GB2444702A - Volatile compositions having an end-of-life indication - Google Patents

Volatile compositions having an end-of-life indication Download PDF

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Publication number
GB2444702A
GB2444702A GB0624857A GB0624857A GB2444702A GB 2444702 A GB2444702 A GB 2444702A GB 0624857 A GB0624857 A GB 0624857A GB 0624857 A GB0624857 A GB 0624857A GB 2444702 A GB2444702 A GB 2444702A
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United Kingdom
Prior art keywords
acid
composition
volatile
composition according
fragrance
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GB0624857A
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GB0624857D0 (en
Inventor
Philippe Blondeau
Alice Bresson Boil
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Givaudan SA
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Givaudan SA
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Priority to GB0624857A priority Critical patent/GB2444702A/en
Publication of GB0624857D0 publication Critical patent/GB0624857D0/en
Publication of GB2444702A publication Critical patent/GB2444702A/en
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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00Disinfection, sterilisation or deodorisation of air
    • A61L9/015Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
    • A61L9/04Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating
    • A61L9/12Apparatus, e.g. holders, therefor
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00Disinfection, sterilisation or deodorisation of air
    • A61L9/01Deodorant compositions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00Disinfection, sterilisation or deodorisation of air
    • A61L9/015Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
    • A61L9/04Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q13/00Formulations or additives for perfume preparations

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)

Abstract

A non-aqueous composition comprising a halochromic dye, a fragrance material, a non-volatile base or acid, and a highly polar, low volatile solvent is disclosed. The composition changes its colour when the predominant part of the fragrance material has evaporated over time. The preferred composition comprises Bromocresol Green as the dye, triethanolamine as the non-volatile base, dipropylenglycole as the solvent, and a fragrance composition. Also claimed is an air-freshener device in which a composition of the present invention is absorbed or adsorbed in a material selected from paper, textiles, felt-type materials, wovens and non-wovens, glass fibre filters and crystals.

Description

ORGANIC COMPOSITION
The present invention is generally directed to volatile compositions having an end-of-life indication and to systems comprising them. Particularly the present invention is generally directed to air-freshener systems useful in dispensing volatile substances, e.g. fragrance materials, which also include an end-of-life indicator.
Air-freshener systems typically include a volatile material, often included within a carrier substance which, when exposed to the air-space of the ambient environment, volatilizes over time, until essentially all of the volatile material has been delivered from the air-freshener system. While such a system is elegant in its simplicity and is effective, it suffers from the shortcoming that typically there is no visibly discernable indicator of the end of the useful life of the air-freshener system provided to the user of the device. There is thus nothing to indicate that a further air-freshener system should be purchased and used in the place of the depleted system, or that the depleted system should be refilled with a fresh ::::: supply of volatile material.
* . To overcome this shortcoming, the prior art has proposed various solutions. Indicator systems specially intended for air freshener systems are, for example, described in US * 20 Patent 4,128,508, which indicator system is based on the change in color of a pH indicator *** * combined with a slowly evaporating acid or base. Such systems have the disadvantage that the choice of suitable volatile acids and bases is limited, inter alia, because they often have * .: a strong and usually undesirable smell of their own. In addition, this system only works for aqueous-based perfume compositions.
International Patent application WO 03/031966 describes a system, which is based on volatile dyes, which are coated on a substrate thereby coloring the substrate. As the volatile dye evaporates over time, the substrate changes color. While such a system provides certain advantages, nonetheless it requires that a substrate be coated in a first step before the fragrance is added.
While the prior art provides certain useful systems, nonetheless there remains a real and continuing need in the art to provide further means which provide an indication of the consumption of a volatile, in particular a fragrance.
Surprisingly it has been found that halochromic dyes, i.e. materials which are known to the person skilled in the art as materials that change their color when pH changes occur, when used with non-aqueous composition, change their color as the volatile material evaporates over time, thus indicating that the composition has become ineffective.
Accordingly, the present invention refers in one of its aspects to a non-aqueous composition comprising a halochromic dye, a fragrance material, a non-volatile base or acid, and a highly polar, low volatile solvent, said composition changing its color when the predominant part of the fragrance material has evaporated over time. I0
By "non-aqueous composition" is meant a composition, in particular a liquid, which is essentially free of water, i.e. containing less than 1% by weight of water based on the total composition.
: *., 15 Suitable fragrance materials may be selected from the extensive range of natural products **..
and synthetic molecules currently available, such as essential oils, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, macrocylces and heterocycles. Such *.: fragrance materials are described, for example, in S. Arctander Perfume Flavors and Chemicals Vols. 1 and 2, Arctander, Montclair NJ USA 1989.
S..... * .
By "non-volatile" is meant any material having a maximum vapor pressure of 0.025mm Hg (preferably a maximum of 0.01mm Hg) at 20 C. Non-volatile bases may be selected from the non-limiting list consisting of tnethanolamine (TEA), 4-methyiphenyl amine and 4-dimethylaminopyridine (DMAP). Non-volatile acids may be selected from the non-limiting list consisting of citric acid, lauric acid, stearic acid, linoleic acid, acrylic acid, pyruvic acid, nicotinic acid, acetylsalicylic acid, and the like.
Examples of highly polar, low volatile solvents include dipropylenglycole (DPG), triethyleneglycol (TEG), propyleneglycol (PG), glycerine, 2-methyl-i,3-propanediol, tripropyleneglycol methyl ether (Dowanol TPM), and the like.
Preferably, the highly polar, low volatile solvent has a maximum vapor pressure of 0.1mm Hg at 20 C. By "highly polar" is meant that the selected solvent is able to solubilize more or at least 0.1 weight % of the halochromic dye which is intended to be used in the composition..
The composition according to the present invention preferably comprises at least 40 weight %, e.g. 80 weight % or more, preferably 90 weight % or more, such as 95%, of a fragrance material based on the total composition.
By "halochromic dye" is meant any material known to be a material that changes color when pH changes occur. Suitable halochromic dyes may be selected from the non-limiting list consisting of 2,4-Dinitrophenol (CAS 51-28-5), Alizarin sodium sulfonate (CAS 130-22-3), Alizarin yellow (CAS 476-66-4), a-Naphtholbenzein (CAS 145-50-6), a-Naphtholphthalein (CAS 596-01-0), a-Naphtyl red (CAS 1260-17-9), Azolitmin (CAS 1395-18-2), Oracet blue 2R (CAS 4395-65-7), Bromocresol green (CAS 76-60-8), Bromocresol purple (CAS 115-40- 2), Bromophenol blue (CAS 115-39-9), Bromothylmol blue (CAS 76-59-5), Clorophenol red ::. 15 (CAS 4430-20-0), Congo red (CAS 117-92-0), Cresol red (CAS 1733-12-6), Crystal violet * *, (CAS 548-62-9), Diazo violet (CAS 6528-37-6), Methyl yellow (CAS 60-11-7), Methyl orange *.S.
(CAS 547-58-0), Methyl red (CAS 493-52-7), Methyl violet 2B (CAS 8004-87-3), Neutral red (CAS 553-24-2), Nile blue (CAS 3625-57-8), p-Ethoxychrysoidine (CAS 94-10-0), p- *: Nitrophenol (CAS 100-02-7), Pentamethoxy red (GAS 1755-51-7), Phenol red (CAS 143-74- 8), Phenolphthalein (GAS 77-09-8), Poirrier's blue (GAS 1400-96-0), Rosolic acid (CAS 603-S..
45-2), Salicyl yellow (CAS 584-42-9), Tetrabromphenol blue (CAS 4430-25-5), Thymol blue (CAS 76-61-9), Thymolphthalein (CAS 125-20-2) and Trinitrobenzoic acid (CAS 129-66-8) In a preferred embodiment, the halochromic dye is selected from the triphenylmethane family of so-called triarylmethane dyes, for example, Bromocresol green.
Extensive research revealed that halochromic dyes used in compositions according to the present invention change their color as a consequence of to the Hansen polar solubility parameter () and the Hansen hydrogen bonding solubility parameter (8H) of the fragrance material in which the dye is dissolved. These parameters may be evaluated as disclosed, for example, in Hansen Solubility Parameters: A User's Handbook" (Charles M. Hansen, CRC Press, 2000) or/and by using software available on the market, such as Molecular Modeling Pro from www.Chemistry-Software.com. The data given in Table 1 below have been calculated using the algorithm of Molecular Modeling Pro from Chemistry ChemSW for calculating 8 and E based on group contribution as described on page 9-10 of "Hansen Solubility Parameters: A User's Handbook" (Charles M. Hansen, CRC Press, 2000).
Fig. 1 illustrates, graphically, the data presented in Table 1, and more specifically the relation between the solubility parameters H and 6p.
As is further illustrated by the examples, Bromocresol green provides a clearly visible color change indicator from yellow to blue as the fragrance material evaporates over time, and is thus preferred. It has been found that non-aqueous compositions comprising -Bromocresol green -fragrance materials having a polar solubility parameter (8p) <= 7.5(MPa)"2, a hydrogen bonding solubility parameter (oH) <= 30 (MPa)"2 and 0H < -4 * Op + 30, -high polar, low volatile solvant, and -a non-volatile base, such as triethanolamine, : * : :: 15 change their color from yellow to blue when the predominant part of the fragrance material has evaporated over time thus indicating that the composition has become ineffective. * S..
By "predominant part" is meant that more than 50 weight % of the fragrance material, preferably at least 75%, e.g. at least 80%, is evaporated. S..
Accordingly, the present invention refers in a further aspect to a non-aqueous composition S. * . .: compnsing a) Bromocresol green, b) a fragrance composition consisting of at least 30 weight %, preferably at least 50 weight % , e.g. 60, 70 or 80 weight %, of a fragrance material having a polar solubility parameter (Op) < 7.5(MPa)"2, a hydrogen bonding solubility parameter (OH) < 30 (MPa)112 and 0H <= -4 * +30; c) high polar, low volatile solvent; and d) a non-volatile base.
The composition according to the present invention may further comprise excipients generally used in combination with air-freshener compositions, such as malodorant counteracting compounds, antibacterials and insect repellents.
The composition provided by this invention can be absorbed into absorbent bases such as paper, textiles, felt-type materials, wovens and nonwovens, bonded or sintered synthetic or natural polymer powders, cellulose or unglazed ceramics, or adsorbed onto glass fiber filters, or crystals such as rock salt crystals or silica gel crystals.
The invention is now further described with reference to the following non-limiting examples.
These examples are for the purpose of illustration only and it is understood that variations and modifications can be made by one skilled in the art.
Example 1: non-aqueous compositions comprising Bromocresol green g of a volatile material as indicated in the table below were mixed with 5 g of a blend of Bromocresol green, triethanolamine (TEA) and dipropylene glycol (DPG) (0.7 weight % TEA, 0.1 weight % Bromocresol green and 99.2 weight % DPG), resulting in a yellow or green : *". 15 compositions. Each individual mixture changed its color to blue after approximately 90 *.S.
i... weight % of the volatile material was evaporated over time. *S..
Table 1: solubility parameters and 6H of volatile materials
S
* S.... * .
volatile material color of the mixture * S ::. acetophenone 6.7 4.2 green : isopropyl alcohol 6.6 16.2 green phenyl ethyl alcohol 4.4 13. 2 green aldehyde c12 mna (2-methylundecanal) 3.4 4.4 yellow capronaldehyde 5.9 5.8 yellow citronellyl acetate 2.2 5.6 yellow ethyl acetate 4.8 8.3 yellow cis-3-hexen-1-ol 2.9 6.4 yellow undecavertol (4-methyl-3-decen-5-ol) 2.5 10.0 yellow Mapping the two solubility parameters 6p and oH the curve (OH = -4 Op +30) shows a clear defined boundary between volatile compounds showing a yellow coloration when mixed with a mixture comprising Bromocresol green, DPG and TEA and a green coloration respectively (see Figure 1). * ** * * * *.*. **** * * **** 0* * * * * * **
S
* ***.S * * *** * I * S.. I. * * .. **

Claims (12)

  1. Claims 1. A non-aqueous composition comprising a halochromic dye, a
    fragrance material, a non-volatile acid or base, and a highly polar, low volatile solvent, said composition changing its color when the predominant part of the fragrance material has evaporated over time.
  2. 2. A composition according to claim 1 wherein the highly polar, low volatile solvent has a maximum vapour pressure of 0.1mm Hg at 20 C.
  3. 3. A composition according to claim 1 or claim 2, wherein the non-volatile acid or base has a maximum vapour pressure of 0.01 mm Hg at 20 C.
  4. 4. A composition according to any one of the preceding claims wherein the highly polar low volatile solvent is selected from the list consisting of dipropylenglycole, triethyleneglycol, propyleneglycol, glycerine, 2-methyl-i,3-propanediol and * ** tripropyleneglycol methyl ether. *
  5. 5. A composition according to any one of the preceding claims wherein the non-volatile acid is selected from the group consisting of citric acid, lauric acid, steanc acid, linoleic acid, acrylic acid, pyruvic acid, nicotinic acid and acetylsalicylic acid.
    **.*s* * * *
  6. 6. A composition according to any one of claims 1-4 wherein the non-volatile base is *:*. selected from the group consisting of triethanolamine, 4-methylphenyl amine and 4-dimethylaminopyridine.
  7. 7. A composition according to claim 1 wherein the halochromic dye is Bromocresol green and the non-volatile base is triethanolamine.
  8. 8. A composition according to claim 7 comprising a) Bromocresol green, b) a fragrance composition consisting of at least 30 weigh % of a fragrance material having a polar solubility parameter (6p) <= 7.5(MPa)1'2, a hydrogen bonding solubility parameter (SH) <= 30 (MPa)112 and oH -4 * Op 30; c) triethanolamine; and d) dipropylenglycole.
    U
  9. 9. An air-freshener device comprising a composition as defined in any one of the preceding claims.
  10. 10. An air-freshener device according to claim 9 further comprising a means to which the composition is absorbed or adsorbed.
  11. 11. A device according to claim 10 wherein the absorbent is selected from paper, textiles, felt-type materials, wovens and nonwovens.
  12. 12. A device according to claim 10 wherein the adsorbent is selected from glass fiber filters and crystals. * S. * S S... *5*S * S S...
    S * S * I.
    S
    S..... * S S.. S * 5 * S. S *5
GB0624857A 2006-12-13 2006-12-13 Volatile compositions having an end-of-life indication Withdrawn GB2444702A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011101182A1 (en) * 2010-02-18 2011-08-25 Henkel Ag & Co. Kgaa Stabilized perfume oils
EP2630974A1 (en) 2012-02-27 2013-08-28 Symrise AG Stable room fragrances with usage endpoint display
EP2803369A1 (en) 2013-05-14 2014-11-19 Symrise AG Two-phase Expiration Indicator for Fragrance Delivery Systems
EP2918295A1 (en) 2014-03-11 2015-09-16 Symrise AG Release system for fragrances with optical terminal display
US12036341B2 (en) 2019-07-17 2024-07-16 The Procter & Gamble Company Freshening compositions and methods of atomizing freshening compositions with a thermally-actuated microfluidic cartridge

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1581333A (en) * 1976-07-02 1980-12-10 Unilever Ltd Colour change systems
EP0309173A2 (en) * 1987-09-23 1989-03-29 S.C. Johnson & Son, Inc. Time-color indicators

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1581333A (en) * 1976-07-02 1980-12-10 Unilever Ltd Colour change systems
EP0309173A2 (en) * 1987-09-23 1989-03-29 S.C. Johnson & Son, Inc. Time-color indicators

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011101182A1 (en) * 2010-02-18 2011-08-25 Henkel Ag & Co. Kgaa Stabilized perfume oils
US9845449B2 (en) 2010-02-18 2017-12-19 Henkel Ag & Co. Kgaa Stabilized perfume oils
EP2630974A1 (en) 2012-02-27 2013-08-28 Symrise AG Stable room fragrances with usage endpoint display
EP2630975A1 (en) 2012-02-27 2013-08-28 Symrise AG Stable room fragrances with usage endpoint display
EP2803369A1 (en) 2013-05-14 2014-11-19 Symrise AG Two-phase Expiration Indicator for Fragrance Delivery Systems
WO2014184100A1 (en) 2013-05-14 2014-11-20 Symrise Ag Two-phase exhaustion indicator for fragrance release systems
US9700645B2 (en) 2013-05-14 2017-07-11 Symrise Ag Two-phase exhaustion indicator for fragrance release systems
EP2918295A1 (en) 2014-03-11 2015-09-16 Symrise AG Release system for fragrances with optical terminal display
US12036341B2 (en) 2019-07-17 2024-07-16 The Procter & Gamble Company Freshening compositions and methods of atomizing freshening compositions with a thermally-actuated microfluidic cartridge

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Publication number Publication date
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