Title of Invention

COLOURED ANHYDROUS GEL ELEMENT

Abstract The present invention relates to a process for preparing co loured anhydrous gel I element for perfuming or deodorizing air or enclosed spaces which comprises cross-linking a functionalized liquid polymer selected from maleinised polybutadiene, maleinised polyisoprene or a copolymer of ethylene and maleic anhydride with a cross-linking agent which contains at least one complementary functional group in the presence of a non-aqueous perfume or deodorizing base and at least one metal-free solvent dye which is soluble in the non-aqueous perfume or deodorizing base, or which is provided as a solution in a non-aqueous solvent which is compatible with the non-aqueous perfume or deodorizing base.
Full Text

The present invention relates to a process for preparing colored anhydrous gel element which are capable of diffusing perfume or deodorizing components into the surrounding air.
The use of various devices for the diffusion of volatile compounds, for example perfumes deodorising compositions, insect repellents, and the like, into the atmosphere has become increasingly popular in recent years. For example, air-freshening devices.or deodorisers are currently used in practically all households to mask bad odours, or to impart fragrances to the ambient air. Various different types of devices are known for the diffusion of volatile compounds into the surroundings. For example, devices of the spray type, such as aerosol sprays, may be used to dispense a liquid composition into the ambient air. Other devices comprise housings enclosing the active ingredients in liquid form. Typically, the diffusion of the active ingredients takes place through membranes permeable to the vapours of said ingredient, or through a wick which is placed in a reservoir containing the ingredients.
Solid state devices are also known which comprise solid materials or carriers impregnated with an active ingredient, such devices may be formed of various materials which are capable of absorbing the ingredient and subsequently releasing it in a more or less controlled manner. Examples of such known materials include gels, such as agar-agar or sodium stearate gels, synthetic polymer resins, or blocks of mineral material, e.g. plaster or silica.

Solid state devices have the advantage that they are easy to handle and can be easily shaped. Typically/ the solid state devices are enclosed within a housing with one or more grills which communicate with the surrounding air.
The main disadvantage with solid state devices is that the release of active ingredients from the blocks is not constant with time and drops dramatically over the lifetime of the device. Furthermore, such devices are inefficient in that the device may cease to diffuse the active ingredient into the surrounding atmosphere when the outside of the block is spent, even though considerable amounts of the active ingredient may still reside within the core of the block. The residual active ingredient, such as perfume, is thus totally lost.
WO 96/05870 discloses a device for perfuming, deodorising or sanitising air or enclosed spaces which comprises an anhydrous gel element. Such a device is capable cf diffusing volatile substcmces at a relatively constant rate throughout the entire lifetime of the device and, furthermore, is capable of releasing substantially all of the volatile substance into the air or enclosed space within its effective lifetime.
The devices of WO 96/05870, although practically very useful, are unattractive since they are in the form, of substantially colourless gels. However, because of the manner in which the gels are formed we found chat it was difficult to incorporate dyes or colourants ir.to the gels. Many dyes would not disperse within the system and resulted in unattractive non-homogenous products in which the dye was not uniformly dispersed therethrough. Neither the colourless gels of WO 96/05870, nor the non-homogenous coloured gels would be attractive to the purchaser of such devices which generally will be on

display in the room or space which they are intended to perfume or deodorise.
We have now found that homogenous, 'coloured anhydrous gels can be prepared from the components as disclosed in WO 96/05870-if a very careful selection is made of the dyes for incorporation therein. The present invention is predicated upon this finding.
Accordingly/ the present invention provides a coloured anhydrous gel element for perfuming or deodorising air or enclosed spaces which gel element is formed by cross-linking a functionalised liquid polymer selected from maleinised pclybutadiene/ maleinised polyisoprene or a copolymer of ethylene and maleic anhydride with a cross-linking agent which contains at least one complementary functional group in the presence of a non-aqueous perfume or deodorising base and at least one metal-free solvent dye whi-h is soluble in the nonaqueous perfume or deodorising base cr which is provided as a solution in a non-aqueous solvent which is compatible which the non-acuecus perfume or deodorising base.
The present invention also provides a process for preparing a coloured gel element as defined above which comprises cross-linking the functionalised liquid polymer with the cross-linking agent in the presence of the nonaqueous perfume or deodorising base and at least one metal-free solvent dye.
By the term "functionalised liquid polymer" as used herein is meant a material which is liquid at room temperature and which has a viscosity of not more than 5 PaS at 25oC preferably from 0.25 to 1.0 Pas.

purchaser of such devices which generally will be on display m the room or space which they are intended to perfume or deodorise.
We have now found that homogenous, coloured anhydrous gels can be prepared from the components as disclosed.in WO 96/05870 if a very careful selection is made of the dyes for incorporation therein. The present invention is predicated upon this finding.
Accordingly the present invention provides a process for preparing coloured anhydrous gel element for perfuming or deodorizing air or enclosed spaces which comprises cross-linking a functionalized liquid polymer selected from maleinised polybutadiene, maleinised polyisoprene or a copolymer of ethylene and maleic anhydride with a cross-linking agent which contains at least one complementary functional group in the presence of a non-aqueous perfume or deodorizing base and at least one metal-free solvent dye which is soluble in the non-aqueous perfume or deodorizing base, or which is provided as a solution in a non-aqueous solvent which is compatible with the non-aqueous perfume or deodorizing base^
By the term "functionalised liquid polymer" as used herein is meant a material which is liquid at room temperature and which has a viscosity of not more than 5 Pas at 25°C, preferably from 0.25 to 2.0 Pas.

for example JEFFAMINE D-400, JEFFAMINE EDR-14 and Jeffamine D-2000;
polyoxyalkylenetriamines such, as those sold under the trade name JEFFAMINE (Huntsman Corporation) in particular the T series, for example JEFFAMINE T-403.
It is also possible to use as the cross-linking agent polybutadiene having a hydroxylic functionality known as H?PB (Revertex Limited) which gellifies when admixed with maleinised polybutadiene. Sometimes the use of specific catalysts allow a better control of the gel formation and examples of such catalysts are the tertiary amines (e.g. DAMA 1010; origin: Albermarle SA) . Mixtures cf Kycar CTBN 1300 x 21 which is an amine terminated liquid polybutadiene/acrylonitrile copolymer (origin: E.F. Goodrich) and maleinised polybutadiene are particularly advantageous.
The functionalised liquid polymer and the cross-linking agent are mixed in a molar ratio of between 3:1 and 5:1 preferably of about 1:1, based on the molar ratio cf the functional groups which are present.
The perfume base which is used in the device of the invention nay comprise any of the current bases used in perfumery. These can be discrete chemicals; more often, however, they are more or less complex mixtures of volatile liquid ingredients of natural or synthetic origin. The nature of these ingredients can be found in specialised books of perfumery, e.g. in S. Arctander Perfume and Flavor Chemicals, Montclair N.J., USA 1969) or Perfumery, Wiley-Intersciences, New York, USA 1994.

The perfume base may be replaced by a deodorising base, such as a base which comprises a deodorising composition.
The characteristic feature of all the compositions of the present invention is that the liquid polymer cros's-linking agent and dye which are used in the preparation of the gellified composition are all soluble in the perfume or deodorising base. Optionally, one or more of the liquid polymer, cross-linking agent or dye may be dissolved in a solvent which is compatible with the perfume of deodorising base, but generally this is not necessary since the components will dissolve in the active base.
The perfume or deodorising base is non-aqueous and will generally constitute from 50 to 95V by weight, preferably from 60 to 90% by weight, more preferably from 70 to 85% by weight of the gel element.
Optional additives which may be included in the gel composition include plasticisers such as diethylphthalate.
Examples of suitable classes of dyes which may be used in the present invention are monoazo dyes, diazo dyes, anthraquinone dyes or methine dye, provided that the dyes are metal-free solvent dyes. Specific examples of dyes which may be successfully used in rhe presenz invention are:
Chemical Characterization Trade Names
C.I. Solvent Red 27 Fat Red 5B-02
(Clariant) C.I. Solvent Red 111 Sandoplast Red PFS
(Clariant) C.I. Solvent Yellow 14 Fat Orange R-Ol

C-I- Solvent Yellow 93
C.I. Solvent Violet 13
C.I. Solvent Violet 37
C.I. Solvent Green 3
C.I. Solvent Green 28
C.I. Solvent Blue 104

(Clarianr)
Sandoplasc Yellow 3G
(Clariant}
Iragon Violet SV113
(Ciba)
Sandoplasw Violet FBLP
(Clariant)
Iragon Green SGR3
(Ciba)
Sandoplasc Green G
(Clariant)
Sandoplasr Blue 2B
(Clariant)

Dyes such as those listed above are generally in powder form. Accordingly, in order to be useful in the present invention the dye is generally soluble in the perfume or deodorising base. Hovrever, it may be possible to use some dyes which are either net soluble in or insufficiently soluble in the said base by using the dyes as concentrated solutions in a ncn-aqueous solvent which is compatible with the base.
Generally a relatively small amount of dye will be sufficient to colour the anhydrous gel, for example amounts of from 0.01 to 1.0% by weight, typically about 0.05% by weight based on the eel elemen", may be used.
Many dyes cannot be used in the present invention. Examples of such dyes which either are not metal-free solvent dyes and/or are not scluble in the perfurr.e or deodorising base, are giver, below

Chemical Characterization C.I- Solvent Orange 63
C.I. Solvent Red 179

Trade Names Hostalsol Red GG (Clariant) Sandoplast Red 2GP

C.I. Solvent Red 89
C.I. Solvent Red 91
C.I. Solvent Red 127

(Clariant)
Savinyl Fire Red GLSP
(Clariant)
Savinyl Red 3BLS P
(Clariant)
Savinyl Pink 6BLS P
(Clariant)

The anhydrous gel element of the present invention may be used as the active element of a solid state air freshening or deodorising device with the gel element being incorporated within a housing with one or more grilles which communicate with the ambient air.
Alternatively^ the gel element may be formed in sit within the recesses or grooves of a solid casing or housing. This type of device does not require the use c a grille to cover the gel element. The recesses or grooves of the solid casing or housing are filled with, the mixture of functionalised liquid polymer, cross-linking agent, perfume or deodorising base and dye and the cross-linking reaction to form the gel takes place in situ. The gel so-formed thus adheres to the sides and/or bottom of the recesses or groove in order to provide an integral structure.
The present invention will be further described wit reference to the following Examples.
EXAMPLE 1
To a vessel containing 63.975g of a perfume base (Lavandair 150.120D; origin - Firmenich SA, Geneva, Switzerland) was added 0.025g of dye (Iragon Violet SVI13; origin -Ciba Speciality Chemicals, Switzerlemd) with stirring. 17.0g of Lithene N4-B-10MA was then added manually and mixed. In another vessel 16.0g of the

perfume base (Lavender 150.120D) and 3, Og of ief famine D-400 were mixed and then added to the original vessel with stirring- After about 5 minutes at room temperature, a purple gel resulted encapsulating the perfume base. Gel setting was complete in about 20 minutes.
EXAMPLE 2
To a vessel containing 63.9lg of perfume base (Solar Splash 150.555; origin - Firmenich SA, Geneva, Switzerland) was added 0.09g of dye (Sanoplast Yellow 3G; origin - Clariant UK Ltd, United Kingdom) with stirring. 17.0g of Lithene N4-B-10MA was then added manually and mixed. In another vessel 16.Og of the perfume base (Solar Splash 150.555), 1.12g of Jeffamine EDR-148 and 1.88 g of diethyl phthalate were mixed and then added to the original vessel with stirring. After about 5 minutes at room temperature, a yellow gel resulted encapsulating the perfume base. Gel setting was complete in about 20 minutes.
EXAMPLE 3
To a vessel containing 63.97g of a perfume base (Summer Fruits 150.535; origin - Firmenich SA, Geneva, Switzerland) was added 0.03g of dye (Fat Red 5B02; origin - Clariant UK Ltd, United Kingdom) with stirring. 17.0g of Lithene N4-B-10MA was then added manually and mixed. In another vessel 16.0g of the perfume base (Summer Fruits 15.535), 2,40g of Jeffamine D-400, 0.22g of Jeffamine EDR0148 and 0.38g of diethyl phthalate were mixed and then added to the original vessel with stirring. After about 5 minutes at room temperature, a deep red gel resulted encapsulating the perfume base.. Gel setting was complete in about 20 minutes.

EXAMPLE 4
To a vessel containing 63.98g of a perfume base (Nile Blossom 438.910; origin - Firmenich SA, Gene—a: Switzerland) was added 0.02g of dye dragon Green; origin - Ciba Speciality Chemicals, Switzerland) with stirring. 17.Og of Lithene N4-B-10MA was then added manually and mixed. In another vessel 16.Og of the perfume base (Nile Blossom 438,910), 2.40g of Jeffamine D-400, 0.22g of Jeff amine EDR-148 and 0.38g of diethyl phthalate were mixed and then added to the original vessel with stirring. After about 5 minutes at room temperature, a blue/green gel resulted encapsulating the perfume base. Gel setting was complete in about 20 minutes,
EXAMPLE 5
To a vessel containing 63.97 of a perfume base (Summer Fruits 150.535; origin - Firmenich SA, Geneva, Switzerland) was added 0.03g of dye (Savinyl Fire Red GLSP; origin - Clariant UK Ltd, United Kingdom) wirh stirring. I70g of Lithene N4-B-10MA was then added manually and mixed. In another vessel 16.Og of the perfume based Summer Fruits 150,535), 240g of Jeffs-mine D-400, 0,22g of Jef famine EDR-148 and 0.38g of die-hyl phthalate were mixed and then added to the original vessel with stirring. After about 5 minutes at rcom temperature, a gel resulted, but the colour was nc-homogeneously distributed throughout resulting in ^n unattractive aspect. Gel setting was complete in 5.bout 20 nrdnutes .
EXAMPLE 6
To a vessel containing 3.998g of a perfume base (Lavandair 150,120D; origin - Firmenich SA, Geneva., Switzerland) was added 0.00156g of dye dragon Violet

SVI13; origin - Ciba Speciality Chemicals, Switzerland) with stirring. 1.0625g of Lithene N4-E-10MA was then added manually and mixed. In another vessel 1.0c of the perfume base (Lavandair 150.120D) and o;'1875g of Jeffamine D-400 were mixed and then added to the original vessel with stirring. Once a homogeneous mix was attained, the mixture was added to a suitable decorative device containing grooves which the liquid mix could run through. After about 5 minutes at room temperature, a purple gel, in the shape of the device, resulted encapsulating the perfume base. Gel setting was complete in about 20 minutes.


WE CLAIM ;
1. A process for preparing coloured anhydrous gel element for perfuming or deodorizing air or enclosed spaces which comprises cross-linking a functionalized liquid polymer selected from maleinised polybutadiene, maleinised polyisoprene or a copolymer of ethylene and maleic anhydride with a cross-linking agent which contains at least one complementary functional group in the presence of a nonaqueous perfume or deodorizing base and at least one metal-free solvent dye which is soluble in the non-aqueous perfume or deodorizing base, or which is provided as a solution in a non-aqueous solvent which is compatible with the non-aqueous perfume or deodorizing base,
2. The process for preparing coloured anhydrous gel element as claimed in claim 1 wherein the dye is C.I. Solvent Red 27, CI. Solvent Red 111, C.L Solvent Yellow 14, CI. Solvent Yellow 93, CI. Solvent Violet 13, CL Solvent Violet 37, CI. Solvent Green 3, CL Solvent Green 28 or CL Solvent Blue 104.
3. The process for preparing coloured anhydrous gel element as claimed in claim 1 or claim 2 wherein the dye is used so as to constitute from 0.01 to 1.0%) by weight of the gel element.
4. The process for preparing coloured anhydrous gel element as claimed in any one of the preceding claims wherein the perfume or deodorizing base used in an amount so as to constitute from 60 to 95% by weight of the gel element.
5. The process for preparing, coloured anhydrous gel element as claimed in claim 4 wherein the perfume or deodorizing base constitutes from 70 to 80%) by weight of the gel element.

6. The process for preparing coloured anhydrous gel element as claimed in any one of the preceding claims wherein the functionalized liquid polymer is a maleinised polybutadiene having a number average molecular weight in the range of from 5,000 to 20,000, or a maleinised polyisoprene having a number average molecular weight of from 200,000 to 500,000.
7. The process for preparing coloured anhydrous gel element as claimed in any one of the preceding claims wherein the cross-linking agent is an alkylpropylamine, an ethoxylated or propoxylated primary fatty amine, a polyoxyalkylenediamine or a polyoxyalkylene triamine.
8. The process for preparing coloured anhydrous gel element as claimed in any
one of the preceding claims wherein the liquid polymer and cross-linking agent are
soluble in the perfume, deodorising or sanitising base.
9. A device wherein a coloured gel element prepared by the process as claimed in any one of claims 1 to 8 has been incorporated.
10. The device as claimed in claim 9 which is an air freshener.
11. The device as claimed in claim 9 which is a deodorizer.
12. A process for preparing a device as claimed in claim 9 which comprises preparing the colour anhydrous gel element in the device by a process as claimed in any one of claims 1 to 8.
13. A process for preparing coloured anhydrous gel element for perfuming or
deodorizing air or enclosed spaces such as herein described.


Documents:

in-pct-2002-1842-che-claims duplicate.pdf

in-pct-2002-che-1842-abstract.pdf

in-pct-2002-che-1842-claims original.pdf

in-pct-2002-che-1842-correspondance others.pdf

in-pct-2002-che-1842-correspondance po.pdf

in-pct-2002-che-1842-description complete duplicate.pdf

in-pct-2002-che-1842-description complete original.pdf

in-pct-2002-che-1842-form 1.pdf

in-pct-2002-che-1842-form 19.pdf

in-pct-2002-che-1842-form 26.pdf

in-pct-2002-che-1842-form 3.pdf

in-pct-2002-che-1842-form 5.pdf

in-pct-2002-che-1842-pct.pdf


Patent Number 204234
Indian Patent Application Number IN/PCT/2002/1842/CHE
PG Journal Number 26/2007
Publication Date 29-Jun-2007
Grant Date 13-Feb-2007
Date of Filing 11-Nov-2002
Name of Patentee RECKITT BENCKISER (UK) LIMITED
Applicant Address 103-105 Bath Road Slough Berskhire SL1 3UH
Inventors:
# Inventor's Name Inventor's Address
1 SHAH, Syed, Ashfaq, Ali 96 Trapstyle Road Ware Hertfordshire SG12 0BB
PCT International Classification Number A61L9/04
PCT International Application Number PCT/GB2001/001775
PCT International Filing date 2001-04-19
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 0009577.8 2000-04-19 U.K.