JP4480991B2 - Oily gel drug - Google Patents

Description

  The present invention relates to an oily gel-like drug used as a fragrance, a deodorant, and an insect repellent. Specifically, it is strong against impacts such as dropping, and does not cause cracking during molding. Along with this, the present invention relates to a gel-like drug that shrinks while maintaining its original shape, has excellent fragrance retention properties, and can withstand storage and transportation at high temperatures.

  Conventionally, gelled hardened castor oil, sodium stearate, 12-hydroxystearic acid, amino acids, etc. as olepene gel fragrances, volatile hydrocarbon compounds such as terpene hydrocarbons, paraffin hydrocarbons, etc. What mix | blended the agent is known (patent documents 1-3). However, these conventional gel-like fragrances have had the problem that the appearance deteriorates, such as cracking on the surface and inside during molding, and deformation of the shape during volatilization. Moreover, the fragrance retention property at the time of volatilization was poor, and there was a problem that a significant difference in the fragrance tone occurred at the start and end of volatilization.

  In order to solve these problems, the present applicant provides an oily gel-like fragrance composition comprising hardened castor oil, Fischer-Tropsch wax, fatty acid aluminum, a volatile hydrocarbon compound, and a fragrance. (Patent Document 4).

However, although this oil-based gel fragrance composition has solved the above problems, it is weak against external impacts such as dropping during storage or transportation, and the gel may crack in the container. In addition, there has been a problem that the gel dissolves when it reaches a high temperature state.
JP 58-78662 A JP 55-141243 JP 55-102438 A JP2002-210001

  Therefore, the present invention provides an oily gel-like drug that solves the above-mentioned conventional problems and maintains a good gel state even during storage or transportation during impacts from outside such as dropping or storage at high temperatures. Offering is the subject.

  The present inventor conducted intensive research to solve the above problems, and by adding a specific thermoplastic elastomer to a composition comprising a hydrogenated fatty acid triglyceride, a volatile hydrocarbon compound, and a volatile agent, The inventors have found that the above problems can be solved and have reached the present invention.

  That is, the present invention provides an oily gel-like drug containing a hydrogenated fatty acid triglyceride, a volatile hydrocarbon compound, a thermoplastic elastomer and a volatile drug.

  The oily gel-like drug of the present invention is strong against impacts such as dropping, does not crack during molding, shrinks while maintaining its original shape during volatilization, has excellent fragrance retention properties, and at high temperatures It is possible to provide an oily gel-like drug that can withstand storage and transportation of

  The hydrogenated fatty acid triglyceride used in the oily gelled drug of the present invention is not particularly limited as long as it has an action as a gelling agent, but the melting point is preferably in the range of 80 ° C to 90 ° C. Is preferably in the range of 175 to 185.

  Preferred hydrogenated fatty acid triglycerides include, for example, hydrogenated castor oil obtained by hydrogenating castor oil.

  The blending ratio of the hydrogenated fatty acid triglyceride in the oily gelled drug of the present invention is not particularly limited, but is preferably 2 to 20% by mass (hereinafter simply referred to as “%”), particularly preferably 5 to 5%. 15%. If it is less than 2%, the strength of the gel may be insufficient. If it exceeds 20%, the residue will be excessive, and the end point of the use of the oily gel will become difficult to understand.

  The volatile hydrocarbon compound used in the composition of the present invention is used as a base material, and examples thereof include terpene hydrocarbons, paraffin hydrocarbons, and mixtures thereof. Paraffinic hydrocarbon is preferable.

  Among these, examples of the terpene hydrocarbon include α-pinene, β-pinene, d-limonene, l-limonene, dipentene, p-menthane, pinane, and mixtures thereof.

  The paraffinic hydrocarbon may be either an isoparaffinic hydrocarbon or a normal paraffinic hydrocarbon, and the carbon number is not particularly limited, but is preferably 8 to 18, and more preferably 10 to 16. Preferably as a commercial item, normal paraffin N-10 (made by Nikko Petrochemical Co., Ltd.), IP solvent (made by Idemitsu Petrochemical Co., Ltd.), etc. are mentioned.

  The blending ratio of the volatile hydrocarbon compound in the oily gelled drug of the present invention is not particularly limited, but is preferably 25 to 96%, particularly preferably 50 to 90%. If it is less than 25%, the gel does not shrink at the time of volatilization and the end point of use may be difficult to understand, and if it exceeds 96%, a gel having sufficient strength may not be formed.

  The thermoplastic elastomer used for the oily gelled drug of the present invention is a block copolymer composed of a hard block and a soft block and having a hard block phase at the terminal.

  Preferable thermoplastic elastomers include styrene thermoplastic elastomers in which the hard block is a polystyrene phase and the soft block is a rubber intermediate phase.

  Here, the rubber intermediate is preferably polyolefin or hydrogenated polyolefin. The polyolefin preferably includes polybutadiene, polyisoprene and the like, and the hydrogenated polyolefin preferably includes polyethylene / butylene copolymer, polyethylene / propylene copolymer, polyethylene / propylene / butylene copolymer and the like. It is done. Particularly preferred is a polyethylene / propylene / butylene copolymer.

The block copolymer includes diblock of hard block phase-soft block phase, hard block phase-soft block phase-triblock of hard block phase,-(hard block-soft block) _n -multiblock, and the like. However, any of them can be used.

  Further, the content ratio of the hard block phase and the soft block phase in the thermoplastic elastomer is not particularly limited, but is preferably 1: 9 to 5: 5, and particularly preferably 2: 8 to 4: 6. .

  The number average molecular weight of the thermoplastic elastomer is preferably 100,000 or more, more preferably 2,000,000 or more.

  Suitable commercially available thermoplastic elastomers include the Septon series (manufactured by Kuraray Co., Ltd.), the Kraton series (manufactured by Shell Chemical), and the like.

  The blending ratio of the thermoplastic elastomer in the oily gelled drug of the present invention is not particularly limited, but is preferably 0.1 to 10%, particularly preferably 1 to 5%. If the amount is less than 0.1%, the gel strength is insufficient, and the sufficient effect of the present invention may not be obtained. If the amount is more than 10%, the residual amount increases so that the end point of use of the oily gel-like drug is reached. It may be difficult to determine.

  The volatile drug used for the oily gel-like drug of the present invention is a drug that volatilizes at room temperature, and is not particularly limited as long as it vaporizes and gives a desired effect to the space. , Insecticides, fungicides and the like. A fragrance, a deodorizing agent or an insect repellent is preferable.

  Examples of the fragrances include natural fragrances, artificial fragrances, and blended fragrances thereof, and the natural fragrances may be animal fragrances or plant fragrances.

  Examples of animal fragrances include musk, ghost cat fragrance, and Ryu nobori. Examples of plant fragrances include abies oil, akjon oil, almond oil, angelica root oil, pagele oil, bergamot oil, perch. Oil, bore bellows oil, kayabuchi oil, gananga oil, capsicum oil, caraway oil, cardamom oil, cassia oil, celery oil, cinnamon oil, citronella oil, cognac oil, coriander oil, cumin oil, camphor oil, jill oil, estgolan oil Eucalyptus oil, fennel oil, garlic oil, ginger oil, grapefruit oil, hop oil, lemon oil, lemongrass oil, nutmeg oil, mandarin oil, peppermint oil, orange oil, sage oil, star anise oil, turpentine oil, etc. It is done.

  The artificial fragrance is a synthetic fragrance or an extracted fragrance, for example, a hydrocarbon-based fragrance such as pinene or limonene; an alcohol-based fragrance such as linalool, geraniol, citronellol, menthol, borneol, benzyl alcohol, anis alcohol, β-phenethyl alcohol; Phenolic fragrances such as anethole and eugenol; Aldehyde fragrances such as n-butyraldehyde, isobutyraldehyde, hexyl aldehyde, citral, citronellal, benzaldehyde, cinnamaldehyde; Ketone fragrances such as carvone, menthone, camphor, acetophenone, and ionone; Lactone-based fragrances such as γ-butollactone, coumarin, and cineol; octyl acetate, benzyl acetate, cinnamyl acetate, butyl propionate, methyl benzoate, etc. Examples include tellurium fragrances.

  Moreover, the mixing | blending fragrance | flavor which mixed 2 or more types of above-mentioned natural fragrance | flavor and artificial fragrance | flavor can be used.

  The deodorizing agent is not particularly limited as long as it has a deodorizing effect, but preferably, for example, lauryl methacrylate, geranyl chloride, citronellyl senecionate, terpene aldehydes, pyruvate esters, 2-ethyl Examples thereof include zinc hexanoate and zinc ricinoleate, and these can be used alone or in combination.

  The insect repellent is not particularly limited as long as it has an insect repellent effect, but preferably, for example, paradichlorobenzene, naphthalene, camphor, allethrin, praletrin, phthalthrin, resmethrin, permethrin, phenothrin, fenvalerate, cypermethrin, cypermethrin Phenothrin, empentrin, terrareslin, imiprosulin, transfluthrin, phenpropatoline, fenfluthrin, 2,3,5,6-tetrafluoro-4-methylbenzyl (1R) -trans-3- (2-chloro-2- Fluorovinyl) -2,2-dimethylcyclopropanecarboxylate and the like, and one or more of these may be used in combination.

  The antifungal agent is not particularly limited as long as it has an antifungal effect. For example, thymol, α-bromocinnamic aldehyde, parachlorometaxylenol, orthophenylphenol, 3-iodo-2-propylbutylcarbamate , N- (fluorodichloromethylthio) -phthalimide, N-dichlorofluoromethylthio-N ′, N′-dimethyl-N-phenylsulfamide, etc., and one or more of these may be used in combination. Can do.

  Although the compounding quantity of the volatile chemical | medical agent in the oily gel-like chemical | medical agent of this invention does not have limitation in particular, Preferably, it is 0.01 to 40%, Most preferably, it is 0.1 to 30%.

  Furthermore, Fischer-Tropsch wax can be blended with the oily gel-like drug of the present invention for the purpose of preventing cracking of the gel, preventing deformation during volatilization, and improving fragrance retention. The Fischer-Tropsch wax is not particularly limited, but preferably has a softening point of 70 ° C. or higher, and particularly preferably about 105 ° C. FT-100 (made by shell MDS) etc. are mentioned as a commercial item.

  The blending ratio of the Fischer-Tropsch wax in the oily gelled drug of the present invention is not particularly limited, but is preferably 0.1 to 10%, particularly preferably 1 to 5%. If it is less than 0.1%, preferred physical properties of the oily gel-like drug to be obtained may not be obtained.

  In addition to the above-described components, the oily gel-like drug of the present invention includes, as optional components, dyes, pigments, antioxidants, ultraviolet absorbers and the like that are generally used for oil-based gel drugs, which hinder the effects of the present invention It can be added as appropriate within the range.

  The method for preparing the oily gel-like drug of the present invention is not particularly limited. For example, hydrogenated fatty acid triglyceride such as hydrogenated castor oil, thermoplastic elastomer, volatile hydrocarbon, and, if necessary, Fischer-Tropsch wax are mixed by heating. Stir until dissolved completely, then add the desired volatilizing drug, stir well, and then allow to cool to obtain an oily gel-like drug.

  The oily gel-like drug of the present invention thus obtained can be made into a fragrance, a deodorant, an insecticide, an insecticide, an antifungal agent or the like depending on the volatilizing drug to be blended. These fragrances, deodorants, insecticides, insecticides, fungicides, etc. are installed and used indoors, in cars, in toilets, in clogs, in closets, in chests, around kitchens, in bathrooms, etc. can do. Preferably, a fragrance, a deodorant, and an insect repellent are used.

  EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by these Examples.

Example 1
Oily gel fragrance:
Using each component shown in Table 1 in the amount shown in the same table, an oily gel-like fragrance was prepared by the following production method.

<Manufacturing method>
Ingredients other than the fragrance shown in Table 1 were heated to a temperature of about 90 ° C., stirred until completely dissolved, then cooled to about 85 ° C., and then the fragrance shown in Table 1 was added and stirred sufficiently. . Thereafter, the container was filled in a metal container, covered, and allowed to cool to obtain an oily gel fragrance.

The components in Table 1 are as follows.
Septon 4044:
Kuraray Co., Ltd. Styrenic thermoplastic elastomer Styrene-ethylene / butylene-styrene block copolymer,
Styrene: Rubber = 32:68
Clayton G-1651:
Kuraray Co., Ltd. styrene thermoplastic elastomer styrene-polyethylene / propylene-styrene block copolymer,
Styrene: Rubber = 33: 67
Fischer-Tropsch wax:
Product name FT-100 manufactured by Shell MDS
Isoparaffin:
IP solvent fragrance made by Idemitsu Petrochemical Co., Ltd .:
Lemon flavor made by Hasegawa flavor

The obtained oily gel fragrance was evaluated by the following method. The results are shown in Table 2.
<Evaluation method>

Gel shape of oily gel fragrance :
The gel shape change at the time of molding and volatilization was visually determined according to the following evaluation criteria.
Evaluation Judgment No cracks on gel surface and inside: ○
Cracks only on the surface of the gel: △
Cracks even inside the gel: ×

Gel shape after dropping :
In a state where the fragrance container filled with the oily gel-like medicine was covered, it was dropped from the height of 60 cm six times in total, front, back, left, right, top and bottom, opened, visually observed for gel shape change, and judged according to the following evaluation criteria.
Evaluation Judgment No cracks or cracks in the gel: ○
There is only a crack in the gel: △
There are cracks and cracks in the gel: ×

High temperature storage :
With the lid of the fragrance container filled with the oily gel-like drug, leave it in the thermostatic layer at 60 ° C. for 1 month, then take it out, open it immediately after taking it out, and visually observe the gel shape. Judgment was made based on evaluation criteria.
Evaluation Judgment No gel dissolution: ○
Gel is dissolved: ×

Odor intensity and preference :
The fragrance sample was placed in an evaluation room of 0.9 m × 0.9 m × 2.0 m (about 1.62 m ³ ) and allowed to stand for 30 minutes, and evaluated by 5 or 6 levels by 10 panelists to obtain an average value. . The same test was performed after 30 days and 60 days, and changes in odor intensity and odor preference were determined by the following equations.

Evaluation of odor intensity Value: Evaluation 5: Strong 4: Slightly strong 3: Neither 2: Slightly weak 1: Slight 0: No odor Scent intensity = (value after n days / value at opening) × 5

Evaluation of odor preference Value: Evaluation 5: Like 4: Somewhat like 3: Neither 2: Somewhat dislike 1: Some dislike odor preference = (value after n days / value at opening) × 5

<Evaluation results>

  As is clear from the above results, all the products of the present invention were not cracked on the surface or inside of the gel for 60 days after the volatilization from the time of molding, and the gel was cracked even when dropped. There wasn't. The melting point of the gel was higher than that of the comparative product and could withstand high temperature storage. Furthermore, the odor intensity and palatability also showed little change from the beginning to the end of volatilization.

Example 2
Oily gel deodorant:
<Manufacturing method>
200 ml of 9.0 g of hardened castor oil, 1.5 g of thermoplastic elastomer (manufactured by Septon 4044 Kuraray) and 84.0 g of IP solvent (manufactured by Idemitsu Petrochemical Co., Ltd.), 2.5 g of Fischer-Tropsch wax (manufactured by FT-100 Shell MDS) The mixture was placed in a beaker and stirred at 90 ° C. until it was uniformly dissolved. Next, after cooling to 85 ° C., 3.0 g of lauryl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Inc.) is added as a deodorizing agent, stirred well, filled into a metal container, closed with a lid, allowed to cool, and An oily gel deodorant was obtained.

<Evaluation results>
The deodorant container was dropped from the height of 60 cm six times in the front, rear, left, and right directions, and then opened, but the gel was not cracked or cracked.

  Further, when this oily gel-like deodorant was left in a constant temperature layer at 60 ° C. for 1 month and then opened, the gel was not dissolved. When this deodorant was placed in the toilet, the odor of the toilet was deodorized for about 3 months after opening, and no cracks were generated on the gel surface and inside from the beginning to the end of volatilization.

Example 3
Oily gel insect repellent:
<Manufacturing method>
200 ml of 9.0 g of hardened castor oil, 1.5 g of thermoplastic elastomer (manufactured by Septon 4044 Kuraray) and 84.0 g of IP solvent (manufactured by Idemitsu Petrochemical Co., Ltd.), 2.5 g of Fischer-Tropsch wax (manufactured by FT-100 Shell MDS) The mixture was placed in a beaker and stirred at 90 ° C. until it was uniformly dissolved. Next, after cooling to 85 ° C., 3.0 g of paradichlorobenzene was added as an insect repellent, stirred well, filled into a metal container, the lid was closed, and then allowed to cool to obtain the oily gel repellent of the present invention.

<Evaluation results>
This oily gel-like insect repellent was dropped six times in total, front, back, left, and right from the height of 60 cm, and then opened, but the gel was not cracked or cracked. Further, when this insect repellent was left in a constant temperature layer of 60 ° C. for 1 month and then opened, no gel dissolution was observed. And when this insect repellent is placed in a chiffon, it has an insect repellent effect against clothing pests for about 3 months after opening, and no cracks occur on the gel surface and inside from the beginning to the end of volatilization. It was.

According to the present invention, it is strong against impacts such as dropping, is not cracked at the time of molding, is reduced while maintaining its original shape at the time of volatilization, has excellent fragrance retention, and is stored at a high temperature. An oily gel-like medicine that can withstand transportation can be provided.
more than

Claims (7)

2 to 20% by mass of hydrogenated fatty acid triglyceride, 25 to 96% by mass of volatile hydrocarbon compound, 0.1 to 10% by mass of a block copolymer composed of a hard block and a soft block and having a hard block phase at the end, and An oily gel-like drug comprising 0.01 to 40% by mass of a volatile drug. A block copolymer composed of a hard block and a soft block and having a hard block phase at the end is a hard block phase-diblock of a soft block phase, hard block phase-soft block phase-triblock of a hard block phase, or- (Hard block-soft block) _n The oily gelled drug according to claim 1, which is a multi-block of-. The oily gelled drug according to claim 1 or 2, further comprising 0.1 to 10% by mass of Fischer-Tropsch wax. The oily gel-like drug according to any one of claims 1 to 3 , wherein the hydrogenated fatty acid triglyceride is hydrogenated castor oil. The oily gelled drug according to any one of claims 1 to 4 , wherein the volatile hydrocarbon compound is a paraffinic hydrocarbon. 6. The oily gel-like drug according to any one of claims 1 to 5 , wherein the hard block constituting the block copolymer is polystyrene , and the soft block is polyolefin or hydrogenated polyolefin. The oily gel-like drug according to any one of claims 1 to 6 , which is a fragrance, a deodorant or an insect repellent.