AU608286B2 - Aerosol products - Google Patents

Description

AUAI411591/B 8 WORLD [INTELLECTUAL PROPERTY ORGANIZATION Inte~rnationl Bureau

PCT

q4 INTERNATIONAL APPL I[CATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4: 1)ItrainlPbiafn .ne: W 8 49 A23C 9/00, 23/00, A23L 1/42 A 31 a t tion Ub o e: 14 July 1988 (14,07.8811 C09K 3/30n (21) Inteenationvl Application Number: PCT/AU8S/00003 (81) Designated State,-. AT (European patent), AU, BE (Eu- (22) International Filirg Date: 5 January 1988 (05.01.88) pean patent), FR (European patent), GB (European patent), IT (European patent), JP, LU (European pa- (31) Priority App~ication Number: P975tent), NL (European patent), SE (European patent).

(32) Priority Date: 8 January 1987 (08.0 1.87) Published With international search report, (33) Priority Country: AU Before the expiration of the time limntt for amending the claims and to be republished in the event of die receipt (71) Applicant: SQLTEC RESEARCH PTY, LTD. [A U/ of amendments.

AU]; 7 Brand Road, Knoxfield, VIC 3 180 (AU), (72) Inventors: HALLS, Neil, Graham 30 Stableford Avenlue, Glen Waverley, VIC 3 (50 TOMINSON, Roderick, Peter 1,32 Highwood Drive, Glen Waverley,

A

4 j SEP 198 VIC 3150 (AU), (74) Agent: EDWD, WATERS SONS, 50 Queen Street, Melbourne VIC 3000

AUSTRALIAN

Thii qoipt cnains Lt9 ttn~pL~l~fls mde uder2 7 JUL 1988 eT i sp a nd i co rrta ifrU L~xjj 9ndi orc forit g. _j PATENT orFFICE (54) Title:' AEROSOL PRODUCTS (57) Abstract An aerosol tciispenjable composition comprising in combination, 0,05 to 5 xv/w of a frothing agent*, (ii) 0,05 to ql w/w of a swveetener; (!Iii, 0,05 -to 10 O/ W/w of a thickener: (iv) 0,0 1 to I w/w of a preservative; 0, 1 to 10 w/wv a phosphate buffer system adapted to maintain the pH of the compositions in. the range 8.0 to 8,5; and the balance being selected from other excipients, flavours and colourants, propellan Its and water, r[ WO-88/04896 PCT/A U88/00003 t -1- AEROSOL PRODUCTS FIELD OF THE INVENTION This invention relates to a composition for use in forming milk shake type products.

This invention was conceived as a means for preparing a flavoured thickened foamy milk-based drink as an alternative to the traditional milk shake which was formed by blending milk with syrup powdered flavours and ice-cream in a mechanical blender. It is an object of the invention to provide a similar milk drink using ar aerosol dispenser.

The requirements of a product of this type should include compatibility with exisiting aerosol packaging types in order to minimise manufacturing cost.

(ii) a shelf life in an unrefrigerated condition of at least twelve months.

(iii)full complicance with food regulations.

(iv) consumer acceptable flavours as attractive as possible, convenience in use.

(vi) capability of being thickened and frothed in addition to being flavoured.

In order to achieve these objects, it was realised that many constraints existed preventing the formulation of Sa successful product as discussed below.

Most fla'ours have a limited shelf life in solution due to oxidation, rUJrobial attack, enzymatic breakdown, etc.

The product should be of a low viscosity intially, so that it can be ejected rapidly from the aerosol can to provide the necessary mixing action. This is not easily achieved because the product needs to be concentrated and the thickeners and viscosity builders required in the composition are also concentrated.

Conventional aerosol cans are not produced to food quality specifications and the lining systems are not able to hold pressurized, low pH liquids for adequate periods of WO 88/04896 PCT/AU88/00003 -2time. However, most food products are packed in liquids at a low pH in order to avoid microbial spoilage.

The necessity to provide preservation of the product in the absence of low pH compositions must be Sachieved from the narrow range of food approved added preservatives.

The aerosol propellant is normally restricted to noncondensible gases by food regulations in most countries.

Finally food colours are also affected by some of the above parameters and must be properly regulated.

From the above it can be seen that a large number of difficulties stand in the way of providing an acceptable aerosol product.

In PCT/AU/85/00135 an aerosol dispensable composition is disclosed comprising in combination 0.05 to 5% of a frothing agent, (ii) 0.05 to 75% of a sweetener, (iii)0.05 to 10% of a thickener, (iv) 0.01 to 1% of a preservative, and 2 the balance being other exdipients, flavours and colourants, propellants and water. High levels of sweetener are exemplified and believed necessary to maintain bacterial control. This document also discloses the need to maintain the pH in the neutral range, however, the systems disclosed have failed to eliminate pinhole corrosion within relatively short times e.g. less than six months.

A similar approach is disclosed in U.S. Patent 3,622,354 which relates to a product utilizing high sugar levels to achieve bacterial control and also reveals the use of preservatives at low pH In both instances the product produced is not acceptable primarily due to short shelf life and corrosion.

Accordingly further investigation has taken place concerning stabilizing such mixtures.

SUMMARY OF INVENTION Surprisingly, a particular phosphate buffer system has been discovered which has been found to effectively ~VO .88/04896 P CT/A U88/00003 WO,88/04896 PCT/AU88/00003 -3stabilize the mixture by maintaining pH in the range 8.0 to Accordingly, there is provided an aerosol dispensable composition comprising in combination S(i) 0.05 to 5% w/w of a frothing agent; (ii) 0.05 to 75% w/w )f a sweetener; (iii)0.05 to 10% w/w of e thickener; (iv) 0.01 to 1% w/w of a preservative; 0.1 to 10% w/w a phosphate buffer system adapted to maintain the pH of the compositions in the range 8.0 to and the balance being selected from other excipients, flavours and colourants, propellants and water. Preferably, the phosphate buffer system is present in an amount ranging from 0.1-2.5% w/w. The phospate buffer system typ,cally comprises a mixture of potassium phosphate and sodium phosphate. This system also allows various types of flavour other than chocolate and strawberry to be also practically incorporated. More particularly the bufzer system can comprise a mixture of potassium dihydrogen phosphate and disodium hydrogen phosphate, the ratio of KH 2PO 4 to Na HPO4 being from 1:60 to 1 to 105.

Testing has shown that a.composition of the type disclosed in PCT/AU/85/00135 can be stabilized and no corrosion has been detected either at room temperature or under accelerated high temperature storage conditions.

Thus, the product exhibits very long shelf life.

Preferably, the phosphates are blended in the following ratio to maintain the composition pH in the range 8.0-8.5.

KH

2

PO

4 pH 4.62 as 1% aqueous solution.

Na 2

HPO

4 pH 9.12 as 1% aqueous solution.

KH

2

PO

4 :NaHPO :1.0:87.4 The preferred ingredients for the composition of this invention are as follows: A. Frothing agent is selected from emulsifiers of the socbitol ester, glycerol ester or fatty acid sucrose ester types. Most preferred are glycerol monostearate, sorbitol WO 88/04896 PCT/AU88/00003 monostearate which generally produce the best foam with the least affect on flavour. The frothing agent also aids in the stable dispersion of the flavour agents.

B. The sweetener may be selected from artificial sweeteners such as saccharine, aspartame, dextrose, fructose or from natural sweeteners such as sucrose. Typically artificial sweeteners are used in the range 0.1 to 5% whilst natural sweeteners are normally in the range 5 to 75%. The most reliable sweetener is sucrose and the level of sweetener required is constrained by adequacy in providing sweetening effect at the lower end of the scale and by viscosity and solubility at the upper end of the concentration range. Excessive levels when combined with other excipients can produce crystalline growth in the aerosol cans which results in valve blockages. The most preferred sweetener is sucrose used at a level of between 75%. Typically, a representative formula is Flavour Sucrose 61.0 Water 28.99 AZO Red Dye 0.010 Nitrous Oxide C. Careful selection of the thickener is required because the product is normally used at a dilution of around and with conventional thickeners such as pectin, tragacanth, the ten-fold concentration in the aerosol product would result in a viscosity that was too high to allow proper dispensing from the aerosol can. Thus, preferred thickeners are gums of polysaccharide type particularly those of a grade which undergo interaction with milk to produce a large increase in milk viscosity after contact. A number of the gums tested showed a tendency to age thicken when stored over a period of time. This aging tendency was reduced by addition of water softening components of the phospate type. Preferred thickeners are carragheenan, methylcellulose, hydroxypropylcellulose, and general polysaccharides.

An example of thickeners follows:- Flavour Sucrose Water Xanthane Gum Sodium Hexametaphosphate Nitrous Oxide 50.0 45.95 0.05 '1

*OS*S.

C

e.g.

S S C S 0* 0

S

S

C

C

C

C. CS

C

SCSS

S S CS

C

C

C

0

C

0

CC

C C

S

D. The colouring agents should be present in the range of 0.01 to 5% preferably 0.01 to Variation of the other 15 components of the composition tends to produce variable Effects on colour. Many colours also increase the corrosivity of the formula to the aerosol container. All approved dye stuff are suitable. The preferred colouring agents are azodyes of the ponceau 4R, erythroscine, carmoisine, tartrazine type, brilliant blue Brown HT, allura red and a wide range of natural colouring substances.

E. Typical examples of the buffer system are as follows: Buffer No. 1: Dipotassium Dihydrogen Phosphate 77.2% W/W Potassium Dihydrogen Phosphate 22.7% W/W pH of above combination in water at 2.2% W/W is 8.0 (outside scope of invention) Buffer No. 2: Potassium Dihydrogen Phosphate 79.0% W/W 30 Sodium Hydroxide 21.0% W/W pH of above combination in water at 0.7% W/W is 8.1 Buffer No. 3: Potassium Dihydrogen Phosphate 1.1% W/W Disodium Hydrogen Phosphate 98.9% W/W pH of above combination in water at 1.2% W/W is Each buffer introduces stability and performance to the dispensable composition described. This systen ensures 1 t -6microbiostatic, microbiocidal and fungicidal effect and as well reduce corrosion of lacquered tinplate to the point where shelf life if in excess of twelve months at 20°C are now achievable.

F. The balance of the mixture is made up with purified water.

G. The propellant to be used to dispense the composition from the aerosol can will comprise 2 to 50% by weight and can comprise any food approved propellant.

Preferably nitrous oxide, carbon dioxide and octaflurocyclobutane, or propane may be used. However, the most preferred propellant is nitrous oxide in order to achieve the optimum performance required for this particular composition. Due to its non-condensable nature a higher pressure can be used to ensure mixing with nitrous oxide than with condensable propellants. In addition, the condensable propellants tend to produce a shaving-cream type foam due to their densities and settle out of the system.

Care must be taken if carbon dioxide is used as propellant because it is acidic. However, it could be used where lined aerosol cans are used.

EXAMPLES

0 0 *060 *5 S. 5 5500 S S

*SSS

S

S

S

US S

EXAMPL

E 1

COMPONENT

Flavour Sodium Benzoate (preservative) Polysaccharide Gum Dye Stuff 30 Glyceryl Monostearate Nitrous Oxide sucrose Water Butylated Hydroxy Anisole Disodium Hydrogen Phosphate Potassium Dihydrogen Orthophosphate

W/W

0.1 0.01 5.01 0.001 0.01 0.5 0.1 z-U

BALANCE

0.001 0.01 0.01 i-1 0 0*0*

S

0S

S

0 0000 00 00 0 0 -7- The optional preservative can be selected from among the approved food preservatives which include: Methyl-p-hydroxybenzoate Ethyl-p-hydroxybenzoate Propyl-p-hydroxybenzoate Butyl-p-hydroxybenzoate Potassium Sorbate Sodium Benzoate Sulphur Dioxide EXAMPLE 2

COMPONENT

Flavour Sucrose Sorbitol ester Hydroxy propyl cellulose Buffer No. 1 (aforestated) Colour Water 2 EXAMPLE 3 Flavour Sucrose Sorbitol ester Hydroxy propyl cellulose 25 Buffer No. 2 (aforestated) Colour Water 3.000 50.000 2.000 0.080 2.200 0.008 TO 200% 3.000 50.000 1.000 0.080 0.700 0.008 TO 100% 0 30 In each of the examples, testing over a prolonged period of months has failed to reveal any corrosion spoilage or bacterial spoilage.

Aerosol milk shake compositions utilizing the buffer system achieve a long life and permit a wider range of flavours than previously possible.

DBM:EK(13:39)

L-

Claims (11)

1. 2. The composition according to Claim 1 wherein the phosphate buffer system is present in an amount ranging from 0.i to Z.5% w/w.
2. 3. The composition according to Claim 1 wherein the phosphate buffer system comprises a mixture of potassium phosphates and sodium phosphates.
3. 4. The composition according to Claim i wherein the phosphate buffer system comprises a mixture of disodium hydrogen phosphate and potassium dihydrogen orthophosphate. The composition according to claim 1 wherein the phosphate buffer system comprises a mixture of potassium dihydrogen phosphate and disodium hydrogen phosphate, the ratio of KH PO 4 to Na HPO 4 being from 1:60 to 1 to 105.
4. 6. An aerosol dispensab composition according to Claim 1 wherein the frothing agent is selected from emulsifiers of the sorbitol ester, glycerol ester and fatty acid sucrose ester types. WO.88/04896 PCT/AU88/00003 -9-
5. 7. An aerosol dispensable composition according to Claim 1 wherein the frothing agent is glycerol monostearate and/or sorbitol monostearate.
6. 8. An aerosol dispensable composition according to Claim 1 wherein the sweetener is selected from the group of artificial sweeteners including saccharine, aspartame, dextrose and fructose. S9. An aerosol dispensable composition according to Claim 1 wherein the sweetener is an artificial sweetener present in amounts from 0.1 to An aerosol dispensable composition according to Claim 1 wherein the sweetener is a natural sweetener present in amounts of from 5 to
7. 11. An aerosol dispensable composition according to Claim 1 wherein the thickener is selected from the group of gums of the polysaccharide type including carragheenan, methylcellulose, hydroxypropylcellulose and general polysaccharides.
8. 12. An aerosol dispensable composition according to Claim 1 wherein the colourants are present in the range of 0,01 to
9. 13. An aerosol dispensable composition according to Claim i wherein the colourants are selected from the group of asodyes of the ponceau 4R, erythroscine, carmoisine, tartrazine type, brillian blue F.CF., brown HT and allura red, PCT/AU88/00003
10. 14. An aerosol dispensable composition according to Claim 1 whezein the propellant is selected from nitrous oxide, carbon dioxide, octafluorpcjc.lobutane and propane. INTERNATIONAL SEARCH REPORT IAIVMSIIS.4 AspeiCaeM NO PCT/AU 88/00003 o, CLASSIFICATION OF SU11JECT MATTER11 I Ifoo~' :e,.cui i.sko:Io Sott .Ae4:0 1110 A440111101 to 111ter 018ioneu Patent -Cla s.fteeeoo- fiiPC) oId, S6efl M41ioR4 Classificationl an IPC Int. C1. 4 A236 9/00, 23/00, A23L 1/42, C09K 3/30 IPC A23C 9/00, 23/00, A23L 1/19, 1/14, 1/42, C09K 3/30 us Cl 426/317 lecuiientetien S4e'clthe r the! wP04 inifnom 00clmar9esluon, to the £zlun"Iteu I4Iim Documnfts inclujded on Ino Fields Starched AU IPC as above III, no CUPPORTS CONSICERED1 IrO 118 J11LEVA0MT' Cattgo"V CI~sIoflG Of Oa1CUMR1.n. with 1Ai11CAU41n. WMefo dialt( loo. at the Ftle411~t lossas 11 Rel.ent to C1ito,n 13a X WO,A, 86/:C 1 96 (SOLTEC RESEARCH PTY. LTD, TOM'LINSON) (1-14) 16 Janfuary 1986 (16.01.86) See page 5, lines 18-27,, especially line 25; and claims. X 3622354 (DIAMOND) 23 November 1971 (23.11.71) (1,2,6-14) Se~e especially column 1, lines 15-20; column 3, lines
11. 32-34'; examples 4-8; and claims. X US,A, 4343825 (TAKEDA et al 10 August 1982 (10.08.82) (1-14) See, column 2, lines 29-35. X AU,B, 28005/71 (453541) (CARNATION COMPANY) 26 October (1-14) 1972 (26.10.72) See especially page 15, example 1 and page 8, lines 2-10. A EP,A, 125768 (ASAHI DENKA KOGYO KABUSHIKI KAISHA) 3 April 1985 (03.4.485) See page 8, lines 20-21; page 7, lines 10-14; page 9, line 16; and page 9, 11 ne 2 2. Y US,A, 4571338 (OKONOGI et al) 18 February 1986 (1-.13) (18.02,86) See especially column 2, lines 24-31 and coh, 3, lines 29-33. Y GBA o 1449271 (HERRING et al 15 Septembev, 1976 (14) (15.09,76) See column 1, littes 9-12 (continued) k dCU l 4 44M t he Wajist sa.te 1 6O lled oYOcaad11)prik11,o 11ety Unqlrt;.n theO ".)S4f do E0to ofl of4 Damileia 044fo *its tenetIe~~f 'W dOineiifon C IP I.i(l Pe ti~* ve Along 4 t 00109 (mne 0 441111 461 MOV4 Of CIPSA41 4e COrietE0"d to fl. document Whichl froo WOWt~ daviii on bteelly 41teisf) O# involve &A invent~ive Olga gonom t i ld tof. 664116 w tohetI$ S~O4iC4tI dw of1 0 iet of *y 44tm of sa'Icgulf e rtel, theo claimed iri,.rlien cittioni of V'lew aschi fl fo 6n(s 000401441$ cannot it C111,'e i toi involve am inventive Mtg e l t9OA *01 astumont t:ffihi, Ill sit efoll eIe0$e1utf. us0-6111 11111104" Of doe~l int so oleSYIfs$Ii wiehi *Ae 64 mats 41e19? W44Af 409u- t hat l Med noot s c nh,Smlian og esogeigo to P, iqP4 sren 5144 scuimioitit sj sid SCIoi to to iI flefhtoA4 Oln$ data Oel 1Ai 1116 AM. 144er Ilion the1s tm 4411t O t 'is rk 410isiniorti mooNt of Iei senme 11111eA faily4 tV. CART(VICATION 041# o Is Actual Cemtestee' f t. onfire 00140 AM 34401 1 0a1# of Wading of IMIO lnijrrestonalow erte Roenr 27 April 1988 (27.04.88) 1o"O 9~ Australian Patent Office I .z GRANT) him oc .1 a 16;14 4110 W"440 -oa 'Iternation~al Applicationl No, PCT/AU 88/00003 THUIR INFORMATION CONTINU1111 FROM TI SICONO SHEET A IR.C. -WEAST, "CRC Handbook of Chemistry and Physics", 66th edi-tion, published 1,85, by CRC Press, Inc. (Boca Raton, Florida), See page D-144. 98SARVATIONS WHIMS CIATAIN CLAIMS WER FOUND intwtliontI saarcl tracl fAs$ not 0.*n ollaoilfld In respect Of CurtAIn claims Yndi AIIe,4 17171 for !he following reasons: Claim mnistsr bec.ause limiy 10.iso subject matter not requited to of sa.iriu-,#4 bl this* AYlhotly, (iamsIy: Claim numors because liial' estate lo oarts Of Itis 1nftna~~t4illkslia that do not CO Oly withi Iii orolChibed foQuiro- Mon~t sucri an llf thiat no me sninc; tl mcn tiaional sotarci, CAA 0. carried Out, 4siti4Iii 1 ClarlMUM0 au 00"si Itme sit 001 Clais Vnd We 1141 WOW intp Ac 40c1t a xtai 1ct fd, ANd third 50 'wcn of PCT Al C.441, OsSERVYATIONS WHIMS UNITY O10 INVINTION IS LAC)UHGI IfefalflamicA 5.a,:nlng Aim1fouii found miyftiufl, ctin In tis international application as followli As all ticiieadditional 6eAN11 1s.. we(* tily paid by h fi oplicaft. ti international, alotcflifof 100 ovfe 411 0.arcomo claim$ Of th. 1011farnaional 4041144114%., As only some of the, requited Additional Searchfteet veto timely gold by t. asellcant, fNO International searchs flooft covets only7 Imes@ claimns of tinItstflationsi eooi4stion fot wnin 4* were cciii, 40eccflcally claima: No reqited additional aaarift fees were timely 0o1d by the asellicart, Consoquently, this Informatliinal souht report Is restricted I's th. innorutie first rient~ie i n this 4tainvel It Is coverlet by claim iiuaiiifst As oll searchslbeclaime a ould so soerched witmout 6114A IY41tiyin I 4dilieiiak fee, this IiiIsti9,tiosui 3*1ifiln Authority did not ,aiis Paymenit of any addtiional flo. er% ont Pk'tee The sdiiismal "sigh Iate wer OcciwB"Il~ IT aselllsru'N 11re10l1111 No ,offli aeetwoiol is pa emrfent of 4011114M1tenlarectools.g. CTIISA1210 (Ouaeemointi At (2ef11 W0,4" 11 41l ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INERNATIONAL APPLICATION No. PCT/AU 88/00003 This Annex lists the known publication level patent family members relating to the patent documents cited in the above-e _ntioned intemnational search report. The Australian Patent Office is in no way liable for these particulars which are nrely given foz the purpose of infornation. Patent Document Cited in Search Patent Family Members Report WO 8600196 AU 44995/85 EP 190158 US 3622354 US 4343825 JP 56042555 AU 28005/71 CA 919493 DE 2122033 FR 2091171 GB 1299304 IT 1004011 US 3851071 EP 135768 JP 60064626 US 4571338 DE 3425284 JP 60019452 GB 1449271 CA 1006747 IE 39174 EN) OF ANNEX 23@/110/4