WO2013015293A1 - Agent libérant un parfum - Google Patents

Agent libérant un parfum Download PDF

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Publication number
WO2013015293A1
WO2013015293A1 PCT/JP2012/068751 JP2012068751W WO2013015293A1 WO 2013015293 A1 WO2013015293 A1 WO 2013015293A1 JP 2012068751 W JP2012068751 W JP 2012068751W WO 2013015293 A1 WO2013015293 A1 WO 2013015293A1
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WO
WIPO (PCT)
Prior art keywords
fragrance
alcohol
hydroxyl group
carbon atoms
phenol
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PCT/JP2012/068751
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English (en)
Japanese (ja)
Inventor
田中作弥
阿部秀幸
山崎大輔
本間由利子
Original Assignee
花王株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by 花王株式会社 filed Critical 花王株式会社
Priority to CN201280037150.9A priority Critical patent/CN103717721B/zh
Publication of WO2013015293A1 publication Critical patent/WO2013015293A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0003—Compounds of unspecified constitution defined by the chemical reaction for their preparation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q13/00—Formulations or additives for perfume preparations

Definitions

  • the present invention relates to a fragrance releaser that slowly releases 4- (3-oxobutyl) phenol (raspberry ketone), a method for producing the same, and a fiber treatment composition containing the fragrance releaser.
  • JP-A-54-59498 contains a specific silicate compound and a fatty alkyl quaternary ammonium compound to impart a long-lasting aroma to knitted fabrics.
  • a knitted fabric conditioner composition is disclosed in JP-A-54-93006, which contains a specific silicate compound and a fragrance imparting component that imparts a long-lasting fragrance to the knitted fabric. It is disclosed.
  • a hydrolyzate of silicate ester is used as a fragrance component, and the silicate ester adhering to the fiber product is gradually hydrolyzed by moisture in the air, etc., thereby providing a durable scent to the fiber product.
  • an aqueous product such as a detergent for clothing and a softener.
  • JP 2009-242798 discloses a technique in which two specific types of functional substances to be introduced into a silicate compound are used in combination from the viewpoint of Log P value (1-octanol / water partition coefficient). Discloses a technique using a silicate ester compound in which a hydrocarbon group having a specific chain length is bonded to a silicon atom.
  • International Publication No. 01/79212 discusses the sustained release rate of various functional substances such as fragrances, flavors and antibacterial agents from silicate compounds.
  • the present invention relates to a fragrance releasing agent comprising a silicate compound represented by the following formula (1) [hereinafter referred to as silicate compound (1)], a method for producing the fragrance releasing agent, and the fragrance.
  • silicate compound (1) a silicate compound represented by the following formula (1) [hereinafter referred to as silicate compound (1)]
  • a fiber treatment composition containing a release agent is provided.
  • R 1, the R 2, R 3 and R 4 are independently an alkyl group or an aryl group of hydrogen atom or a carbon atoms which may have a substituent ⁇ 30,, R 1, R 2 , 1 or 2 of R 3 and R 4 is a residue obtained by removing a phenolic hydroxyl group from 4- (3-oxobutyl) phenol, and 2 of R 1 , R 2 , R 3 and R 4 One or three is a residue obtained by removing a hydroxyl group from a secondary or tertiary alcohol.
  • the present invention provides a fragrance releaser for the silicate compound.
  • the present invention relates to a technique for sustained release of raspberry ketone, and provides a flavor release agent that is excellent in storage stability in an aqueous product and can be stably released over a long period of time in an actual use system.
  • the perfume-releasing agent of the present invention is excellent in storage stability in an aqueous product, and can stably and slowly release raspberry ketone over a long period of time in an actual use system regardless of the form and use of the preparation.
  • R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom or an optionally substituted alkyl group or aryl group having 1 to 30 carbon atoms.
  • R 1 , R 2 , R 3 and R 4 are residues obtained by removing the phenolic hydroxyl group from 4- (3-oxobutyl) phenol
  • R 1 , R 2 , R 3 and Two or three of R 4 are residues obtained by removing a hydroxyl group from a secondary or tertiary alcohol.
  • the fragrance-releasing agent of the present invention contains a silicate compound having such a structure, so that it has excellent storage stability in an aqueous product, and the raspberry ketone can be used for a long time in the actual use system regardless of the form and use of the preparation.
  • the reason why the sustained release can be stably performed is not clear, but is considered as follows. That is, a silicate compound substituted with phenol such as 4- (3-oxobutyl) phenol is generally subjected to hydrolysis because the electrons of silicon atoms are attracted to phenol and the electrons are insufficient. Easy and poor stability in water system.
  • the central silicon atom is substituted with two or three secondary or tertiary alcohols, electrons flow into these silicon atoms from these alcohols. It is considered that the electron shortage of atoms is eliminated, and the stability in aqueous systems is improved due to difficulty in hydrolysis. Further, since the secondary or tertiary alcohol is a bulky group, it is considered that the hydration to the central silicon atom hardly occurs and the stability is increased.
  • one of R 1 , R 2 , R 3 and R 4 is a residue obtained by removing a phenolic hydroxyl group from 4- (3-oxobutyl) phenol, and the remaining three are Embodiments in which the hydroxyl group is removed from a secondary or tertiary alcohol are included.
  • one of R 1 , R 2 , R 3 and R 4 is a residue obtained by removing the phenolic hydroxyl group from 4- (3-oxobutyl) phenol, and two of the other three are secondary or 3
  • An embodiment that is a residue obtained by removing a hydroxyl group from a secondary alcohol is also included.
  • the remaining one substituent is preferably a residue obtained by removing a hydroxyl group from a primary alcohol having 1 or more carbon atoms, the suppression of decomposition, and the viewpoint of enhancing the sustained release of a fragrance in an actual use system. Therefore, it is a residue obtained by removing a hydroxyl group from a primary alcohol having 6 or more carbon atoms, more preferably 8 or more carbon atoms. And from the viewpoint of sustainability, preferably a residue obtained by removing a hydroxyl group from a primary alcohol having 15 or less carbon atoms, more preferably 12 or less carbon atoms from the viewpoint of inhibiting decomposition and enhancing the sustained release of a fragrance in an actual use system.
  • a residue obtained by removing a hydroxyl group from a primary alcohol having 1 to 15 carbon atoms more preferably from the viewpoint of suppressing decomposition and enhancing the sustained release of a fragrance in an actual use system.
  • a residue obtained by removing a hydroxyl group from a primary alcohol having 6 to 12 carbon atoms more preferably a residue obtained by removing a hydroxyl group from a primary alcohol having 8 to 12 carbon atoms.
  • Such primary alcohols include lower alcohols such as ethanol and butanol, higher alcohols such as lauryl alcohol and stearyl alcohol, Gerve alcohols such as 2-ethylhexanol and 4-butyloctanol, and perfume alcohols such as geraniol and citronellol.
  • a fragrance alcohol is preferable from the viewpoint of imparting a complex fragrance and flavor, and a fragrance alcohol having a floral fragrance is preferable.
  • a perfume alcohol having an aroma is more preferable.
  • Geraniol or citronellol is preferred, and geraniol is more preferred.
  • the number of carbon atoms in the perfume alcohol is preferably 6 or more, more preferably 8 or more, from the viewpoint of sustainability.
  • the perfume alcohol preferably has 15 or less carbon atoms, more preferably 12 or less.
  • the fragrance alcohol preferably has 6 to 15 carbon atoms, more preferably 6 to 12 carbon atoms, still more preferably 8 to 12 carbon atoms, and even more preferably a terpene fragrance alcohol having 10 carbon atoms.
  • any of the above embodiments i) and ii) has the desired effect of the present application, but the embodiment i) is more preferable from the viewpoint of maintaining the function of 4- (3-oxobutyl) phenol.
  • the electron withdrawing by one phenol with respect to the central silicon atom and the electron donation by three secondary or tertiary alcohols the silicon atom becomes a balanced electronic state and the stability is improved.
  • the controlled release can be easily controlled.
  • the embodiment ii) is preferred.
  • 4- (3-Oxobutyl) phenol is a fragrance component that gives off a refreshing scent and is also excellent in moisturizing effect and blood circulation promotion (see, for example, JP-A-2008-195695). It is a fragrance that can particularly enjoy the effects of the present invention that can continuously exhibit its function in the use of textile product treating agents such as agents and softeners.
  • the silicate compound ( In 1) it is important that two or three of R 1 , R 2 , R 3 and R 4 are residues obtained by removing a hydroxyl group from a secondary or tertiary alcohol.
  • the two or three substituents may be any residue obtained by removing a hydroxyl group from a secondary alcohol, or both may be residues obtained by removing a hydroxyl group from a tertiary alcohol.
  • both a residue obtained by removing a hydroxyl group from a secondary alcohol and a residue obtained by removing a hydroxyl group from a tertiary alcohol may be combined, but 4- (3-oxobutyl) phenol is used in an actual use system. From the viewpoint of realizing sustained release in an amount sufficient to develop a function, it is particularly preferable that any of them is a residue obtained by removing a hydroxyl group from a secondary alcohol.
  • the fragrance releaser of the present invention is used not only when blended in an aqueous product or the like.
  • one of the remaining two is 4- (3-oxobutyl) phenol from the viewpoint of stably releasing the raspberry ketone over a long period of time. It is preferred that one of these is a primary alcohol. This is considered to be because the balance between the suppression of decomposition and the sustained release becomes extremely good by combining the secondary alcohol and the primary alcohol in this way.
  • suitable secondary alcohols include timberol (1- (2,2,6-trimethylcyclohexane-1-yl) -pentan-2-ol), menthol (2-isopropyl-5-methylcyclohexanol), amber Core (1- (2-t-butylcyclohexyloxy) -2-butanol), p-tertbutylcyclohexanol, o-tert-butylcyclohexanol, carveol, kohinol (3,4,5,6, 6-pentamethyl-2-heptanol), sandaroa (3-methyl-5- (2,2,3-trimethylcyclopenten-1-yl) -pentan-2-ol), 2-octyl alcohol, 2-nonyl alcohol, osirol , Forurodia (4-isopropylcyclohexanol), isopulegol, 3-heptanol, 3-octanol, 2-undecanol,
  • the secondary alcohol preferably has 6 or more carbon atoms, more preferably 9 or more from the viewpoint of suppressing decomposition and enhancing the sustained release of the fragrance in the actual use system.
  • the carbon number of the secondary alcohol is preferably 20 or less, and more preferably 14 or less.
  • the secondary alcohol preferably has 6 to 20 carbon atoms, and more preferably 9 to 14 carbon atoms.
  • the secondary alcohol is preferably a fragrance from the viewpoint of providing a complex fragrance and flavor.
  • the perfume preferably has 6 or more carbon atoms, more preferably 9 or more carbon atoms.
  • the fragrance preferably has 20 or less carbon atoms, and more preferably has 14 or less carbon atoms. Further, a fragrance having 6 to 20 carbon atoms is preferable, and a fragrance having 9 to 14 carbon atoms is more preferable.
  • the secondary alcohol preferably has a cyclic hydrocarbon, more preferably has a cyclohexane ring, from the viewpoint of suppressing decomposition and enhancing the sustained release of raspberry ketone in the actual use system.
  • a fragrance having 9 to 14 carbon atoms having a cyclohexane ring More preferred is a fragrance having 9 to 14 carbon atoms having a cyclohexane ring.
  • menthol (2-isopropyl-5-methylcyclohexanol), forlodia (4-isopropylcyclohexanol), amber core (1- (2-t-butylcyclohexyloxy) -2-butanol) is preferred, menthol (2-isopropyl-5-methylcyclohexanol) and forlodia (4-isopropylcyclohexanol) are more preferred, and menthol (2-isopropyl-5-methylcyclohexanol) is even more preferred.
  • tertiary alcohols examples include myrcenol (2-methyl-6-methylene-7-octen-2-ol), terpineol, linalool, 2,6-dimethylheptanol, 2-methyl-3-butene-2 -Ol, ambrinol, dihydrolinalol, tetrahydrolinalol, tetrahydromumol (2,6-dimethyl-2-octanol and 3,7-dimethyl-3-octanol), mugol (2,6-dimethyl-3,5-octadiene) -2-ol and 3,7-dimethyl-4,6-octadien-3-ol), dihydromyrcenol (2,6-dimethyl-7-octen-2-ol), tetrahydromyrcenol (2,6 -Dimethyl-2-octanol), osmenol, 3,6-dimethyl-3-oct
  • the tertiary alcohol preferably has 6 or more carbon atoms, and more preferably 9 carbon atoms from the viewpoint of suppressing decomposition and enhancing the sustained release of a fragrance in an actual use system.
  • the tertiary alcohol preferably has 20 or less carbon atoms, and more preferably 14 carbon atoms from the viewpoint of suppressing decomposition and enhancing the sustained release of the fragrance in the actual use system.
  • the tertiary alcohol preferably has 6 to 20 carbon atoms, more preferably 9 to 14 carbon atoms.
  • the tertiary alcohol is preferably a fragrance from the viewpoint of imparting a complex fragrance and flavor.
  • the perfume preferably has 6 or more carbon atoms, more preferably 9 or more carbon atoms.
  • the fragrance preferably has 20 or less carbon atoms, and more preferably has 14 or less carbon atoms. Further, it is preferably a fragrance having 6 to 20 carbon atoms, more preferably a fragrance having 9 to 14 carbon atoms, and further preferably a fragrance that is a terpene alcohol having 10 carbon atoms.
  • myrcenol (2-methyl-6-methylene-7-octen-2-ol), dihydromyrcenol (2,6-dimethyl-7-octen-2-ol) ), Tetrahydromyrcenol (2,6-dimethyl-2-octanol) is preferred, and tetrahydromyrcenol (2,6-dimethyl-2-octanol) is more preferred.
  • the secondary or tertiary alcohol preferably has 6 or more carbon atoms, more preferably 9 or more carbon atoms. Those having 20 or less carbon atoms are preferred, those having 15 or less carbon atoms are more preferred, those having 14 or less carbon atoms are more preferred, and those having 13 or less carbon atoms are still more preferred. From the viewpoint of obtaining the desired effect of the present application, the secondary or tertiary alcohol preferably has 6 to 20 carbon atoms, more preferably has 6 to 15 carbon atoms, and further has 9 to 14 carbon atoms. Those having 9 to 13 carbon atoms are more preferable.
  • menthol and forrosia which are secondary alcohols by directly bonding hydroxyl groups to skeletal carbon atoms constituting cyclic hydrocarbons, are the fastest of 4- (3-oxobutyl) phenol in aqueous products. This is particularly preferable from the viewpoints of suppressing decomposition / release and promoting sustained release of 4- (3-oxobutyl) phenol in an actual use system.
  • the fragrance releaser of the present invention contains the above silicate compound (1).
  • the content of the silicate compound (1) in the fragrance releaser is preferably 1% by mass or more, more preferably 10% by mass or more from the viewpoint of stably releasing the raspberry ketone over a long period of time. And 100 mass% or less is preferable, and 99 mass% or less is more preferable. Further, from the viewpoint of stably releasing the fragrance over a long period of time, 1 to 100% by mass is preferable, and 10 to 99% by mass is more preferable.
  • the fragrance releaser of the present invention contains, in addition to the silicate compound (1), a by-product produced during the production of the silicate compound, a condensate of the silicate compound, or a production raw material. May be.
  • the perfume release agent of the present invention can be produced by the following method 1 or 2.
  • Method 1 A method of transesterifying an alkoxysilane represented by the following formula (2) [hereinafter referred to as alkoxysilane (2)] with an alcohol, wherein the alcohol is 4- (3-oxobutyl) phenol, a secondary alcohol and A process comprising one or both of tertiary alcohols and optionally further primary alcohols.
  • alkoxysilane (2) an alkoxysilane represented by the following formula (2) [hereinafter referred to as alkoxysilane (2)] with an alcohol, wherein the alcohol is 4- (3-oxobutyl) phenol, a secondary alcohol and A process comprising one or both of tertiary alcohols and optionally further primary alcohols.
  • R a represents an alkyl group having 1 to 6 carbon atoms, and a plurality of R a may be the same or different.
  • Method 2 A method of esterifying a halogenated silane represented by the following formula (3) [hereinafter referred to as halogenated silane (3)] with an alcohol, wherein the alcohol is 4- (3-oxobutyl) phenol and a secondary A method comprising one or both of an alcohol and a tertiary alcohol, and optionally further a primary alcohol.
  • halogenated silane (3) a halogenated silane represented by the following formula (3) [hereinafter referred to as halogenated silane (3)] with an alcohol, wherein the alcohol is 4- (3-oxobutyl) phenol and a secondary A method comprising one or both of an alcohol and a tertiary alcohol, and optionally further a primary alcohol.
  • R a is preferably a methyl group or an ethyl group, and more preferably an ethyl group, from the viewpoint of availability.
  • 4- (3-oxobutyl) phenol used in Method 1 and one or both of a secondary alcohol and a tertiary alcohol, and optionally an alcohol containing a primary alcohol may be mixed and reacted at once. However, they may be added separately and reacted stepwise. Since the transesterification reaction is accompanied by equilibration, a method having almost the same composition distribution can be obtained by any method. It is convenient and preferable to use a mixture of both.
  • the molar ratio of alcohol to alkoxysilane (2) is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1 or more. And 10 or less is preferable, 7 or less is more preferable, and 5 or less is still more preferable.
  • the molar ratio of alcohol to alkoxysilane (2) is preferably from 0.1 to 10, more preferably from 0.5 to 7, still more preferably from 1 to 5.
  • the reaction temperature of the transesterification reaction in Method 1 includes alkoxysilane (2) and alcohols, that is, 4- (3-oxobutyl) phenol, and one or both of secondary alcohol and tertiary alcohol, and optionally further primary alcohol.
  • the boiling point of the alcohols containing is preferably at most room temperature (20 ° C.) or more, more preferably at least 50 ° C., even more preferably at least 90 ° C., particularly preferably at least 110 ° C.
  • 200 degrees C or less is more preferable, 190 degrees C or less is still more preferable, 180 degrees C or less is still more preferable, 170 degrees C or less is especially preferable.
  • reaction temperature of the transesterification reaction in Method 1 is more preferably room temperature (20 ° C.) to 200 ° C., further preferably 50 to 190 ° C., still more preferably 90 ° C. to 180 ° C., and particularly preferably 110 ° C. to 170 ° C. preferable.
  • the transesterification reaction in Method 1 is preferably performed under reduced pressure from the viewpoint that the reaction can proceed rapidly.
  • the degree of vacuum depends on the reaction temperature, but alkoxysilane (2) and alcohols, that is, 4- (3-oxobutyl) phenol, one or both of secondary alcohol and tertiary alcohol, and optionally further primary alcohol. What is necessary is just to perform below the boiling point of alcohol to contain, 1.3 Pa or more is preferable, 130 Pa or more is more preferable, 1.3 kPa or more is still more preferable. And normal pressure (0.1 MPa) or less is preferable, 40 kPa or less is more preferable, and 13 kPa or less is still more preferable.
  • 1.3 Pa to normal pressure (0.1 MPa) is preferable, 130 Pa to 40 kPa is more preferable, and 1.3 kPa to 13 kPa is still more preferable.
  • the reaction may be performed under reduced pressure from the beginning of the reaction or under reduced pressure from the middle.
  • the catalyst include alkali catalysts such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metals such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide and the like.
  • Lewis acid catalysts such as aluminum tetraisopropoxide and titanium tetraisopropoxide can be used.
  • an alkali catalyst It is more preferable to use an alkoxide having a number of 1 to 3.
  • the amount of the alkali catalyst is preferably 0.05 to 0.5 mol% with respect to the alkoxysilane (2).
  • the amount of 4- (3-oxobutyl) phenol is preferably 0.5 mol times or more, more preferably 0.8 mol times or more with respect to the alkoxysilane (2). And it is preferable that it is 2 mol times or less, and it is more preferable that it is 1.3 mol times or less. Further, it is preferably 0.5 to 2 mole times, more preferably 0.8 to 1.3 mole times.
  • examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
  • 4- (3-oxobutyl) phenol one or both of a secondary alcohol and a tertiary alcohol, and optionally further a primary alcohol may be mixed and used separately. And may be reacted stepwise.
  • 4- (3-oxobutyl) phenol or other alcohols may be used first, but the reaction rate is better when 4- (3-oxobutyl) phenol, which is less reactive, is used first. Is preferable from the viewpoint of increasing.
  • the reactivity of the halogenated silane tends to be faster when the first group X is replaced and slower toward the fourth. Therefore, it is preferable that the reaction is performed stepwise separately in that a product having a small distribution of substituents can be obtained. On the other hand, the use of a mixture of alcohols is preferable in that an alcohol having an appropriate distribution of substituents is obtained and the release property is widened.
  • the molar ratio of the alcohol to the halogenated silane (3) is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1 or more. And 10 or less is preferable, 7 or less is more preferable, and 5 or less is still more preferable.
  • the molar ratio of the alcohol to the halogenated silane (3) is preferably from 0.1 to 10, more preferably from 0.5 to 7, still more preferably from 1 to 5.
  • Method 2 since an acid is by-produced as the reaction proceeds, it is preferable to react by adding a base.
  • the base to be used include tertiary amines such as triethylamine, pyridine, imidazole and the like.
  • a solvent may be used from the viewpoint of a large amount of salt by-products, and the reaction temperature may be a low temperature at which the substrate and the solvent do not solidify.
  • various known devices / equipment can be used.
  • desalting a known method such as filtration, extraction, electrodialysis, or the like can be used.
  • the perfume release agent of the present invention obtained by the transesterification reaction of Method 1 and the esterification reaction of Method 2 may contain a silicate compound having a different degree of substitution in addition to the silicate compound (1). It may contain a chain or cyclic polycondensate condensed with siloxane.
  • the fragrance-releasing agent of the present invention containing the silicate compound (1) can suppress the rapid degradation of the fragrance even when incorporated in an aqueous product, and 4- (3-oxobutyl) phenol can be used in an actual use system. Can be sustainedly released over a long period of time, and various functions derived from the fragrance can be continuously expressed.
  • the fragrance releasing agent of the present invention or the composition containing the fragrance releasing agent of the present invention is a fragrance precursor that gradually releases 4- (3-oxobutyl) phenol contained in the fragrance releasing agent of the present invention by hydrolysis. It is preferable that the above-mentioned effect is manifested by a method of slowly releasing 4- (3-oxobutyl) phenol, which is a composition and contained in the fragrance release agent of the present invention, by hydrolysis.
  • fragrance release agent of the present invention it is possible to suppress degradation in a product even in an embodiment in which raspberry ketone, which was extremely poor in stability in an aqueous product, can be suppressed and refreshed in an actual use system.
  • Raspberry ketone that excels in scent and moisturizes and promotes blood circulation can be continuously expressed, and finds its usefulness especially in textile treatments such as garment detergents and softeners. Is.
  • the excellent effect of the fragrance releaser of the present invention has been described mainly in relation to the use of fiber treatment agents such as garment detergents and softening finishes, but only for fiber treatment agents.
  • the perfume release agent of the present invention may be incorporated into various products.
  • non-aqueous products such as oil-based deodorant fragrances, powder detergents, bar soaps, bathing agents, diapers and other non-aqueous products such as aerosol deodorants are naturally excellent in storage stability in aqueous solutions. Therefore, it is used for perfume, colon, water-based deodorant fragrance, tableware detergent, various cosmetics such as liquid soap and lotion, hair products such as shampoo, rinse, conditioner and styling agent, liquid bath agent, etc.
  • various functions of raspberry ketone can be continuously expressed.
  • the content of the fragrance releaser of the present invention in each of these products is not particularly limited, and can be appropriately changed according to the use.
  • a fiber treatment agent composition such as a cleaning composition for clothing or a softener finishing composition
  • the content of the fragrance release agent in the composition is a silicate compound (1 ) Is preferably 0.001% by mass or more, and more preferably 0.01% by mass or more. And 10 mass% or less is preferable, and 5 mass% or less is more preferable. Further, 0.001 to 10% by mass is preferable, and 0.01 to 5% by mass is more preferable.
  • the content of the fragrance releasing agent in the composition is preferably 0.001% by mass or more, and more preferably 0.01% by mass or more. And 90 mass% or less is preferable, and 10 mass% or less is more preferable.
  • the content of the fragrance releaser in the composition is preferably 0.001 to 90% by mass, more preferably 0.01 to 10% by mass. preferable.
  • flavor releasing agent in a composition has preferable 0.0001 mass% or more, and 0.001 mass% or more is more preferable.
  • the content of the fragrance releasing agent in the composition is preferably 0.0001 to 10% by mass, more preferably 0.001 to 5% by mass.
  • composition of perfume release agent The composition of the fragrance releaser shown in the following examples and comparative examples was determined by gas chromatography (GC) analysis under the following analysis conditions.
  • GC device Agilent 7890A Column: manufactured by Agilent, DB-1HT (15 m ⁇ 0.25 mm ⁇ 0.10 ⁇ m) Carrier gas: He (1 ml / min.) Inlet temperature: 300 ° C Injection volume: 1 ⁇ l Injection method: Split (split ratio 100: 1) Oven temperature condition: 100 ° C. ⁇ (10 ° C./min.) ⁇ 340° C. (20 min. Hold) Detector: FID Detector temperature: 300 ° C
  • Example 1 Synthesis of perfume-releasing agent containing Si (ORasp) (OMmentyl) 3
  • a 500 mL four-necked flask 83.33 g (0.40 mol) tetraethoxysilane, 72.25 g (0.44 mol) raspberry ketone, 206.28 g (1.32 mol) menthol, 5.275%
  • a sodium ethoxide ethanol solution (0.71 g) was added, and the mixture was stirred at 135 to 160 ° C. for about 2 hours while distilling ethanol under a nitrogen stream. After 2 hours, the pressure in the tank was gradually lowered to 6 kPa, and the mixture was further stirred at about 160 ° C. for 22 hours while distilling ethanol.
  • Rasp represents a residue obtained by removing one phenolic hydroxyl group from raspberry ketone
  • Menthyl represents a residue obtained by removing one hydroxyl group from menthol. The same applies hereinafter.
  • Example 2 Synthesis of a fragrance releaser containing Si (ORasp) (Ofolosia) 3
  • a 0.55 g% sodium ethoxide ethanol solution was added, and the mixture was stirred at 150 ° C. for about 2 hours while distilling ethanol under a nitrogen stream. After 2 hours, the pressure in the tank was gradually lowered to 4 kPa, and the mixture was further stirred at about 150 ° C. for 15 hours while distilling ethanol.
  • Folrosia is a residue obtained by removing one hydroxyl group from forrosia.
  • Example 3 Synthesis of a perfume release agent containing Si (ORasp) (OMentyl) 2 (OGer) In a 500 mL four-necked flask, 83.33 g (0.40 mol) tetraethoxysilane, 78.82 g (0.48 mol) raspberry ketone, 125.02 g (0.80 mol) menthol Then, 74.04 g (0.48 mol) of geraniol and 0.77 g of a 5.275% sodium ethoxide ethanol solution were added, and the mixture was stirred at 160 ° C. for about 2 hours while distilling ethanol under a nitrogen stream.
  • Ger represents a residue obtained by removing one hydroxyl group from geraniol.
  • Example 4 Synthesis of perfume release agent containing Si (ORasp) (OAmbercore) 3
  • a 0.15 g% sodium methoxide methanol solution was added, and the mixture was stirred at 130 ° C. for about 4 hours while distilling ethanol under a nitrogen stream. After 4 hours, the pressure in the tank was gradually lowered to 1.3 kPa, and the mixture was further stirred at 160 ° C. for 1 hour while distilling ethanol.
  • Ambercore is a residue obtained by removing one hydroxyl group from amber core, and Et is an ethyl group.
  • Example 5 Synthesis of Perfume Release Agent Containing Si (ORasp) (OTHmyrenyl) 3 35 ml of methyl ethyl ketone and 11.89 g (0.07 mol) of tetrachlorosilane were added to a 500 mL four-necked flask. A solution prepared by dissolving 33.24 g (0.21 mol) of tetrahydromyrcenol and 21.45 g (0.32 mol) of imidazole in methyl ethyl ketone (105 ml) was added dropwise to the flask over 10 minutes.
  • THmyrcenyl represents a residue obtained by removing one hydroxyl group from tetrahydromyrcenol.
  • Citronellyl represents a residue obtained by removing one hydroxyl group from citronellol.
  • Evaluation criteria 5 Very strong smell 4: Very strong smell 3: Strong smell 2: Smell (cognitive threshold) 1: Smell slightly (detection threshold) 0: Does not smell
  • Evaluation criteria 5 Very strong smell 4: Very strong smell 3: Strong smell 2: Smell (cognitive threshold) 1: Smell slightly (detection threshold) 0: Does not smell
  • Example 13 Preparation of shampoo as hair cosmetics
  • the perfume release agent of the present invention obtained in Examples 1 to 3 and the comparative perfume release agent obtained in Comparative Examples 1 and 2 were mixed in the beaker at 25 ° C. with the formulation shown in Table 12.
  • a shampoo was prepared.
  • Evaluation criteria 5 Very strong smell 4: Very strong smell 3: Strong smell 2: Smell (cognitive threshold) 1: Smell slightly (detection threshold) 0: Does not smell
  • the present invention further discloses the following agent, composition, production method, method of use or application.
  • a fragrance releaser comprising a silicate compound represented by formula (1).
  • R 1 , R 2 , R 3 and R 4 are each independently a C 1-30 alkyl group or aryl group which may have a substituent, and R 1 , R 2 , R 3 And R 4 is a residue obtained by removing a phenolic hydroxyl group from 4- (3-oxobutyl) phenol, and two or three of R 1 , R 2 , R 3 and R 4 are 2 This is a residue obtained by removing a hydroxyl group from a tertiary or tertiary alcohol.
  • ⁇ 2> The fragrance releaser according to ⁇ 1>, wherein two or three of R 1 , R 2 , R 3 and R 4 are residues obtained by removing a hydroxyl group from a secondary alcohol.
  • ⁇ 3> The fragrance releaser according to ⁇ 2>, wherein the secondary alcohol has preferably 6 or more, more preferably 9 or more, and preferably 20 or less, more preferably 14 or less.
  • ⁇ 4> The fragrance releaser according to ⁇ 2> or ⁇ 3>, wherein the secondary alcohol has a cyclic hydrocarbon.
  • ⁇ 5> The fragrance releaser according to any one of ⁇ 2> to ⁇ 4>, wherein the secondary alcohol has a cyclohexane ring.
  • ⁇ 6> The fragrance releaser according to any one of ⁇ 2> to ⁇ 5>, wherein a hydroxyl group of the secondary alcohol is directly bonded to a skeleton carbon atom constituting the cyclic hydrocarbon.
  • ⁇ 7> The fragrance releaser according to any one of ⁇ 2> to ⁇ 6>, wherein the secondary alcohol is a fragrance.
  • ⁇ 8> The fragrance releaser according to any one of ⁇ 2> to ⁇ 7>, wherein the secondary alcohol is a fragrance having 6 or more carbon atoms, preferably 9 or more, and 20 or less, preferably 14 or less.
  • ⁇ 12> The fragrance releaser according to ⁇ 11>, wherein the primary alcohol has 1 or more, preferably 6 or more, more preferably 8 or more, and 15 or less, preferably 12 or less.
  • ⁇ 13> The fragrance releaser according to ⁇ 11> or ⁇ 12>, wherein the primary alcohol is a fragrance alcohol.
  • ⁇ 14> The fragrance releaser according to any one of ⁇ 11> to ⁇ 13>, wherein the primary alcohol is a fragrance having a rose-like fragrance.
  • ⁇ 15> The fragrance releaser according to any one of ⁇ 11> to ⁇ 14>, wherein the primary alcohol is geraniol.
  • the silicate compound represented by the formula (1) is contained in an amount of 1% by mass or more, preferably 10% by mass or more, and 100% by mass or less, preferably 99% by mass or less.
  • Perfume release agent ⁇ 17> A fragrance precursor composition that releases the 4- (3-oxobutyl) phenol contained in the fragrance releaser according to any one of ⁇ 1> to ⁇ 15> by hydrolysis.
  • ⁇ 18> A fiber product treating agent composition comprising the fragrance releaser according to any one of ⁇ 1> to ⁇ 15>.
  • a softener composition comprising the fragrance releaser according to any one of ⁇ 1> to ⁇ 15>.
  • ⁇ 20> A hair cosmetic containing the fragrance releaser according to any one of ⁇ 1> to ⁇ 15>.
  • ⁇ 21> A method in which the 4- (3-oxobutyl) phenol contained in the fragrance releaser according to any one of ⁇ 1> to ⁇ 15> is gradually released by hydrolysis.
  • ⁇ 22> The method for producing a fragrance releaser according to any one of ⁇ 1> to ⁇ 16>, wherein the alkoxysilane represented by formula (2) and an alcohol are transesterified, wherein the alcohol is 4- (3-oxobutyl)
  • R a represents an alkyl group having 1 to 6 carbon atoms, and a plurality of R a may be the same or different.
  • the molar ratio of the alcohol to the alkoxysilane of the formula (2) is 0.1 or more, preferably 0.5 or more, more preferably 1 or more, and 10 or less, preferably 7 or less, more preferably 5 or less.
  • the transesterification reaction temperature is lower than the boiling points of the alkoxysilane of formula (2) and the alcohol, preferably room temperature (20 ° C) or higher, more preferably 50 ° C or higher, and still more preferably 90 ° C or higher. 110 ° C. or higher, more preferably 200 ° C. or lower, still more preferably 190 ° C. or lower, still more preferably 180 ° C. or lower, and particularly preferably 170 ° C. or lower, ⁇ 22> to ⁇ 24>
  • a method for producing a release agent is lower than the boiling points of the alkoxysilane of formula (2) and the alcohol, preferably room temperature (20 ° C) or higher, more preferably 50 ° C or higher, and still more preferably 90 ° C or higher. 110 ° C. or higher, more preferably 200 ° C. or lower, still more preferably 190 ° C. or lower, still more preferably 180 ° C. or lower, and particularly preferably 170 ° C. or lower, ⁇ 22>
  • the transesterification reaction is carried out under reduced pressure, preferably 1.3 Pa or more, more preferably 130 Pa or more, further preferably 1.3 kPa or more, preferably normal pressure (0.1 MPa) or less, more preferably 40 kPa or less.
  • ⁇ 28> The method for producing a fragrance releaser according to ⁇ 27>, wherein the alkali catalyst is an alkali metal alkoxide having 1 to 3 carbon atoms.
  • the amount of the alkali catalyst is 0.05 to 0.5 mol% with respect to the alkoxysilane of the formula (2).
  • the amount of 4- (3-oxobutyl) phenol is 0.5 mol times or more, preferably 0.8 mol times or more, and 2 mol times or less with respect to the alkoxysilane of formula (2), preferably 1.
  • ⁇ 31> The method for producing a fragrance releaser according to any one of ⁇ 1> to ⁇ 16>, wherein the halogenated silane represented by formula (3) and an alcohol are esterified, wherein the alcohol is 4- (3- A method for producing a fragrance releaser comprising oxobutyl) phenol and one or both of a secondary alcohol and a tertiary alcohol. (In the formula, X represents a halogen atom.)
  • ⁇ 32> The method for producing a fragrance releaser according to ⁇ 31>, wherein the alcohol further contains a primary alcohol.
  • the molar ratio of the alcohol to the halogenated silane of the formula (3) is 0.1 or more, preferably 0.5 or more, more preferably 1 or more, and 10 or less, preferably 7 or less, more preferably 5 or less.
  • ⁇ 35> The fragrance releaser of the silicate compound according to any one of ⁇ 1> to ⁇ 15>.
  • ⁇ 36> Use of a fragrance-releasing agent for a silicate compound obtained by the production method according to any one of ⁇ 22> to ⁇ 33>.

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  • Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Fats And Perfumes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

La présente invention concerne un agent libérant un parfum qui contient un composé de type ester d'acide silicique représenté par la formule (1). Formule (1): Si(OR1)(OR2)(OR3)(OR4) (Dans la formule, chacun des R1, R2, R3 et R4 représente indépendamment l'un de l'autre un atome d'hydrogène, un groupe alkyle comportant de 1 à 30 atomes de carbone, un groupe aryle ou équivalent ; l'un des R1, R2, R3 et R4 représente un résidu résultant de l'élimination d'un groupe hydroxyphénolique d'un 4-(3-oxobutyl)phénol ; et deux ou trois des autres R1, R2, R3 et R4 représentent des résidus résultant de l'élimination d'un groupe hydroxyle d'alcools secondaires ou tertiaires.)
PCT/JP2012/068751 2011-07-26 2012-07-25 Agent libérant un parfum WO2013015293A1 (fr)

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Cited By (3)

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JP2013047325A (ja) * 2011-07-26 2013-03-07 Kao Corp 香料放出剤
JP2017014158A (ja) * 2015-07-02 2017-01-19 花王株式会社 毛髪化粧料
US11447724B2 (en) 2019-03-08 2022-09-20 The Procter & Gamble Company Compositions that include siloxane compounds having pendant silyl ether moieties

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JP7108016B2 (ja) * 2020-12-23 2022-07-27 長谷川香料株式会社 香料前駆体としてのジエステル化合物

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JP2000096078A (ja) * 1993-11-11 2000-04-04 Kanebo Ltd 人体表面用徐放性芳香組成物
JP2002516264A (ja) * 1998-05-28 2002-06-04 フイルメニツヒ ソシエテ アノニム ２−ベンゾイルベンゾエート、２−アルカノイルベンゾエート又はα−ケトエステルを用いる香料中の芳香化合物の徐放
JP2009197055A (ja) * 2008-02-19 2009-09-03 Kao Corp 機能性物質放出剤
JP2009242798A (ja) * 2008-03-14 2009-10-22 Kao Corp 機能性物質放出剤

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AU6601900A (en) * 2000-04-17 2001-10-30 Vyacheslav Vasilievich Kireev Silicon derivatives of fragrant, flavouring and medicinal substances
ES2312635T3 (es) * 2001-12-13 2009-03-01 Firmenich Sa Compuestos para una liberacion controlada de moleculas activas.
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JPH07179328A (ja) * 1993-11-11 1995-07-18 Kanebo Ltd 人体用徐放性芳香組成物
JP2000096078A (ja) * 1993-11-11 2000-04-04 Kanebo Ltd 人体表面用徐放性芳香組成物
JP2002516264A (ja) * 1998-05-28 2002-06-04 フイルメニツヒ ソシエテ アノニム ２−ベンゾイルベンゾエート、２−アルカノイルベンゾエート又はα−ケトエステルを用いる香料中の芳香化合物の徐放
JP2009197055A (ja) * 2008-02-19 2009-09-03 Kao Corp 機能性物質放出剤
JP2009242798A (ja) * 2008-03-14 2009-10-22 Kao Corp 機能性物質放出剤

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013047325A (ja) * 2011-07-26 2013-03-07 Kao Corp 香料放出剤
JP2017014158A (ja) * 2015-07-02 2017-01-19 花王株式会社 毛髪化粧料
US11447724B2 (en) 2019-03-08 2022-09-20 The Procter & Gamble Company Compositions that include siloxane compounds having pendant silyl ether moieties

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CN103717721A (zh) 2014-04-09
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