JPS6238166A - Transparent gel like aroma volatilizing body and its production - 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 (Industrial Field of Application) The present invention relates to a transparent gel-like fragrance volatile material used as an aromatic agent and a method for producing the same.

(Prior Art) Various types of fragrances have been used in practice.

The present inventor previously proposed a granular fragrance volatile material made by impregnating and absorbing a fragrance into granular pellets of ethylene/vinyl acetate copolymer (Japanese Patent Publication No. 60-2064). This perfume volatilizer is widely used today due to its excellent sustained release effect. Japanese Patent Publication No. 59-27784 is also known as an example of such a granular perfume volatilizer.

These granular fragrance volatile materials are easy to manufacture, and because the fragrance is impregnated and absorbed into granular resin, they are more expensive than the type of fragrance volatile material obtained by extrusion molding resin containing fragrance at high temperatures. Although it has the advantage of not causing fragrance deterioration or volatilization loss during the manufacturing process, in order to make it into a product form as a fragrance, it is necessary to use a completely sealed type with a sleeve I of the particle size or smaller due to the granular flow. Therefore, even if it is colored in a beautiful color, it is difficult for the user to see. This cannot be determined.

This is due to the fact that the apparent volume of the granules decreases only slightly due to the volatilization of the fragrance. A liquid fragrance volatilizer is one type of fragrance volatilizer whose end point of volatilization can be easily determined visually. This is used by placing the contents in a transparent container, and the end point of volatilization can be easily determined from the decrease in the contents.

However, because the liquid flavor volatilizer is in a liquid state, there are problems with storage, such as the tendency for it to flow out due to external force during use, and when trying to improve storage stability by devising a container, it becomes difficult to maintain the amount of volatilization. do.

There is a gel-like fragrance volatilization material that does not have such drawbacks and can easily determine the end point of completion of volatilization. A typical example is a so-called aqueous gel, which is made by using carrageenan as a gelling agent and water as a solvent, to which appropriate amounts of a blended fragrance and an emulsifying surfactant are added. Such aqueous gels are usually made by dispersing 2 to 3% by weight of carrageenan powder in water, heating and stirring the mixture to around 100°C to make a complete solution, cooling it to 5°C to 60°C, and then cooling it to 5°C to 60°C. (To avoid thermal deterioration of the product) Add a mixture of 5 to 8% by weight of a blended fragrance and about 1% by weight of an emulsifying surfactant, emulsify it by stirring, and then pour it into an appropriate container and cool it. It is made using a manufacturing method that involves solidifying it into a gel-like shape. Since the solvent is water with a boiling point of 100°C, the rate of volatilization along with the fragrance is fast (and as the volatilization progresses, the volume of the gel contracts, and at the end of the process, it shrinks and dries to less than the initial volume of 171O). It has the great advantage of being able to easily see the end point of volatilization.This is the reason why it has maintained a product lifespan of several years and is still the mainstream of air fresheners.

However, on the other hand, this water gel also has the following drawbacks: a) Because it is an emulsion type that requires the use of a surfactant, its appearance is extremely opaque and thin; It's hard to call it beautiful.

b. If the volatilization is too fast and it is difficult to adjust the volatilization by adjusting the ventilation holes or exposed area, and there is no way to adjust the volatilization, use 1.
It often shrinks to dryness within a week to 10 days.

Since C0 gel has low elasticity, it is easily damaged by external force.

(Problems to be Solved by the Invention) The present invention retains the advantages of conventional carrageenan-based aqueous gels, that is, the property of shrinking and drying to show an end point, but eliminates the disadvantages, and has a transparent (beautiful external appearance). The object of the present invention is to provide a novel gel-like fragrance volatilization material that is highly elastic (resistant to external forces) and has an appropriate volatilization period.

(Means for Solving Problems) The gel-like fragrance volatile material of the present invention consists of a transparent gel-like substance formed by gelling a liquid aliphatic hydrocarbon with a styrene-based thermoplastic elastomer, and a fragrance contained therein. It is something.

The gel-like fragrance volatile material of the present invention uses a styrene thermoplastic elastomer (Stylene Blo-
The present invention is characterized in that it uses a transparent gel-like material obtained from CK Co-poliner (hereinafter abbreviated as SBC) and an odorless or slightly odorless liquid aliphatic hydrocarbon as a gelling solvent.

SBC used as a gelling agent in the present invention is a type of thermoplastic elastomer that exhibits the characteristics of vulcanized rubber at room temperature and that of ordinary thermoplastic resin at high temperatures, and has polystyrene blocks in the hard segment (hard phase). It is a block copolymer that has rubber blocks in the soft segment (soft phase), and polystyrene portions form physical crosslinks (domains) and serve as crosslinking points. Currently, styrene-butadiene-styrene block copolymers (abbreviated as S-B-8, this abbreviation is used below) whose rubber blocks are polybutadiene, and styrene-isoprene-styrene block copolymers whose rubber blocks are polyisoprene (abbreviated as S-B-8),
It is abbreviated as S-t-S. There are three types of styrene-ethylene-butylene-styrene block copolymers (abbreviated as S-E-B-3, hereinafter this abbreviation will be used) whose rubber block is a polyolefin (ethylene, butylene). Mainly on the market. Its main uses include general molding materials, plastic modifiers, adhesives, and adhesive paste polymers. Most are in the form of pellets or crumbs, but some are in the form of powder.

As the gelling agent of the present invention, essentially any SBC can be used, and 5-E-B-3,5-B-3
, S-1-3 are preferably used. All of them give transparent gels, but there are differences in the transparency of the gel produced depending on the rubber block, so if I had to rank them, S-E/B-3 would be completely transparent, and 5-B-3 would be completely transparent. 3 is next, followed by 5-t-S, which tends to fall slightly. S.B.
The amount of C used and the strength of the gel produced are (the polystyrene content of the SBC used (usually expressed as the styrene/rubber ratio)
and molecular weight. When the amount used is constant, the lower the polystyrene content and the lower the molecular weight, the weaker the strength of the resulting gel tends to be. The polystyrene content and molecular weight of SBC should be styrene/rubber ratio of 30/70 or more and molecular weight of 100.000 or more in order to obtain a gel with strength equal to or stronger than ordinary carrageenan-based aqueous gels at an economical usage amount. It is desirable that the styrene/rubber ratio be 35/65 and the molecular weight be 200,000 or more.

In addition, the liquid aliphatic hydrocarbon used as the gelling solvent in the present invention is odorless or has a sufficient amount that does not interfere with the fragrance tone of the fragrance used. ! Any material with a boiling point higher than 100°C is fine, preferably 150°C to 30°C.
Normal paraffins, isoparaffins, etc., which are in the range of 0°C, more preferably in the range of 150°C to 250°C, are desirable. In general, mixed solvents containing saturated aliphatic hydrocarbons as main components, which are commercially available as petroleum-based hydrocarbon solvents, are preferably used. Other solvents such as aromatic hydrocarbons may also be used in combination to the extent that the desired gel can be formed.

The gel-like fragrance volatile material of the present invention is produced by (a) adding alsBc (regardless of pellet form, crumb form, or powder form) to a liquid aliphatic hydrocarbon (hereinafter referred to as 0AHC) and making it viscous by heating and stirring. After making a transparent melt and adding a predetermined amount of fragrance to it and dissolving it uniformly and transparently,
(b) The viscous transparent melt of SBC and 0AHC is cooled to room temperature to form a transparent gel, and the fragrance is absorbed by contact with this gel.
cl A predetermined amount of fragrance is dissolved in 0AHC in advance, SBC is added to this fragrance-containing 0AHC, heated and stirred to form a viscous transparent melt, and this is cooled to room temperature to form a transparent gel-like fragrance volatile material. Method (heat melting method)
Or (b) SB in 0AHC in which a predetermined amount of fragrance has been dissolved in advance.
A method of dispersing the powder of C and leaving it for a short time at a temperature much lower than that required for method (a), but within a range that does not cause thermal deterioration of the fragrance, to form a transparent gel-like volatile material (powder dispersion) W!
It can be manufactured by a hot water method or the like. Method (a) of (b) is often used in the production of aqueous gels such as carrageenan, and can be said to be the simplest production method.

However, as will be described later, in SBC, the glass transition point of polystyrene forming domains (physical crosslinks) is as high as about 90°C, so it is quite difficult to melt SBC to 0AHC in the heat melting method (a). It requires a high level of 1. When the amount of SBC used is small, for example 5% by weight or less, it is barely possible to melt it at a temperature below 100°C, but when the amount used is large, for example around 10% by weight, A high temperature of about 120°C to 150°C is required.

Therefore, in the former case, the f, l and FCI manufacturing methods in (a) are barely possible, but in the latter case, thermal deterioration of the fragrance is unavoidable, so the fbl method in (a) must be used. However, you have no choice but to endure a loss of 24 to 72 hours for the contact and absorption of the fragrance.

The powder dispersion and swelling method (b) is a more advantageous manufacturing method devised to eliminate such manufacturing inconveniences.

This method is based on the phenomena that occur during the steps (a) and (C) of the heat melting method (a) carried out using SBC powder.
-0AHC1 with S B C powder dispersed and the same <
All perfumers' 0AHC in which SBC powder is dispersed contains SBG powder when it reaches a temperature (approximately 1/2 of the temperature required for complete melting of SBC). It remains cloudy, but once it rapidly turns into a gel, the stirring propeller and stirring bar must be stopped. When heating is continued after this immersion, as the temperature rises, this cloudy gel gradually begins to melt transparently from the area close to the heating surface, leading to complete melting. The inventor of the present invention stopped raising the temperature at the time when the above-mentioned cloudy gelation occurred, and after that, when the temperature at which the cloudy gelation was formed was maintained, the cloudy gel gradually became transparent, and finally it became completely transparent and molten. The result was a transparent gel that was exactly the same as the transparent gel made by cooling the liquid. That is, according to this manufacturing method, for example, 10% by weight of SBC powder is used and 14% is heated and melted.
Even if a temperature of 0°C is required, transparent gelation is possible at 70°C, which is half of that temperature. Therefore, a predetermined amount of SBG powder and fragrance can be dissolved in advance without worrying about thermal deterioration of the fragrance. By heating a product container filled with a predetermined amount of 0AHC in an air bath at the required temperature for a certain period of time, an air freshener product based on the transparent, highly elastic gel-like fragrance N1 can be produced. It can be manufactured. It goes without saying that a more beautiful gel can be obtained if the gel is heated and degassed under reduced pressure.

In the case of the heat melting method, the form of SBC to be used may be in the form of pellets or crumbs, but in order to shorten the melting time, powder form is preferable. 1llll molecules! In the case of the hydration method, it is necessary to use a powdered material due to the gelling mechanism.

Mechanism of transparent gelation in the dispersion swelling method; According to the inventor's experiments and observations (11S B C powder particles 0
It is thought that the following processes occur: swelling due to absorption of AHC, (2) opaque gelation due to fusion of saturated and two wet particles, and (3) transparency.

It is essential for the fragrance used in the present invention to dissolve transparently in OAHC, which is the solvent to be gelled, but ordinary mixed fragrances contain components that are easily soluble in hydrocarbons, such as hydrocarbons, esters, and ethers. Since it is contained in sufficient quantity, there are almost no problems. Additionally, insect repellents, flame retardants, and other appropriate ingredients may be used together with fragrances.

The optimal content of each component in the transparent gel-like fragrance volatile material of the present invention thus obtained varies depending on each combination, but usually 5BC 5 to 25% by weight, fragrance 3 to 10% by weight,
0AH092-65% by weight.

Coloring of the transparent gel can be easily achieved, if necessary, by pre-dissolving an oil-soluble dye of the desired color in the fragrance or 0AHC to be used.

(Effect of the invention) The effects of the present invention are listed below.

a The greatest advantage of the carrageenan-based aqueous gel fragrance volatile material, that is, the characteristic that it shrinks and dries up as it evaporates, indicating the end point of the end of evaporation, remains intact.

b. The appearance is beautiful and transparent, and the transparency is maintained until the end of volatilization.

C gel is extremely elastic and strong against external forces.

d. The volatilization tendency is an ideal sustained release type, so volatilization can be controlled more easily than carrageenan.

(Example) The present invention will be described in more detail and more specifically with reference to Examples, but the present invention is not limited thereto.

Example-1 5-E-B-3 manufactured by Shell Chemical Co., Ltd. as a styrene-based thermoplastic elastomer was placed in a commercially available empty container (capacity 160 cc) of an aqueous gel air freshener with a cone-cut type sliding top and bottom lid.
Filled with 13.2 g (12 parts) of powder (16 mesh or less) of the trade name Kraton G-1651,
4℃, dry point 207℃ isoparaffin (made by Shell Chemical,
A mixed solution of 1 g (80 parts) of 81 parts (trade name 5 hellsol 71) and 8.8 g (8 parts) of an osmanthus-based blended fragrance colored orange with an oil-soluble dye was injected, defoamed at 100 m of mercury, and then sealed. , leave it for 35 minutes in a constant temperature bath set to 100℃ and heat it (according to the measurement results using the sample for temperature rise measurement, the content temperature at the 35th minute was 73℃).
℃), wait for it to cool to room temperature, and then remove the lid.
It was finished as an orange-colored, completely transparent, elastic, aromatic gel body.This aromatic gel body in a container was subjected to a 24-hour abuse test at 50°C and -10°C with the container upside down. There was no evidence of gel flow or deformation due to high temperatures, or syneresis due to low temperatures.Also, volatilization and sensory tests were conducted with the lid half open, placed in a flush toilet with 4 volumes, at an average temperature of 15℃, and for 60 days. However, the fragrance intensity within the period was 4.
0 to 2.75 (values according to the 6-stage odor intensity display method, hereinafter expressed simply by numerical values. See Note 1), volatilization rate (volatilization amount/total amount of volatile components, hereinafter simply abbreviated as volatilization rate).

) 94%, which was an extremely good result. The gel residue after volatilization became darker in color, but still maintained its beautiful transparency.

For comparison, a carrageenan-based aqueous gel fragrance volatile material was poured into the container used in this example, cooled, and gelled (2.2 g of carrageenan powder, 1.1 g of surfactant, 8.8 g of osmanthus-based mixed fragrance, and 979 g of water). A total of 110g) was subjected to volatilization and sensory tests under exactly the same conditions as in the case of the SBC gel described above, but the volatilization rate reached 96% as early as 30 days.
The appearance was completely shrunk to dryness, and the aroma intensity within the period was 425 to 275.

Example-2 110 parts of 5-E-B-3 (trade name: Greton G-165 manufactured by Shell Chemical Co., Ltd.) was placed in a suitable container, and the menarche was heated at 174°C.
, 90 parts of isoparaffin (manufactured by Shell Chemical Co., Ltd., trade name: 5Hellsol 7) at a temperature of 207°C was added and melted while heating and stirring.When it became a completely transparent and highly viscous solution at 140°C, it was heated to a diameter of 75°C. between, depth 23
Pour 65g into a pull-top can with a capacity of 100cc.
After cooling slowly at room temperature until it became a completely transparent gel, 5 g of an osmanthus-based blended fragrance colored orange with an orange oil-soluble dye was added, and the bottom of the can was closed using a sealing machine. After leaving this filled and sealed can at room temperature for 72 hours, I measured the fragrance from the pull-top surface and found that the fragrance had completely impregnated and absorbed into the gel body to the point where my fingers did not get wet even if I touched it with my hands. The finished product was a completely transparent, highly elastic, aromatic gel body. Volatilization and sensory tests were carried out on this aromatic gel body in an opened can by placing it in a flush toilet with a volume of 4 rri' at an average temperature of 15°C for 60 days, and the aroma intensity within the period was 3.5 to 2°5. A volatilization rate of 78% was obtained, and the contracted gel body that remained in the direction was still in a state in which the aroma could be volatilized for 10 to 20 days, and still maintained its original beautiful transparency.

Example-3 Into the empty air freshener container used in Example-1, Shell Chemical Co., Ltd.
-B-3 (Product name: Cariflex TR-1184, styrene/rubber ratio 30/70, Publication II 150.000)
Filled with 22g (20 parts) of powder (16 mesh or less), and filled with 22g (20 parts) of powder (16 mesh or less), which was heated at 174°C at menarche and at 207°C at 207°C.
．． 88 g (80 parts) of a mixed solution of 2 g (72 parts) and 8.8 g (8 parts) of a green apple-based blended fragrance that had been previously colored pale green with a green oil-soluble dye was injected, and 1100 n of mercury was added.
After defoaming with +, seal the container tightly and leave it in a constant temperature bath set at 70℃ for 45 minutes to warm it up (the temperature of the contents at the 45th minute is 68℃).
), and when the lid was removed after cooling to room temperature, a pale green, almost transparent, highly elastic, fragrant gel was obtained. For this aromatic gel body in a container, 50%
℃ and -10℃ for 24 hours, but no fluidity or deformation of the gel due to high temperatures, or filtration and syneresis due to low temperatures were observed. In addition, volatilization and sensory tests were conducted for 60 days with the lid half open, placed in a flush toilet with a volume of 4 m'', and an average temperature of 15°C.
Very good results were obtained with a volatilization rate of 92%. The gel residue after evaporation became darker in color, but still maintained its original transparency.

Example-4 In a suitable container, 5-iS manufactured by Shell Chemical Co., Ltd. (trade name: Cariflex TR-1113, styrene/rubber ratio 21/79)
, molecular weight 100.000), to which were added 75 parts of isoparaffin (manufactured by Shell Chemical, trade name 5Hellsol 71) with a menarche of 174°C and a temperature of 207°C.
The solution was melted while heating and stirring, and when it became an almost transparent and highly viscous solution at 130°C, 65g of this was poured into a pull-top can with a diameter of 75 mm, depth of 23 mm, and volume of 100 cc, and slowly cooled at room temperature. After waiting until it became an almost transparent and highly elastic gel body, lemon-based blended fragrance 56 colored yellow with a yellow oil-soluble dye was added thereto, and the bottom of the can was closed using a sealing machine. After leaving this filled sealed can at room temperature for 72 hours, when I connected the line from the pull-top side, the fragrance turned into a gel.
It was completely impregnated and absorbed to the point that it did not wet my fingers even when I touched it with my hands, and it was finished as a pale yellow, almost transparent, highly elastic, aromatic gel body. Regarding this unsealed electrified aromatic gel body,
We conducted a volatilization and sensory test for 60 days in a flush toilet with a volume of 4m'' at an average temperature of 15℃, and the results showed that the aroma intensity within the period was 35-25% and the volatilization rate was 76%. The contracted gel body remaining within the line was still in a state where the aroma could be volatilized for about 10 to 20 days, and still maintained its original transparency.

Example-5 4 parts of powder of 5-E-B-3 (trade name: Kraton G-1651 manufactured by Shell Chemical Co., Ltd.) was placed in a suitable container, and an initial layer of 1
A mixture of 86 parts of isoparaffin (manufactured by Shell Chemical, trade name 5Hellsol 71) at 74°C and a temperature of 207°C and 10 parts of an osmanthus-based blended fragrance previously colored orange with an orange oil-soluble dye was added and heated. When the mixture was melted while stirring, it became a transparent, highly viscous solution at 85°C. This has a diameter of 75 mm and a depth of 23 guns with a capacity of 100 cc.
When 65g of the gel was poured into a pull-top can and slowly cooled at room temperature, it became an orange, completely transparent, highly elastic, fragrant gel, although its strength was slightly reduced. In this state, we conducted a volatilization and sensory test for 60 days at an average temperature of 15°C in a flush toilet with a volumetric volume of 4m'', and the results showed that the volatilization rate was 96% and the aroma intensity during the period was 35 to 275. .

The gel residue that had been completely volatilized still retained its original transparency.

5 strong? (What's the smell?

Claims (4)

[Claims] (1) A transparent gel-like fragrance volatile material comprising a transparent gel-like material formed by gelling a liquid aliphatic hydrocarbon with a styrene-based thermoplastic elastomer, and a fragrance contained therein. (2) The transparent gel-like fragrance volatile material according to claim 1, wherein the liquid aliphatic hydrocarbon has a boiling point higher than 100°C. (3) Styrenic thermoplastic elastomer content is 5 to 25
The transparent gel-like fragrance volatile material according to claim 1 or 2, which is % by weight. (4) Styrenic thermoplastic elastomer powder is dispersed in a liquid aliphatic hydrocarbon in which a fragrance has been dissolved in advance, and the dispersion is maintained at a temperature that does not deteriorate the fragrance for a sufficient period of time to form a transparent gelled monolith. A method for producing a transparent gel-like fragrance volatile material, which is characterized by allowing it to stand still.