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Europäisches Patentamt

(19)

European Patent Office

*EP001319412A1*

Office européen des brevets

(11)

EP 1 319 412 A1

EUROPEAN PATENT APPLICATION

(12)
(43) Date of publication:

(51) Int Cl.7:

18.06.2003 Bulletin 2003/25

A61L 9/04

(21) Application number: 02258587.1
(22) Date of filing: 12.12.2002
(84) Designated Contracting States:

(72) Inventors:

AT BE BG CH CY CZ DE DK EE ES FI FR GB GR
IE IT LI LU MC NL PT SE SI SK TR
Designated Extension States:
AL LT LV MK RO

(30) Priority: 13.12.2001 US 15367

(74) Representative: Mercer, Christopher Paul et al

(71) Applicant: INTERNATIONAL FLAVORS &
FRAGRANCES INC.
New York New York 10019 (US)

(54)

• Williams, Virgil A. G.
Leonardo, Monmouth County, NJ 07737 (US)
• Stumpf, Craig M.
Branchburg, Sommerset County, NJ 08876 (US)

Carpmaels & Ransford
43, Bloomsbury Square
London WC1A 2RA (GB)

Gel air freshener
lyzed protein gel material such as gelatin or a polysaccharide gel material such as gellan gum; a system-compatible air freshener fragrance composition contained in
one or more of the icons and/or contained in the gel matrix air freshener body; and a surfactant contained in the
body.

EP 1 319 412 A1

(57)
Described is a substantially rigid aqueous clear
gel matrix air freshener article having included therein
one or more gel matrix icons, the dimensions of which,
on use of the article, decrease in proportion to the dimensions of the body of the air freshener article in which
the icons are suspended and imbedded. The article contains water; gel matrix material which can be a hydro-

Printed by Jouve, 75001 PARIS (FR)

the prior art does not specifically or implicitly teach the advantages of icon construction from gel matrix materials and use of such icons in conjunction with substantially rigid clear gel matrix aqueous air freshener articles. as a result of emission of at least water and. Such candles fabricated using non-aqueous ester-terminated polyamide systems are disclosed in Berger et al.063. optionally. 6. U. in the alternative. either or both of a polysaccharide gel matrix material and/or a hydrolyzed protein gel matrix material. each of which icon comprises (i) water. icons which are botanicals. the dimensions of each of the icons imbedded in the air freshener gel matrix body must.S. therefrom. 10 BACKGROUND OF THE INVENTION 15 20 25 [0002] Clear candles with included icons that appear opaque and visually distinct from the clear matrix of the candle are highly desirable and are known in the prior art. decrease in proportion to the dimensions of the air freshener gel matrix body in order (i) to maintain its physical integrity and (ii) to achieve a continuously aesthetically pleasing appearance of the article. [0003] The prior art does disclose substantially rigid clear aqueous and non-aqueous polymeric air freshener articles which contain visibly detectable icons. such prior art aqueous and non-aqueous polymeric icon-containing air freshener articles do not have the unexpected and non-obvious advantages that the aqueous gel matrix icon-containing articles of our invention have. and water emission therefrom with respect to the volumetric reduction of the air freshener body which envelops said icons as a result of fragrance emission. such as those disclosed for clear candles. a clear gel matrix material which is. a surfactant.. as a result of the emission of at least water and. dVI/dθ < 0. with the proviso that the system-compatible air freshening fragrance compositions are present in at least one of said icons. However. and. Indeed. (ii) a clear gel matrix material which is. the volume fraction of said icons in said air freshener article being φ = VI / (VI + Vo).334. to a substantially lesser extent fragrance. (c) fragrances. Thus. [0005] More particularly.294. as a result of water and fragrance emission therefrom into the environment surrounding the articles. the rate of change of the air freshener body volume with respect to time. are not available or known for rigid aqueous gel matrix air freshener systems. or in at least one of said icons and in said air freshener body. a system-compatible air freshening fragrance composition. therefrom. and water emission therefrom is a constant. one or more gel matrix icons that decrease in volume in proportion to volume of the air freshener body gel matrix on use of the air freshener article. on use thereof. in which the icons are imbedded.162 and 6.071.(iii) optionally. the physical and chemical properties of each of said icons and said air freshener body being such that on use of said air freshener article. as (i) water and (ii) air freshener fragrance composition is emitted from the air freshener article on use thereof. optionally.90. icon-containing systems which provide desirable clear appearances. in the alternative.01 ≤ φ ≤ 0. optionally.EP 1 319 412 A1 Description FIELD OF THE INVENTION 5 [0001] This invention relates to substantially rigid. dVo/dθ < 0.S. on use of the air freshener. one or both of a polysaccharide gel matrix material and/or a hydrolyzed protein gel matrix material. 6. or in said air freshener body. a system-compatible air freshening fragrance composition and (iv). 30 SUMMARY OF THE INVENTION 35 40 45 50 55 [0004] Our invention provides a substantially rigid aqueous gel air freshener article having included in the gel matrix air freshener body thereof. For such articles to be useful. if any. Patent 6. as disclosed in U.309. PCT Application WO 00/73408 A1. optionally. wherein 0. to a substantially lesser extent. according to the equations: ∂VI / ∂Vo 2 . there exists a need for substantially rigid aqueous gel matrix-containing air freshener articles which include one or more icons imbedded therein which are visibly detectable from without the air freshener article at visible wavelengths. as well as DeStefano et al.214. However. the dimensions of which decrease in proportion to the dimensions of the body of the air freshener article.715. (i) the rate of volumetric reduction of each of said icons as a result of fragrance emission. Patents 5. the total volume of which is VI which decreases on use of said air freshener article whereby. for example. our invention provides a substantially rigid aqueous gel air freshener article comprising: (a) an air freshener body having a volume Vo which decreases on use of said air freshener article whereby.506. all hereby incorporated by reference as if set forth in their entirety. one or more gel matrix icons which are each visibly distinct over the range of visible wavelengths when contained within said air freshener. comprising water.. (b) fully imbedded within said air freshener body. a surfactant. if any. clear gel matrix air freshener articles having included therein one or more gel matrix icons.679. the rate of change of the icon volume with respect to time.

gel matrix icons that. DETAILED DESCRIPTION OF THE INVENTION 50 55 [0016] The substantially rigid gel matrix clear air freshener provided in accordance with our invention has included therein one or more visibly detectable gel matrix icons the dimensions and volume of which decrease in proportion to the dimensions and volume of the gel matrix air freshener body surrounding the icons and in which the icons are imbedded.5 in the case of the gel matrix air freshener article body and the components of which have an average Clog10P of 4.5 in the case of the gel matrix air freshener article icon. the antimicrobial materials. the components of which have an average Clog10P of 2. gel matrix material which is gellan gum. the substantially rigid gel matrix air freshener article of our invention can have a gel matrix air freshener body which additionally comprises at least one additive such as an antimicrobial agent. that is one or more icons. a C2-C6 alkylene glycol. are intended to be fully enclosed by an air tight packaging material whereby water molecules and fragrance composition molecules that are contained in the gel matrix icons and in the gel matrix air freshener body can not be transported outwardly from the article of our invention to the environment surrounding the article. a lower alkanol. a lower alkanol. a chelating agent. (b) cooling the icon to a temperature below the solidification point thereof. [0013] It is a further object of the invention to provide a novel gel matrix clear air freshener article having included in the gel matrix air freshener body. the substantially rigid gel matrix air freshener article of our invention can include icons which additionally comprise at least one additive such as an opacifying agent. and system-compatible air freshener fragrance. both the gel matrix icons and the gel matrix air freshener body are prepared from water. [0011] In one embodiment of the invention. the icons are placed in a jar and solidified or even frozen. a non-gelling hydrocolloid. the chelating agent.EP 1 319 412 A1 5 10 15 20 25 30 35 40 45 =φ / (1 . an anti-oxidant. an anti-oxidant. In a preferred embodiment. a C2-C6 alkylene glycol. tri-potassium citrate. and a C2-C6 (mono. [0012] It is thus an object of the invention to provide a novel gel matrix clear air freshener article. [0014] It is a still further object of the invention to provide a novel gel matrix clear air freshener article having included in the gel matrix air freshener body. (c) providing the gel matrix air freshener body in the liquid phase. (ii) the integrity of the fragrance compositions emitted from said air freshener body and said icons is maintained and (iii) the distinguishing visibility of the icons in said air freshener from without said air freshener. As used herein the word icon is also understood to include icon plural. gel matrix icons. removing the gel matrix air freshener article 3 . decrease in volume in proportion to the volume of the gel matrix air freshener body. [0010] Our invention also provides a process for preparing such air fresheners comprising the steps of: (a) providing at least one gel-matrix icon. [0008] The substantially rigid gel matrix air freshener article of our invention may be fully encompassed by a clear substantially solid or semi-solid microporous boundary surface which surface permits passage of water molecules and air freshener fragrance composition component molecules therethrough on the use of the article. on use of the air freshener article. Pigment is added to the icon material in an amount effective for making the icon material opaque and then the material is molded to form icons. prior to use. nonoxynol-15 (o(hydroxy(ethoxy)15)) nonylphenyl ether or PEG-15 nonylphenyl ether. and a C2-C6 (mono. in the case of the gel matrix air freshener article icon. and (d) immersing totally the solidified icon in the gel matrix air freshener body. PEG-4 nonylphenyl ether.or di-) alkylene glycol-C2-C4 alkyl ether. On removal of such air tight packaging material from around the gel-matrix air freshener article of our invention. is maintained. where P is the n-octanol/water partition coefficient for each of the components of the fragrance. on use of the gel matrix air freshener article. [0009] In addition. ethyl alcohol. [0006] Furthermore. [0007] In addition.φ) and ∂ 2VI/∂Vo2=0. on use of the article. decrease in dimensions and volume in proportion to the dimensions and volume of the gel matrix air freshener article. [0015] Still other objects and advantages of the invention will in part be obvious and will in part be apparent from the following detailed description and the appended claims.or di-)alkylene glycol mono-C2-C4 alkyl ether. [0017] The substantially rigid gel matrix air freshener articles contemplated by our invention. the substantially rigid gel matrix air freshener article of our invention may be externally supported by means of an external support comprising a solid base having vertically-disposed solid sidewalls extending therefrom such as a vertically disposed cylindrical glass jar open at the top. methylchloroisothiazolinone and methylisothiazolineone. a chelating agent. Hot gel matrix material is poured over the frozen icons to provide a gel air freshener having included icons that. the surfactant. a nongelling hydrocolloid. propylene glycol. at visible wavelengths. in the case of the gel matrix air freshener article body or nonoxynol-4. an anti-microbial agent.

[0025] More specifically. sodium alginate or potassium alginate. di-sodium salt. the Pomona 92 database. However. the tri-sodium salt. glutaraldehyde.g. Leo in Comprehensive Medicinal Chemistry. the log10P values are most conveniently calculated by the "CLOGP" program. the di-sodium salt. partially glycerated anionic polysaccharide. hereafter referred to as "Clog10P" is determined by the fragment approach of Hansch and Leo cf. p. [0018] The gel matrix air freshener article of our invention preferably contains. Eds. [0019] The air freshener article of our invention may. a chelating agent. it is used in an amount of between about 0. an alkali metal salt of alginic acid.. the ammonium. di-sodium salt.G.295. Missouri. an alkali metal salt of ethylenediamine tetraacetic acid. g.. [0023] Preferably. preventing syneresis and improving clarity in the gel matrix on use of the gel matrix air freshener article of our invention. B. the tri-sodium salt. most preferably in an amount of about 5% by weight. the atom connectivity and the chemical bonding. the mono-ammonium. a non-gelling hydrocolloid and a C2-C6 alkylene glycol or a C2-C6 (mono. an alkaline earth metal salt of alginic acid. e. di-sodium salt. e..A. Ramsden. at that point in time. a lower alkanol. Where such air freshener fragrance is used.g. a linear high molecular weight extracellular partially acetylated. an ammonium salt of citric acid. e. an ammonium salt of N-hydroxyethylenediaminetriacetic acid..g. contains many. P. starch or carboxymethylcellulose. e. an antimicrobial agent. Pergamon Press. e. e. di-sodium salt.. e.5-dimethoxy-2. 1-(3-chloroallyl)-3.. di-sodium citrate. This program also lists experimental log10P values when they are available in the Pomona 92 database. also available from Daylight CIS.1% and about 20% by weight of the composition. The C2-C6 alkylene glycol is preferably 1. e. e. the gel matrix air freshener article of our invention can contain an air freshening fragrance composition within the gel matrix air freshener body immediately prior to use of the article. tri-sodium citrate or tri-potassium citrate. that is. Vol. a type 'B' gelatin. The preferred non-gelling hydrocolloid is one of locust bean gum. ammonium. e. a lower alkanol. an alkali metal salt of iminodisuccinic acid. along with citations to the original literature. preferably in an amount between about 1% and about 10% by weight.g.3-diol. At least one of the gel matrix icons can also contain an antimicrobial agent. e.EP 1 319 412 A1 5 10 15 20 25 30 35 40 45 50 55 of our invention from the surrounding air tight packaging material. California. an ammonium salt of iminodisuccinic acid. of the non-gelling hydrocolloid is as a processing aid for gelling. The chelating agent is preferably one or more of an alkali metal salt of citric acid. C.4-imidazolidinedione.. The C2-C6 (mono. that is. preferably ethanol. [0022] As stated herein.or di) alkylene glycol C2-C4 alkyl ether. guar gum. "in use" in accordance with the practice of our invention. in the gel matrix air freshener body and/or icon. The fragment approach is based on the chemical structure of each perfume ingredient. Louis. The antimicrobial agent is preferably one or more of potassium dimethyldithiocarbamate. Taylor and C. A. the gel matrix air freshener article of our invention is. o-phenyl phenol. contain in the gel matrix air freshener body and/or in the gel matrix icon a hydrolyzed protein gel matrix material composed of gelatin having an isoelectric point of from about 4 up to about 7. 4..g. and takes into account the numbers and types of atoms.g. Irvine..N'-dimethyl-5. an alkali metal salt of ethylenediamine disuccinic acid. the dipotassium. J. The Clog10P value which are the most reliable and widely used estimates for this physiochemical property. when the article is still contained in an air tight packaging material..or di-) alkylene glycol C2-C4 alkyl ether is preferably dipropylene glycol n-butyl ether. for example. 2-bromo-2-nitropropane-1. for example.g. in the gel matrix air freshener body and/or in the gel matrix icon. an ammonium salt of ethylene diamine tetraacetic acid.5 wherein P is the n-octanol/water partition coefficient for each of the fragrance components.5. as an alternative to the gel matrix material which is a polysaccharide. a chelating agent. e.7-triaza-1-azoniaadamantane chloride. Hansch. mono-sodium salt. [0020] The gel matrix clear air freshener article of our invention preferably contains..g. and/or carageenan. a non-gelling hydrocolloid and a C2-C6 alkylene glycol or a C2-C6 (mono. available from Daylight Chemical Information Systems.. KELCOGEL® gum trademark of the Monsanto Company of St.. xanthan gum.5 and (ii) the average "Clog10P" in the gel matrix air freshener article icon(s) is about 4. hereafter referred to as "Daylight CIS". methylchloroisothiazolinone and/or methylisothiazolinone.or di-) alkylene glycol C2-C4 alkyl ether. 1990. a clear gel matrix material which is a polysaccharide which may be at least one of a gellan gum. calcium alginate or magnesium alginate. the design of the fragrance employed in the gel matrix air freshener article body should differ from the design of the fragrance employed in the gel matrix air freshener article icon(s) whereby (i) the average "Clog10P" for the fragrance components in the gel matrix air freshener article body is about 2.g. and an ammonium salt of ethylene diamine disuccinic acid. [0021] The purpose of the presence. N. the mono-ammonium. [0024] The log10P of many perfume ingredients has been reported. Sammens.g. e. in the gel matrix air freshener body. an air freshener fragrance composition is included in either the gel matrix air freshener body or in at least one gel matrix icon or in both the gel matrix air freshener body and in at least one gel matrix icon. the mono-ammonium..g. and the air freshening fragrance composition that would be contained in the gel matrix air freshener body preferably consists essentially of fragrance components each of which has a C log10P of from about 1 up to about 4 wherein P is the octanol/water partition coefficient for each of said fragrance 4 . g. Inc.2-propylene glycol. The "calculated log10P". an alkali metal salt of N-hydroxyethylenediamine triacetic acid. The lower alkanol is. are preferably used instead of the experimental log10P values for the selection of perfume ingredients which are useful in the gel matrix air freshener articles of our invention.

760 Dihydromyrcenol 3.820 Nerol 2.480 Benzyl acetate 1. [0028] Specific examples of preferred fragrance components useful in the gel matrix air freshener icons and their respective Clog10P values are as follows: Fragrance Component Clog10P value Amyl salicylate 4.712 β-Phenylethyl alcohol 1.235 Musk ketone 3.120 α-Irone 3.183 α-Terpineol 2.014 Musk tibetine 3.649 2-Methoxynaphthalene 3.771 Benzophenone 3.307 [0027] As stated herein.649 Cis-jasmone 2.547 Linalyl acetate 3.436 5 . [0026] Specific examples of preferred fragrance components useful in the gel matrix air freshener body and the Clog10P of each of these components is as follows: 5 Fragrance Component 10 15 20 25 30 35 40 45 50 55 Clog10P value Benzaldehyde 1.601 Benzyl salicylate 4.960 Laevo-carvone 2. and the air freshening fragrance composition preferably consists essentially of fragrance components.830 Amyl cinnamate 3.569 δ-Nonalactone 2.831 Myristicin 3.478 1-Phenyl hexanol-5 3.383 β-Caryophyllene 6.200 6-Phenyl heptanol-2 3.333 Cedrol 4.03 δ-Undecalactone 3.EP 1 319 412 A1 components. the gel matrix air freshener article of our invention can contains an air freshening fragrance composition in one or more of the gel matrix icons contained in the gel matrix air freshener body prior to use of the article.299 α-Santalol 3.800 Iso-eugenol 2.530 Cedryl acetate 5.083 Geraniol 2.500 Eugenol 2. each of which has a Clog10P of from about 1 up to about 8 wherein P is the octanol/water partition coefficient for each of said fragrance components.

in the case of gel matrix air freshener article icon. SURFONIC T-50.g..233 [0029] In the gel matrix air freshener article of our invention.. Such gellan gum is..EP 1 319 412 A1 (continued) Fragrance Component 5 10 15 Clog10P value Cedryl formate 5. CAS #9003-11-6. in the case of the gel matrix air freshener article body. Missouri..g.3...888 Geranyl anthranilate 4. nonoxynol-15.530 5-Acetyl-1. [0032] The water that is used to prepare both the icons and the gel matrix material is preferably deionized water or distilled water and is used in an amount between about 50% and about 90% by weight of the composition. HLB=14. a methyl oxirane polymer. 6 .g. Utah. Hot gel matrix material is poured over the frozen icons to provide a gel air freshener having included icons that shrink in proportion to the gel matrix material.g.820 Linalyl benzoate 5. KELCOGEL® F a low acyl clarified product and KELCOGEL® AFT produced by the KELCO Biopolymer Division of the Monsanto Company. with the microorganism Sphingomonas elodea followed by de-acetylation and alcoholic precipitation. Huntsman Petrochemical Corp.5 in the case of the gel matrix air freshener article icon. formed by inoculating a fermentation medium having.8. e.359 Ethyl undecylenate 4. when at least one of the gel matrix icons contained in the gel matrix air freshener body contains an air freshening fragrance composition prior to use of the article.246 d-Limonene Cis-p-t-butylcyclohexyl acetate 4.977 Cyclopentadecanolide 6.216 α-Irone 3. most preferably in an amount between about 75% and about 80%.g. poly C2-C4 alkylene glycol mono-C10-C20 alkanoic acid esters. both the icons and the gel matrix material are prepared from water. and fragrance composition. the icon containing the air freshener fragrance composition may also contain a surfactant having a hydrophile/lipophile balance of less than about 10. HLB=15. the components of which have an average Clog10P=2. nonoxynol-15. nonoxynol-4. KELCOGEL® F gellan gum.g. ethyl alcohol. Illinois. e. poly C2-C4 alkylene glycol sorbitan mono-C10-C20 alkanoic acid esters. HLB=24. e.233 Patchouli alcohol 4.g.1. Louis. propylene glycol.ω-poly C2-C4 alkylene glycols.g. in the case of the gel matrix air freshener article body. [0031] In a preferred embodiment of the invention. KELCOGEL® LT-100 a high acyl unclarified product.6-hexamethyl indane 5. HLB=17. [0033] Preferred gel matrix polysaccharide materials useful in the practice of our invention are gellan gums.265 γ-Dodecalactone 4. SURFONIC TOFA-20. Utah. Chicago. as a substrate. PEG-40 stearate. Preferred surfactants are poly (C2-C4 alkylene glycol)6-30 mono([C8-C10 alkyl]phenyl)ethers. e.019 Amyl cinnamic aldehyde 4..232 20 25 30 35 40 45 50 55 4.e. POLOXAMER-108. e. Huntsman Petrochemical Corp. e. e. C11-15 PARETH-20 and CETEARETH-55. KELCOGEL® LT a low acyl unclarified product. Pigment is added to the icon material in an amount effective for making the icon material opaque and then the material is molded to form icons. 1. POLYSORBATE-20. tall oil fatty acid ethoxylate.2. methylisothiazolineone. and poly C2-C4 alkylene glycol mono-C10-C20 alkyl ethers. most preferably. Salt Lake City. [0030] In the gel matrix air freshener body of the gel matrix air freshener article of our invention. potassium citrate. the surfactant has a hydrophile/lipophile balance in the range of from about 10 up to about 30. glucose.5.. fragrance composition.3.070 Cyclohexyl salicylate 5. poly C2-C4 alkylene glycol esters of tall oil fatty acids. poly C2-C4 alkylene glycol tallow amines. the components of which have an average Clog10P=4.1% and about 10% by weight of the composition.324 Linalyl benzoate 5..8. preferably in an amount between about 70% and about 85% by weight. The icons are placed in a jar and frozen.. Salt Lake City. HLB=30. methylchloroisothiazolinone. a low acyl clarified product of the Monsanto Company of St. The gellan gum is used in an amount between about 0.

Once the mixture is completely clear. preferably in an amount between about 1% and about 20% by weight. The surfactant is used in an amount between about 0. Pennsylvania.. most preferably in an amount of about 0. the most preferred chelating agent is tri-potassium citrate. to one or more of the icon molds containing the icon portion while the icon portion is in the liquid state. [0037] By the same token.1% and 1% by weight. it is used in an amount between about 0. [0038] When chelating agents are used in the air freshener body and in the gel matrix icon(s) of our invention. to prepare the gel matrix icon and gel matrix air freshener article body material. Then the remaining ingredients are added with stirring. Philadelphia. propanol.0% by weight. preferably in an amount between about 1% and about 5% by weight. is used in an amount between about 0. and most preferably in an amount of about 3% by weight. it is used in amount between about 0.05% and 4. is nonoxynol-4. which is optional in the case of the presence thereof in the icon. Cranbury. the gellan gum.EP 1 319 412 A1 5 10 15 20 25 30 35 40 45 50 55 preferably in an amount between about 0.90 and wherein VI' is the volume of the "icon" portion and Vo' is the volume of the body portion.1% and about 25% by weight of the composition. (c) maintaining the body portion in the liquid state at a temperature of from about 65°C up to about 80°C (d) pouring the icon portion into one or more icon molds.0% by weight of the composition. The nonoxynol-15 is a non-ionic surfactant and the amount that is required is dependent on the character of the particular fragrance that is used. When used. and (ii) a body portion. and by way of example. In the gel matrix air freshener body of the air freshener article. [0040] More specifically.1% and 25% by weight of the icon composition. 7 . When used.g. and (i) within a time period sufficiently short in length to prevent the melting of the one or more suspended icons. New Jersey.. and the like can be used. Cranbury. Alternatively. (b) dividing the resulting solution into two portions: (i) an icon portion. As stated herein. the icons have a higher concentration of gellan gum than the surrounding matrix. the preferred alkylene glycol is propylene glycol... wherein 0. or "PEG-15 nonylphenyl ether" which is marketed under the trademark IGEPAL® CO730 by Rhodia. preferably in amount between about 0.03% by weight. preferably in an amount between about 1% and about 10% by weight. [0034] The most preferable antimicrobial agents used in the practice of our invention are methylchloroisothiazolinone and methylisothiazolineone that are marketed in combination under the trademark KATHON® CG by Rohm and Haas Co. [0039] A preferred embodiment of the process of our invention comprises the steps of: (a) admixing the clear gel matrix material. when used. herein. or PEG-4 nonylphenyl ether which is marketed under the trademark IGEPAL® CO430 by Rhodia.2% by weight. isopropanol. o-(hydroxy(ethoxy)4) nonylphenyl ether. preferably in an amount between about 0. When it is used. the volume fraction φ of the icon portion being φ = VI' / (Vo' + VI'). cooling the resulting suspension to a temperature in the range of from about 10°C up to about 30°C. New Jersey. the propylene glycol is used in an amount between about 0. Inc. the water is added to a steam-jacketed vessel with a mechanical stirrer. most preferably in amount of about 0. most preferably in an amount of about 1% by weight. [0036] Optionally the gel matrix air freshener body and/or the gel matrix icon can contain a lower alkanol such as ethanol. (g) removing the one or more icons in the solid state from the one or more icon molds. [0035] When a C2-C6 alkylene glycol is contained in the gel matrix air freshener body or in the gel matrix icon. In one embodiment of the invention. The nonoxynol-4 is a non-ionic surfactant and the amount that is required is dependent on the character of the particular fragrance that is used. other lower alkanols such as methanol.1% and about 20% by weight of the composition. The gellan gum is sprinkled into the vortex and heated to about 70°C.0% by weight of the composition.01% and about 1. A preferred lower alkanol useful in this context is 190 proof ethanol and. in the practice of our invention in the gel matrix air freshener icon of the air freshener article of our invention. (f) cooling the icon portion to a temperature below the solidification temperature of the icon portion whereby one or more icons in the solid state are formed. (e) optionally adding one or more of the same or different pigments as set forth in Examples 1-9. (h) permanently submerging the entirety of the one or more icons in the body portion whereby the one or more frozen icons is suspended in the body portion. they are optionally present in the composition and can be used in an amount between about 0. e.5% and about 20% by weight of the composition. whereby the resulting suspension is transformed to the solid or semi-solid phase. a preferred surfactant is nonoxynol-15 o-(hydroxy(ethoxy)15))nonylphenyl ether.01 ≤ φ ≤ 0.5% and about 2% by weight. Inc. preferably in an amount between about 1% and 20% by weight. most preferably in an amount of between about 5% and 15% by weight. the heat is removed and the aqueous gellan gum solution is cooled to about 60°C. most preferably in an amount of between about 5% and about 15% by weight. a preferred surfactant. with water at a temperature in the range of from about 65°C up to about 80°C to form an aqueous gel matrix solution. most preferably in an amount of about 4% by weight.001% and about 7.

EP 1 319 412 A1 5 10 [0041] The icons are prepared by pouring the hot formula into molds and permitting the formula to solidify. wherein co1 is the average perfume composition component concentration in gram-moles per liter in the air freshener body at time θ1. pigment is added to the icon material in an amount effective for rendering the icon visually distinct from the surrounding gel matrix. graphtol blue powder. graphtol green powder. titanium dioxide. iron oxide cosmetic russet. wherein co is the average perfume composition component concentration in gram-moles per liter in the air freshener body at time θ. or the algorithm: -υ 45 50 55 -υ (c I2 c o2 )/(c I1 c o1 ) = exp[k 2 ∆θ + ∆(Vo ) + ∆(VI )] wherein VI is the total volume of the icons at time θ.c o [∂V o /∂θ])dθ}= 15 20 25 30 35 40 k 1 ∆(c o V o )+(1-φ)∫ ∫ [∂E o /∂V o ]dV o dθ+φ)∫ ∫ [∂E I /∂V I ]dV I dθ wherein VI is the total volume of the icons at time θ. wherein Vo is the total air freshener body volume at time θ. iron oxide yellow. wherein Eo is the elastic modulus of the air freshener body at time θ. The gel matrix air freshener article body material is poured into the container having the solidified icons therein and allowed to solidify to room temperature before being capped. wherein Vo is the total air freshener body volume. wherein co2 is the average perfume composition component concentration in gram-moles per liter in the air freshener body at time θ2. the operation of the gel matrix air freshener article of our invention is in accordance with the algorithm: ∫ {(v I [∂c I /∂θ]-V o [∂c o /∂θ] +c I [∂V I /∂θ] . wherein k1 is a constant. wherein EI is the average elastic modulus of each of the icons at time θ. wherein co is the average perfume composition component concentration in gram-moles per liter in the air-freshener body at time θ. wherein cI is the average perfume composition component concentration in gram-moles per liter in all of the icons at time θ. All fragrance materials set forth 8 . [0043] The following non-limiting examples are presented for purposes of illustration. and mixtures of the pigments. wherein Vo is the total air freshener body volume at time θ. cloisonne super rouge. wherein cI is the average perfume composition component concentration in gram-moles per liter in all of the icons at time θ. and positioned in an air freshener container. cloisonne super rouge with polyflake. The icon is then removed from the mold. [0042] When each of the gel matrix icons and the gel matrix air freshener body of the air freshener article of our invention contains a system-compatible air freshener fragrance composition prior to use of the gel matrix air freshener article of our invention. While the formula is maintained in a hot liquid state. wherein cI2 is the average perfume composition component concentration in gram-moles per liter in all of the icons at time θ2. wherein cI1 is the average perfume composition component concentration in gram-moles per liter in all of the icons at time θ1 . or the algorithm: -υ -υ ∆(Vo ) +∆(VI )-∆(ln c I )-∆(ln c o )=-k 2 (∆θ) wherein VI is the total volume of the icons at time θ.and wherein k2 is a constant. in a solidified state. but are not limited to. Suitable pigments include. and wherein φ is the volume fraction of the icons. and wherein k2 is a constant.

00% by weight ethanol in water. it was permitted to cool. Hazlet.0 Eugenol 8.77% by weight deionized water to a steam-jacketed vessel with a mechanical stirrer. were added to the gellan gum solution with stirring when the solution reached 60°C. Once the aqueous gellan gum solution was completely clear. also known as nonoxynol-15 or PEG15 nonylphenyl ether. 10. 3. was sprinkled into the vortex and heated to about 70°C.EP 1 319 412 A1 in the examples are available from International Flavors & Fragrances Inc.0 2-Methoxynaphthalene 3. [0047] Three one-hundredths percent 0.03% by weight KATHON® CG. it was permitted to cool. Rhone-Poulenc Surfactants and Specialties L.00% by weight KELCOGEL® AFT gellan gum. Pennsylvania).0 β-Caryophyllene 14. Cranbury. [0048] PART B: A gel matrix air freshener article icon gel matrix material was prepared by adding 76. New Jersey.. EXAMPLE A 5 PREPARATION OF AIR FRESHENER FRAGRANCE FOR GEL MATRIX AIR FRESHENER ARTICLE BODY [0044] The following fragrance is prepared for use in Part "A" of EXAMPLES 1-9. Monsanto Company of St.0 Cedryl acetate 16. 190 proof.0 Benzaldehyde 2. [0049] Three one-hundredths percent 0.0 Geranyl anthranilate 3. The stirrer was turned on and 1. and 5.P.0 Cyclohexyl salicylate 4. supra.0 γ-Dodecalactone 3. infra: Ingredients 30 Parts by Weight Amyl salicylate 35 4.00% by weight IGEPAL® CO730. Philadelphia. Louis..0 β-Phenylethyl alcohol 20 12.0 Myristicin 4.0 Isoeugenol 2. 4..0 40 EXAMPLES 1-9 45 50 55 [0046] PART A: A gel matrix air freshener article body gel matrix material was prepared by adding 76.00% by weight KELCOGEL® AFT gellan gum was sprinkled into the vortex and heated to about 70°C. also known as nonoxynol-4 or PEG-4 nonyl- 9 . 190 proof.0% by weight propylene glycol.0 EXAMPLE B 25 PREPARATION OF AIR FRESHENER FRAGRANCE FOR GEL MATRIX AIR FRESHENER ARTICLE ICON(S) [0045] The following fragrance was prepared for use in Part "B" of Examples 1-9.00% by weight IGEPAL® CO430. 10.0% by weight propylene glycol. The stirrer was turned on and 1. 3. 0. Once the aqueous gellan gum solution was completely clear. Missouri. N.00% by weight ethanol in water.0 α-Irone 10. 4.00% by weight of the fragrance formulation of EXAMPLE A.0 Nerol 7.77% by weight deionized water to a steam-jacketed vessel with a mechanical stirrer.03% by weight KATHON® CG (Rohm and Haas Co. infra: Ingredients 10 15 Parts by Weight α-Irone 7.J.02% by weight potassium citrate.

a surfactant. The icons were placed in a jelly jar and the jar was filled with clear base material. the volume fraction of said icons in said air freshener article being φ = VI / (VI + Vo). Cloisonne super rouge with polyflake (polyester glitter). The following pigments were used: 5 1. and water emission therefrom is a constant. violet-like undertones. on use provided aestheticlly pleasing rose. except that the icons were molded in the form of a heart. (ii) the integrity of the fragrance compositions emitted from said air freshener body and said icons is maintained and (iii) the distinguishing visibility of the icons in said air freshener from without said air freshener. according to the equations: ∂VI / ∂Vo =φ / (1 . the invention is not limited except as by the appended claims. (iii)optionally. 4. 2. 8. and water emission therefrom with respect to the volumetric reduction of the air freshener body which envelops said icons as a result of fragrance emission.00% by weight of the fragrance formulation of EXAMPLE B. a system-compatible air freshening fragrance composition and (iv)optionally. or in said air freshener body. all of the cubes maintained their form without any migration of pigment with the exception of the cube #6 containing cloisonne super red. Accordingly. 7. if any. a very slight haze was observed at the edge of the cube. The icons maintained their form after three days. (b) fully imbedded within said air freshener body. at visible wavelengths. and 5. is maintained. a clear gel matrix material selected from the group consisting of a polysaccharide gel matrix material and a hydrolyzed protein gel matrix material. optionally. A substantially rigid aqueous clear gel matrix air freshener article comprising: (a)an air freshener gel matrix body having a volume Vo which decreases on use of said air freshener article whereby dVo/dθ < 0 comprising water. Iron oxide yellow from Sun Chemical. 5. various modifications may be made without deviating from the spirit and scope of the invention. [0050] Pigments were added to separate portions of the material in an amount effective to render the material opaque. Iron oxide cosmetic russet from Sun Chemical. Graphic blue powder. were added to the gellan gum solution with stirring when the solution reached 60°C. or in at least one of said icons and in said air freshener body. 0. 6.02% by weight potassium citrate. a surfactant.90. [0053] The resulting gel matrix clear air freshener articles. woody aromas with sweet floral balsamic topnotes and orris. supra. Titanium dioxide. [0052] Clear gel matrix material prepared according to Part A was poured over each of the colored cubes. In that instance. a system-compatible air freshening fragrance composition. with the proviso that the system-compatible air freshening fragrance compositions are present in at least one of said icons. After three (3) days. the total volume of which is VI which decreases on use of said air freshener article whereby dVI/dθ < 0 each of which icon comprises (i) water. Cloisonne super rouge. and. EXAMPLE 10 25 30 [0054] Seven (7) icons containing cloisonne super rouge and seven icons containing titanium dioxide were prepared as described in connection with Examples 1-9.EP 1 319 412 A1 phenyl ether. the physical and chemical properties of each of said icons and said air freshener body being such that on use of said air freshener article. it will be appreciated that. [0055] From the foregoing. Cloisonne super red. although specific embodiments of the invention have been described herein for purposes of illustration. Claims 35 40 45 50 55 1. (i) the rate of volumetric reduction of each of said icons as a result of fragrance emission.φ) and ∂ 2VI/∂Vo2=0.and 9. wherein 0. if any. 10 15 20 [0051] Each portion of individually colored material was molded into the form of a cube and frozen. 10 . (ii) a clear gel matrix material selected from the group consisting of a polysaccharide gel matrix material and a hydrolyzed protein gel matrix material. 3.01 ≤ φ ≤ 0. Lake pigments. one or more icons which are each visibly distinct over the range of visible wavelengths when contained within said air freshener. Iron oxide cosmetic russet with titanium dioxide.

or di-) alklyene glycol C2-C4 alkyl ether is dipropylene glycol-n-butyl ether. and carageenan. an ammonium salt of ethylene diamine tetraacetic acid. The air freshener article of any one of claims 1 to 5 wherein the air freshener body is fully surrounded by a clear substantially solid or semi-solid microporous boundary surface permitting passage of water molecules and fragrance composition component molecules therethrough on use of said article. a poly C2-C4 alkylene glycol sorbitan mono-C10-C20 alkanoic acid ester. The air freshener article of claim 11 wherein the surfactant contained in the gel matrix air freshener body is a poly (C2-C4 alkylene glycol)6-30 mono ([C8-C10 alkyl]phenyl)ethers. The air freshener article of any one of claims 1 to 7 wherein an air freshening fragrance composition is contained within said air freshener body immediately prior to use of said article.5. the chelating agent is selected from the group consisting of an alkali metal salt of citric acid. and the antimicrobial agent is selected from the group consisting of potassium dimethyldithiocarbamate. 4. a poly C2-C4 alkylene glycol tallow amine.or di) alkylene glycol C2-C4 alkyl ether and a C2-C6 alkylene glycol. 9. 1-(3-chloroallyl)-3. 5 10 15 20 25 30 35 40 45 50 55 10.2-propylene glycol. 6. The air freshener article of any one of claims 1 to 3 wherein the clear gel matrix material is a hydrolyzed protein gel matrix which is gelatin having an isoelectric point of from 4 up to 7. a lower alkanol.5-dimethoxy-2. a 1. a C2-C6 alkylene glycol. a poly C2-C4 alkylene glycol mono-C10-C20 alkanoic acid ester.4-imidazolidinedione. 2-bromo-2-nitropropane-1. 11. The air freshener article of claim 2 wherein the icons comprise at least one opacifying agent and the opacifying 11 . the C2-C6 alkylene glycol is 1. 8. an alkali metal salt of ethylenediamine disuccinic acid and an ammonium salt of ethylene diamine disuccinic acid. an ammonium salt of citric acid. glutaraldehyde. The air freshener article of claim 2 wherein the air freshener body comprises an antimicrobial agent.N'-dimethyl-5. The air freshener article of any one of claims 1 to 9 wherein at least one of said icons contains an air freshening fragrance composition prior to use of said article. and the air freshening fragrance composition consists essentially of fragrance components. or a poly C2-C4 alkylene glycol mono-C10-C20 alkyl ether. an ammonium salt of iminodisuccinic acid. an alkali metal salt of ethylenediamine tetraacetic acid. each of which has a Clog10P of from 1 up to 8 wherein P is the octanol/water partition coefficient for each of said fragrance components. 3. alkaline earth metal salts of alginic acid. 7. 5. a poly C2-C4 alkylene glycol ester of tall oil fatty acid. an anti-oxidant. The air freshener article of any one of claims 1 to 8 wherein at least one of said icons contains an air freshening fragrance composition prior to use of said article.or di-) alkylene glycol-C2-C4 alkyl ether.7-triaza-1-azoniaadamantane chloride. and the air freshening fragrance composition consists essentially of fragrance components each of which has a C log10P of from 1 up to 8 wherein P is the octanol/water partition coefficient for each of said fragrance components. in addition. The air freshener article of any one of claims 1 to 6 supported by means of an external support comprising a solid base having vertically-disposed solid sidewalls extending therefrom. an alkali metal salt of N-hydroxyethylenediamine triacetic acid. a chelating agent. a non-gelling hydrocolloid. an alkali metal salt of iminodisuccinic acid. 13. and a C2-C6 (mono. and. The air freshener article of any one of claims 1 to 3 wherein the clear gel matrix material is a polysaccharide and the polysaccharide is selected from the group consisting of gellan gum. an ammonium salt of N-hydroxyethylenediaminetriacetic acid. N.EP 1 319 412 A1 2. a lower alkanol.ω-poly C2-C4 alkylene glycol. o-phenyl phenol. methylchloroisothiazolinone and methylisothiazolinone. 12. a C2-C6 (mono. The air freshener article of claim 1 wherein the air freshener body additionally comprises at least one additive selected from the group consisting of an opacifying agent. an antimicrobial agent.3-diol. and the air freshening fragrance composition consists essentially of fragrance components each of which has a C log10P of from 1 up to 4 wherein P is the octanol/water partition coefficient for each of said fragrance components. alkali metal salts of alginic acid. The air freshener article of any one of claims 1 to 10 wherein the surfactant contained in the gel matrix air freshener body has a hydrophile/lipophile balance in the range of from 10 up to 30. a chelating agent. and the C2-C6 (mono. a surfactant having a hydrophile/lipophile balance of less than about 10.

17. the weight percent of clear gel matrix material is from 0. 15. wherein co is the average perfume composition component concentration in gram-moles per liter in the air-freshener body at time θ. wherein co is the average perfume composition component concentration in gram-moles per liter in the air freshener body at time θ. cloisonne super rouge with polyflake. the operation of the air freshener article is in accordance with the algorithm: ∫ {(v I [∂c I ∂θ]-V o [∂c o /∂θ] +c I [∂V I /∂θ] .1% up to 20% by weight of said article and the weight percent of surfactant in said article is from 0. cloisonne super rouge. The air freshener article of any one of claims 1 to 13 wherein the weight percent of water in said article is from 50% up to 90% of said article. wherein Vo is the air freshener body volume at time θ. 16. and on use of said article. the operation of the air freshener article is in accordance with the algorithm: 45 -υ -υ (c I2 c o2 )/(c I1 c o1 ) = exp[k 2 ∆θ + ∆(Vo ) + ∆(VI )] 50 55 wherein VI is the total volume of the icons at time θ. wherein EI is the average elastic modulus of each of the icons at time θ. wherein cI is the average perfume composition component concentration in gram-moles per liter in all of the icons at time θ. wherein k1 is a constant. The air freshener article of any one of claims 1 to 14 wherein each of said icons and said air freshener body contains a system-compatible air freshening fragrance composition prior to use of said article.1% up to 25% by weight of said article. and on use of said article. and wherein φ is the volume fraction of the icons. iron oxide cosmetic russet. and on use of said article. wherein Eo is the elastic modulus of the air freshener body at time θ. wherein Vo is the air freshener body volume. the operation of the air freshener article is in accordance with the algorithm: 30 -υ -υ ∆(Vo ) +∆(VI )-∆(ln c I )-∆(In c o )=-k 2 (∆θ) 35 40 wherein VI is the total volume of the icons at time θ. the weight percent of system-compatible fragrance in said article is from 0. 5 10 14.and wherein k2 is a constant. wherein cI2 is the average perfume composition component concentration in gram-moles per liter in all of the icons at time θ2.EP 1 319 412 A1 agent is iron oxide yellow. The air freshener article of any one of claims 1 to 14 wherein each of said icons and said air freshener body contains a system-compatible air freshening fragrance composition prior to use of said article. wherein co1 is the average perfume composition component concentration in gram-moles per liter in the air freshener body at time θ1. titanium dioxide or a Lake color.c o [∂V o /∂θ])dθ} = k 1 ∆(c o V o )+(1-φ)∫ ∫ [∂E o /∂V o ]dV o dθ+φ∫ [∫ ∂E I /∂V I ]dV I dθ 15 20 25 wherein VI is the total volume of the icons at time θ. wherein co2 is the average perfume composition component concentration in gram-moles per liter in the air freshener body at time θ2. graphtol blue powder. The air freshener article of any one of claims 1 to 14 wherein each of said icons and said air freshener body contains a system-compatible air freshening fragrance composition prior to use of said article. graphtol green powder. wherein cI1 is the average perfume composition component concentration in gram-moles per liter in all of the icons at time θ1. wherein cI is the average perfume composition component concentration in gram-moles per liter in all of the icons at time θ. and 12 .1% up to 10% by weight of said article. wherein Vo is the total air freshener body volume at time θ.

(c) maintaining the "body" portion in the liquid state at a temperature of from about 65°C up to about 80°C (d) pouring the "icon" portion into one or more icon molds. (b) dividing the resulting solution into two portions: (i) an "icon" portion. (c) providing said air freshener body in the liquid phase. whereby the resulting suspension is transformed to the solid or semi-solid phase. (f) cooling the "icon" portion to a temperature below the solidification temperature of the "icon" portion whereby one or more frozen icons in the solid state are formed. and (i) within a time period sufficiently short in length to prevent the melting of the one or more suspended icons. A process for preparing the air freshener article of any one of claims 1 to 17 comprising the steps of: 5 10 15 20 25 (a) providing at least one icon. wherein 0. (e) optionally adding one or more of the same or different pigments to one or more of the icon molds containing the "icon" portion while the "icon" portion is in the liquid state. cooling the resulting suspension to a temperature in the range of from 10°C.90 and wherein VI' is the volume of the "icon" portion and Vo' is the volume of the "body" portion. 30 35 40 45 50 55 13 . The process of claim 18 comprising the steps of: (a) admixing the clear gel matrix material with water at a temperature in the range of from 65°C up to 80°C to form an aqueous gel matrix solution. the volume fraction φ of the "icon" portion being φ = VI' / (Vo' + VI'). 19. up to 30°C. (b) cooling said icon to a temperature below the freezing point thereof. (g) removing the one or more frozen icons in the solid state from the one or more icon molds. 18. and (ii) a "body" portion.01 ≤ φ ≤ 0. and (d) immersing said icon in said air freshener body. (h) permanently submerging the entirety of the one or more frozen icons in the "body" portion whereby the one or more frozen icons is suspended in the "body" portion.EP 1 319 412 A1 wherein k2 is a constant.

EP 1 319 412 A1 14 .

EP 1 319 412 A1 15 .