable polymer containing a fragrance as an active ingredient. More specifically, the present invention relates to a persistent fragrance containing a fragrance as an active ingredient in a photodegradable polymer, particularly an ethylene/carbon monoxide copolymer or a photodegradation accelerator-added polyethylene.

[Prior Art] In recent years, the consumption of fragrances and deodorizers in daily life has increased rapidly, and they are now being used not only for fragrances and deodorization in toilets but also for indoors, automobiles, public facilities, etc. With the expansion of these fields of application, much research has been conducted on various fragrances.

The fragrances used in these products are usually mixed fragrances, which are composed of a wide variety of ingredients such as natural fragrances and synthetic fragrances. Contains a considerable amount of easy-to-understand ingredients. Moreover, among the constituent ingredients of the blended fragrance, those with low boiling points volatilize quickly, so the balance of the blended fragrance becomes unbalanced as the period of use increases.

The problem was that the grain quality changed significantly.

In order to solve these problems, many studies have been made not only in the development of perfumes themselves but also in terms of materials for supporting perfumes.

Flavor carrier materials are broadly classified into liquid type, solid type, and impregnated type 311U.

As solid type supporting materials, for example, vinyl chloride, polystyrene, polymethyl methacrylate, polyvinyl acetate, ethylene-vinyl acetate co-polymer resin, etc. are known. Air fresheners are known (Japanese Unexamined Patent Publication No. 52-1
45530, Japanese Patent Publication No. 60-2064).

[Problems to be Solved by the Invention] The above-mentioned conventionally proposed thermoplastic resins, such as polyvinyl chloride, have 11 Ff! There are problems such as it takes a long time for impregnation and absorption of No. 8, the impregnation rate is extremely low, and the volatilization rate of fragrance is very poor (Japanese Patent Application Laid-open No. 52-145530). Although copolymer resins have a superior fragrance impregnation rate compared to other resins, they have a high fragrance residual rate and a low volatilization rate, and they also have problems such as melting and deterioration depending on the location where they are applied. (Special Publication No. 60-2064)
.

Furthermore, resins other than those mentioned above all have poor fragrance resistance, and when they come into contact with fragrances, they absorb them even at room temperature.
This is unsatisfactory because it causes problems such as softening and deformation.There are various reasons for this, including the fact that there is no compatibility between the fragrance and the resin, and the fragrance leaches onto the surface of the resin and rapidly loses its effectiveness. On the other hand, if the fragrance is completely sealed inside the resin and is not diffused to the surface and does not exert its effect as a fragrance, or if the fragrance interacts physically or chemically with the resin in the fragrance and loses its effect as a fragrance. Possible causes.

In view of these circumstances, the inventors of the present invention have conducted intensive research into resin materials that have a high ability to absorb fragrances, do not cause deterioration of fragrances, and can emit fragrances at an appropriate rate and in a well-balanced manner. We have succeeded in finding a resin material that can solve this problem and have arrived at the present invention.

[Means for Solving the Problems] The present invention provides a persistent fragrance comprising a photodegradable polymer, preferably an ethylene/carbon monoxide copolymer or a photodegradation accelerator-added polyethylene, mixed with a fragrance as an active ingredient. provide.

The present invention uses a photodegradable polymer, which has never been used as a support material for fragrances, as a support material.
The product was successfully completed by providing a long-lasting fragrance that was not available with conventional products.

That is, the present invention provides an aromatic agent in which a fragrance is mixed as an active ingredient with a photodegradable polymer that has recently attracted attention as a non-polluting resin, particularly preferably an ethylene/carbon monoxide copolymer or a photodegradation accelerator polyethylene. The photodegradable polymer is decomposed by light, increasing the surface area of the polymer, and as a result, the fragrance sealed inside the polymer is easily volatilized, and compared to conventional resin materials, the fragrance does not change in quality. Moreover, it has the excellent feature of being able to volatilize fragrance at an appropriate speed and in a well-balanced manner.

The photodegradable polymer used in the present invention, such as a photodegradable ethylene/carbon monoxide copolymer, is
(GP, 863.711) obtained by copolymerizing ethylene and carbon monoxide under conditions of about atmospheric pressure, for example, Eco copoly 7- (Dupont Co., Dow Che
Other photodegradable polymers used in the present invention, such as photodegradation accelerator-added polyethylene, are easily available on the market as products manufactured by Mica1 and UCC. Transition metal salts (e.g. iron dibutyldithiocarbamate, iron acetylacetonate, zirconium neodecanoate, etc.), photosensitized 1FI
(e.g. benzophenone, 2-phenylacetophenone, etc.), oxidation promoters, etc., and these are also easily available on the market.1 These photodegradation promoters are usually sold as masterbatches; Examples of photodegradable polymers include DXM (manufactured by UCC),
Polygrade (manufactured by Ambasset), 31056 (manufactured by Ambasset), Polygrade III (manufactured by Ambasset), Ecolite S (manufactured by Eco Plastics), Bonacol (manufactured by Bonacol, British, Litalace (Plastibon)) Plastic, Vo 1.4, which is easily available as a product with a product name such as (manufactured by Technology Co., Ltd.)
0. No. 9. See pages 63-70, Nikkei Business, 10
9th issue, pp. 22-23, 1989).

The fragrance to be mixed and absorbed into the photodegradable polymer is not particularly limited, and any of natural fragrances, synthetic fragrances, and blended fragrances can be used. Examples of natural fragrances include the following fragrances.

Jasmine oil, orange oil, lemon oil, peppermint oil, bergamot oil, cedarwood oil, cinnamon oil, lavender oil,
Sandalwood oil, citronella oil, garlic oil, ginger oil, hop oil, lemongrass oil, star anise oil, grapefruit oil, turpentine oil, abinis oil, cananga oil, cumin oil, bore rose oil, caraway oil, eucalyptus oil, etc.

Examples of synthetic fragrances include the following fragrances.

Hydrocarbons such as limonene, pinene, camphene, myrcene, and terbinolene; Alcohols such as cis-3-hexenol, linalool, geraniol, hydroxycitronel, myrcenol, menthol, benzyl alcohol, and α-amyl cinnamic alcohol; methylhebutenone, Ketones such as ionone, carvone, acetophenone, acetonaphthone, piperitone; nonagenal,
Citral, hydroxycitronellal, α-cinnamic aldehyde, cyclamenaldehyde, liral,
Aldehydes such as Lilial; cyclopentadecanone,
Cyclic compounds such as cyclopentadecanolide, ethylene brasylate, phanthalide, galaxolide, etc.: Esters of the above alcohols with various alcohols, etc.

The blended fragrance can be obtained by appropriately blending one or more of the above-exemplified fragrances. Examples of these are as follows.

Mixed fragrances commonly used in cosmetics such as rose, jasmine, and muguet; flavor tags such as strawberry, grapefruit, melon, lemon, orange, and chocolate; etc.

These fragrances are appropriately selected and used depending on the place of application.

The above-mentioned fragrances may be used either by themselves or by dissolving them in various solvents if desired.8 Examples of commonly used solvents are as follows.

Dipropylene glycol, propylene glycol, hexylene glycol, glycerin, ethyl phthalate, benzyl benzoate, dimethyl phthalate, barcolin, diethylene glycol monoethyl ether, diacetyl, limonene dimer, isoparaffin, etc.

In addition to the above solvents, pigments, antioxidants, stabilizers, deodorants,
Bactericides, insecticides, etc. may be added as appropriate.

The method for producing the long-lasting fragrance of the present invention will be described below.

Pellets of a photodegradable polymer, such as an ethylene/carbon monoxide copolymer or polyethylene added with a photodegradation accelerator, for example, and a fragrance are mechanically mixed or mixed under conditions below the melting temperature of the pellets. Manufactured by kneading. In addition, an ethylene-vinyl acetate copolymer resin with a high fragrance impregnation rate is impregnated with a fragrance under temperature conditions such that the resin does not substantially fuse, and this is used as a masterbatch to be applied to the photodegradable polymer of the present invention. It may be manufactured by mixing or kneading separately.

As a method for mixing or kneading, processing equipment used in the synthetic resin processing industry, rubber processing industry, etc. can be used. In addition, the molding operation is preferably carried out at a temperature of 150°C or lower, preferably 100°C or lower, to prevent the fragrance from volatilizing.
Examples of processing devices include Henschel mixer, Dalton mixer, kneader-tween roll, and the like. Further, the aromatic agent of the present invention may be formed into any shape such as powder, granule, solid block, sheet, string, cylinder, or semicylindrical shape.

The ethylene/vinyl acetate copolymer resin used as a masterbatch preferably has a vinyl acetate content of about 19 to 40% by weight, and the particle size is usually 1 to 10 mm.
It is preferable to use one with a certain degree. In order to adsorb the fragrance to the resin, it is sufficient to place a certain amount of the fragrance and the resin in a suitable container and allow it to be impregnated at room temperature. impregnated with fragrance.

The temperature during impregnation is 40-50℃, and the impregnation time is about 1-5.
The persistent fragrance of the invention is obtained by mixing or kneading the masterbatch thus produced, which may take a short time, into a photodegradable polymer. Compared to the method of directly mixing or kneading fragrances into photodegradable polymers, the method of using this masterbatch is less likely to change the fragrance due to heat during production or volatilize the fragrances, resulting in less false photodegradable polymers. It is good because it makes it easy to mix uniformly! This is a new method.

The present invention will be explained in more detail below based on Examples.

In each case below, parts and percentages are by weight unless otherwise specified.

(Example) Example 1 Ethylene/vinyl acetate copolymer resin (trade name: EVAFLE)
X-150, vinyl acetate content 33%.

70 g of transparent pellets (manufactured by Mitsui Polychemical Co., Ltd.), orange-based blended fragrance (70 parts orange, 5 parts octanal, 1 part nonanal, 8 parts decanal, 5 parts citronellal)
1 part, 4 parts of methyl henatenone, and 7 parts of citral) was sealed in an eggplant-shaped flask (volume 21) of an evaporator and rotated at 35 revolutions per minute at room temperature (23°C).

The beret absorbs and absorbs the fragrance in about 25 minutes, but as the rotation continues, the fragrance penetrates into the inside, and the wet surface of the beret gradually dries, and after an hour, a smooth and fluid fragrance-impregnated beret is obtained. It was done.

15g of this pellet and DXM (product name, manufactured by UCC) 1
00g at about 100℃ using twin rollers for about 1
Five portions were combined to obtain a kneaded product. This kneaded mixture was passed through a pulverizer to obtain a granular fragrance with a uniform particle size of 1.5 mm in average particle size. This air freshener was placed in a mesh container and then placed in the interior of a car. A panel specializing in this indoor fragrance
Tested by 10 people. As a result, all panelists answered 3
It was determined that the initial aroma balance and aroma intensity were maintained even after several months.

Example 2 In Example 1, ethylene/carbon monoxide copolymer (trade name: ECO1Dow Ch) was used instead of DXMloog.
A granular fragrance was produced in the same manner as in Example 1, except that 100 g (manufactured by emica 1) was used11).

This air freshener was placed in a mesh container and placed in the reception room. The aroma in this room was regularly inspected by 10 expert panelists. As a result, all panelists judged that the initial aroma balance and aroma strength were maintained even after 3 months.

Example 3 Ethylene/carbon monoxide copolymer (trade name: ECO).

500 g of jasmine fragrance (40 parts of benzyl acetate, 15 parts of benzyl propionate,
10 parts of benzyl alcohol, 18 parts of linalool, 5 parts of linalyl acetate, 3 parts of indole (10% dipropylene glycol solution), 2 parts of dihydrojasmone, 5 parts of methyl dihydrojas supernate, methyl anthranilate (10% dipropylene glycol solution) ) 2 parts > 50g were added and kneaded in a kneader at about 130°C for 15 minutes, then 1
The portion was taken out and compression molded at 130° C. to obtain a molded product with a width of 5 cm, a thickness of 0.5 cm, and a length of 5 cm.

Each molded product weighs 9.1g and contains 0.00% fragrance.
A molded product containing 95g was placed indoors and the weight loss was measured over 3 months.The weight loss was 0 at the 51st month.
．． 26g, 0.41g in the second month, '0.6 in the third month.
It was 0g. Also, the aroma during this time is well-balanced,
He also exuded a positive vibe with an appropriate amount of strength.

Example 4 A molded product was obtained in the same manner as in Example 3, except that 500 g of photodegradable polyethylene (trade name: DXM, manufactured by UCC) was used instead of the ethylene/carbon monoxide copolymer.

The obtained molded product was placed in the interior of a car, and the aroma in the interior was periodically inspected by a panel of 10 experts. ``Each expert panelist determined that the initial aroma balance and strength had been maintained over the three-month period.

[Effects of the Invention] According to the present invention, there is provided a long-lasting fragrance that does not cause deterioration of the fragrance and can volatilize a well-balanced fragrance at an appropriate rate for a long period of time.

Further, according to the present invention, there is provided a long-lasting fragrance that does not waste the fragrance and has a high utilization rate of the fragrance.

Claims (2)

[Claims] (1) A long-lasting fragrance made by containing a fragrance as an active ingredient in a photodegradable polymer. (2) The persistent fragrance according to claim (1), wherein the photodegradable polymer is an ethylene/carbon monoxide copolymer or polyethylene added with a photodegradation accelerator.