JPH0563184B2 - - Google Patents

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).
issue). 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 volatile material. 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. It has the advantage that there is no deterioration or volatilization loss of the fragrance during the manufacturing process, but in order to make it into a product as a fragrance, it must be in a completely sealed container with a slit smaller than the particle size because it is granular. Therefore, even if it is colored in a beautiful color, it has the disadvantage that it is difficult for the user to see, and the most disadvantageous point is that the end point of the end of volatilization cannot be determined visually. There is no such thing. This is due to the fact that the apparent volume of the granules decreases only slightly due to volatilization of the fragrance. A liquid fragrance volatilizer is one type of perfume volatilizer whose end point of volatilization can be easily determined visually. This is used by placing the amount of the contents in a container that can be seen through, and the end point of volatilization completion 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 fact that it tends to flow out due to external force during use, and if storage is attempted to be improved by devising a container, it becomes difficult to maintain the amount of volatilization. is derived. 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 carrageenan as a gelling agent, water as a solvent, and an appropriate amount of blended fragrance and emulsifying surfactant added thereto.
There is a so-called aqueous gel. Such aqueous gels usually contain 2
~3% by weight of carrageenan powder is dispersed in water, heated and stirred to around 100°C to make a complete solution, and once cooled to around 55°C to 60°C (to avoid thermal deterioration of the fragrance), 5~ A mixture of 8% by weight of blended fragrance and about 1% by weight of emulsifying surfactant is added, stirred and emulsified, poured into an appropriate container, cooled and solidified into a gel-like shape in the shape of the container. It is made using the same manufacturing method. the boiling point of the solvent
Since the water is at 100℃, the rate of volatilization along with the fragrance is fast, and as the volatilization progresses, the volume of the gel shrinks and dries to less than 1/10 of its initial volume, so it is difficult to volatilize. It has the great advantage of being able to easily see the termination endpoint. This is the reason why it has maintained a product lifespan of more than ten years and is still the mainstream of air fresheners. However, on the other hand, this water gel also has the following drawbacks. a) Since it is an emulsion type that requires the use of a surfactant, its appearance is extremely opaque, and therefore it cannot necessarily be said that it is beautiful even if it is colored in various tones. b. The volatilization rate is too fast, making it difficult to adjust the volatilization by adjusting the ventilation holes or exposed area. If the volatilization cannot be adjusted properly, it often shrinks to dryness within a week to 10 days. c Because the 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 appearance) gel. ) 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 the 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) as a gelling agent.
It is characterized in that it uses a transparent gel-like material obtained from Block Co-polymer (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 properties 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, there are styrene-butadiene-styrene block copolymers (abbreviated as S-B-S, hereinafter used) whose rubber blocks are polybutadiene, and styrene-isoprene-styrene block copolymers (S-I-S) whose rubber blocks are polyisoprene. A styrene-ethylene-butylene-butylene block copolymer whose rubber blocks are polyolefins (ethylene, butylene) (abbreviated as S-E-B-S, hereinafter this abbreviation will be used). ) are mainly on the market. Its main uses include general molding materials, plastic modifiers, and base polymers for adhesives and adhesives. The form is mostly pellet-like or crumbs (bread crumbs)
There is also a powder form. As the gelling agent of the present invention, essentially any SBC can be used, and S-E, B-
S, S-B-S, and S-I-S are all preferably used. All of them give a transparent gel, but there is a slight difference in the transparency of the gel produced depending on the rubber block.
B-S is completely transparent, followed by S-B-S, and S-I-S tends to be slightly transparent. SBC
The amount used and the strength of the resulting gel depend on the polystyrene content (usually expressed as the styrene/rubber ratio) and molecular weight of the SBC used. 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 to obtain a gel with the same or higher strength than ordinary carrageenan-based aqueous gels at an economical usage amount.
It is desirable that the molecular weight be 100,000 or more, and it is even more desirable that the styrene/rubber ratio be 35/65 and the molecular weight be 200,000 or more. The liquid aliphatic hydrocarbon used as a gelling solvent in the present invention may be of any kind as long as it is odorless or has a slight odor that does not interfere with the fragrance tone of the fragrance used, but it may have a boiling point higher than 100°C. , preferably a boiling point in the range of 150°C to 300°C, more preferably 150°C
Normal paraffin, isoparaffin, etc. in the range of ℃ to 250℃ are preferable. 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 as long as the desired gel can be formed. The gel-like fragrance volatile material of the present invention can be obtained by adding (a) SBC (regardless of pellet, crumb, or powder form) to liquid aliphatic hydrocarbon (hereinafter referred to as OAHC) and heating and stirring to make it viscous. Create a viscous transparent melt, add a predetermined amount of fragrance, dissolve uniformly and transparently, and then cool to room temperature.
or (b) cooling a viscous transparent melt of SBC and OAHC to room temperature to form a transparent gel, and allowing the fragrance to be absorbed by contact with this, or (c) dissolving a predetermined amount of fragrance in OAHC in advance. leave it alone,
SBC is added to this fragrance-containing OAHC and heated and stirred to form a viscous transparent melt, which is then cooled to room temperature to form a transparent gel-like fragrance volatile material (heat melting method) or (b) prepared in advance. OAHC in which a fixed amount of fragrance is dissolved
A method of dispersing SBC powder and leaving it for a short period of time at a temperature far lower than that required for method (a), within a range that does not cause thermal deterioration of the fragrance, to form a transparent gel-like volatile material (powder dispersion swelling) It can be manufactured by the following methods. 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 explained later in SBC, the glass transition point of the polystyrene that forms the domains (physical crosslinks) is as high as approximately 90°C.
Considerable high temperatures are required to melt SBC into OAHC. When SBC usage is low, for example 5
If the amount is less than 100℃, it is possible to melt it at a temperature below 100℃, but if the amount used is large, for example, around 10% by weight, it is possible to melt at a temperature of 120℃ or less.
Requires high temperatures of around 150°C. Therefore, in the former case, the production methods in (a) and (c) of (a) are barely possible, but in the latter case, it is difficult to avoid thermal deterioration of the fragrance, so the method (b) of (b) is possible. However, they have no choice but to endure a loss of 24 to 72 hours for 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 heating melting method (a) carried out using SBC powder.
--Both OAHC with SBC powder dispersed and fragrance-containing OAHC with SBC powder dispersed contained SBC powder when the temperature reached about 1/2 of the temperature required for complete melting of SBC. Once the liquid is cloudy, it quickly turns into a gel, causing the stirring propeller and stirring bar to stop. After this, when heating is continued, this cloudy gel gradually begins to melt transparently from a portion close to the heating surface as the temperature rises, leading to complete melting. The present inventor stopped the temperature increase at the time of the above-mentioned cloudy gelation,
After that, when we tried to maintain the temperature at which the cloudy gel formed, the cloudy gel gradually became transparent, and in the end it became a transparent gel that was exactly the same as the transparent gel that was created by cooling a completely transparent molten liquid. It is. In other words, with this production method, for example, even if 10% by weight SBC powder is heated at 140°C using the heating melting method, it is possible to form a transparent gel at 70°C, which is half of the temperature required, and therefore the fragrance can be made into a transparent gel. without worrying about thermal deterioration.
A transparent, highly elastic gel-like fragrance can be produced by simply heating a product container containing a specified amount of SBC powder and a specified amount of OAHC in which the fragrance has been dissolved in an air bath at the required temperature for a certain period of time. It is possible to manufacture fragrance products using volatile substances as a base material. It goes without saying that a more beautiful gel can be obtained by defoaming by reducing pressure before heating. The form of SBC to be used may be pellets or crumbs in the case of the heat melting method, but it is preferable to use powder form in order to shorten the melting time. In the case of the dispersion swelling method, it is necessary to use powdered material due to the gelation mechanism. According to the inventor's experiments and observations, the mechanism of transparent gelation in the dispersion swelling method is (1) swelling due to absorption of OAHC by SBC powder particles, (2) opaque gelation due to mutual fusion of saturated swollen particles. (3) It seems to follow the same process as transparency. The fragrance used in the present invention is a gelling solvent.
Transparent dissolution in OAHC is an essential condition, but there is almost no problem since ordinary blended fragrances contain sufficient components that are easily soluble in hydrocarbons, such as hydrocarbons, esters, and ethers. In addition, insect repellents, flame retardants, and other appropriate ingredients can also 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 the respective combination, but is usually 5 to 25% by weight of SBC, 3 to 10% by weight of fragrance, and 92 to 65% by weight of OAHC. %. To color the transparent gel, use an oil-soluble dye of the desired color, incense, or
This can be easily achieved by pre-dissolving it in OAHC. (Effects 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, and therefore 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 A commercially available empty container (capacity: 160 c.c.) of an aqueous gel air freshener with a cone-cut type sliding top and bottom lid was filled with S-E/B- manufactured by Ciel Chemical as a styrene thermoplastic elastomer. Filled with 13.2 g (12 parts) of Kraton G-1651 powder (16 mesh or less) and 88 g of isoparaffin (Shell Chemical Co., Ltd., trade name Shellsol 71) with an initial distillation temperature of 174°C and a dry point of 207°C ( Inject a mixed solution of 80 parts) and 8.8 g (8 parts) of an osmanthus-based blended fragrance colored orange with an oil-soluble dye.
After defoaming with 100 mm of mercury, seal the cap and leave it in a constant temperature bath adjusted to 100 for 35 minutes to heat it (according to the measurement result of the sample for temperature rise measurement, the content temperature at the 35th minute was 73℃. After waiting for it to cool to room temperature, I removed the lid and found that it had finished as an orange, completely transparent, highly elastic, aromatic gel. This aromatic gel body in a container was tested at 50℃ and -10℃ under the condition of upside down container.
A 24-hour abuse test at ℃ was conducted, but no gel flow or deformation caused by high temperatures or syneresis caused by low temperatures were observed. In addition, we conducted a volatilization and sensory test for 60 days with the lid partially open, the toilet placed in a flush toilet with a volume of approximately ^4m3 , and an average temperature of 15℃.
2.75 (value based on the 6-level odor intensity display method, hereinafter:
Expressed simply by numbers. (See Note 1) and volatilization rate (volatilization amount/total amount of volatile components, hereinafter simply abbreviated as volatilization rate) of 94%, very good results were obtained.
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 (carrageenan powder 2.2 g, sea surfactant 1.1 g) was poured into the container used in this example, cooled, and gelled.
Osmanthus osmanthus blend fragrance 8.8g, water 97.9g, total 110g)
Volatilization and sensory tests were carried out under exactly the same conditions as for the SBC gel mentioned above, but the volatilization rate reached 96% as early as 30 days, and the appearance was completely shrunk and dried. was 4.25 to 2.75. Example 2 10 parts of S-E・B-S (trade name) Kraton G-1651 manufactured by Shell Chemical Co., Ltd. was placed in a suitable container, and isoparaffin (manufactured by Shell Chemical Co., Ltd., trade name Add 90 parts of Shellsol 71) and melt while heating and stirring until it becomes a completely transparent and highly viscous solution at 140℃, then pour 65g of this into a pull-top can with a diameter of 75mm, depth of 23mm, and capacity of 100c.c. death,
Wait for it to slowly cool at room temperature until it becomes a completely transparent gel, then add 5g of an osmanthus-based blended fragrance colored orange with an orange oil-soluble dye.
The bottom of the can was closed using a sealing machine. After leaving this filled sealed can at room temperature for 72 hours, when you open the can from the pull-top side, the fragrance is completely absorbed into the gel body to the point where your fingers won't get wet even if you touch it with your hands. The finished product was a completely transparent, highly elastic, aromatic gel body. Volatilization and sensory tests were conducted on this aromatic gel body in an opened can, placed in a flush toilet with a volume of approximately ^4m3 , at an average temperature of 15℃, for 60 days, and the aroma intensity within the period was 3.5 to 2.5, and the volatilization rate was 78%. After the results are obtained, the shrinkage gel body left in the can is still 10-20
It was in a state where the aroma could be evaporated for several days, and it still retained its original beautiful transparency. Example 3 The empty air freshener container used in Example-1 was filled with S-B-S (trade name: Califrex TR-) manufactured by Ciel Chemical.
1184, styrene/rubber ratio 30/70, molecular weight 150000)
Filled with 22g (20 parts) of powder (not more than 16 mesh),
Add to this 79.2 g (72 parts) of isoparaffin (trade name: Shellsol 71 manufactured by Shell Chemical Co., Ltd.) with an initial distillation temperature of 174°C and a dry point of 207°C.
And, it was colored pale green in advance with green oil-soluble dye,
Mixed solution with 8.8g (8 parts) of green apple-based blended fragrance
Inject 88g (80 parts), degas with 100mm of mercury, seal tightly, and leave to warm in a constant temperature bath adjusted to 70℃ for 45 minutes (content temperature at 45th minute is 68℃). When I waited for it to cool to room temperature and removed the lid, I found a light green, almost transparent, highly elastic, aromatic gel. Regarding this aromatic gel body in a container, under the condition that the container is upside down,
A 24-hour abuse test was conducted at 50°C and -10°C, but no gel flow or deformation due to high temperatures or syneresis due to low temperatures was observed. In addition, the lid is half open, the flush toilet has a volume of approximately ^4m3 , the average temperature is 15℃, and the number of days is 60.
A day-long volatilization and sensory test was conducted, and very good results were obtained, with an aroma intensity of 4.0 to 2.75 and a volatilization rate of 92%. The gel residue after volatilization became darker in color, but still maintained its original transparency. Example 4 In a suitable container, S-I-S manufactured by Shell Chemical Co., Ltd. (trade name Califrex TR-1111, styrene/rubber ratio
21/79, molecular weight 100000), and add the first distillation to this.
Add 75 parts of isoparaffin (Shell Sol 71, manufactured by Shell Chemical Co., Ltd., trade name) with a temperature of 174°C and a dry point of 207°C, and melt it while heating and stirring. When it becomes an almost transparent and highly viscous solution at 130°C, this is added. Pour 65g into a pull-top can with a diameter of 75mm, a depth of 23mm, and a capacity of 100c.c.
The mixture was slowly cooled at room temperature until it became an almost transparent, highly elastic gel, then 5 g of a lemon-based blended fragrance colored yellow with a yellow oil-soluble dye was added, and the bottom of the can was closed using a sealing machine. After leaving the filled sealed can at room temperature for 72 hours, when the can is opened from the pull-top side, the fragrance has been completely absorbed into the gel body to the point where even if you touch it with your fingers, your fingers won't get wet at all. The finished product was a yellow, almost transparent, highly elastic aromatic gel.
Volatilization and sensory tests were conducted on this aromatic gel body in an opened can, placed in a flush toilet with a volume of approximately 4 m ³ at an average temperature of 15°C for 60 days, and the aroma intensity within the period was 3.5 to 2.5, with a volatilization rate of 76. %, and the shrunken gel body remaining in the can 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 S-E・B-S (trade name: Kraton G-1651 manufactured by Ciel Chemical Co., Ltd.) was placed in a suitable container, and to this was added isoparaffin (manufactured by Ciel Chemical Co., Ltd.) with an initial distillation temperature of 174°C and a dry point of 207°C. A mixture of 86 parts of Shellsol (trade name: Shellsol 71) and 10 parts of an osmanthus-based blended fragrance that has been previously colored orange with an orange-based oil-soluble dye is added, and the mixture is heated and stirred until melted. It became a highly viscous solution. This is 75mm in diameter and 23mm in depth.
When 65g of the product was poured into a pull-top can with a capacity of 100c.c. and slowly cooled at room temperature, it became an orange, completely transparent, highly elastic, aromatic gel, although its strength decreased slightly. In this state, volatilization and sensory tests were conducted in a flush toilet with a volume of approximately 4 m ³ at an average temperature of 15°C for 60 days.The volatilization rate was 96%, and the aroma intensity during the period was 3.5 to 2.75.
The result was obtained. The gel residue after volatilization still maintained its original transparency. 【table】

Claims (1)

[Scope of 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~
The transparent gel-like fragrance volatile material according to claim 1 or 2, which has a content of 25% by weight. 4 Disperse powder of styrenic thermoplastic elastomer in liquid aliphatic hydrocarbon in which fragrance has been dissolved in advance, and leave the dispersion to stand for a sufficient time to form a transparent gelled solid under temperature conditions that do not deteriorate the fragrance. 1. A method for producing a transparent gel-like fragrance volatile material.