AU673668B2

AU673668B2 - Compositions and method for dilute cleaning of hard surfaces

Info

Publication number: AU673668B2
Application number: AU39194/93A
Authority: AU
Inventors: Johan Karel Emma De Waele; Louise Gail Scott
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1992-03-17
Filing date: 1993-03-15
Publication date: 1996-11-21
Anticipated expiration: 2013-03-15
Also published as: WO1993019148A1; NO943414L; CN1080951A; DE69231555D1; EP0561103A1; IE930201A1; FI944316A0; EP0561103B1; BR9306091A; DE69231555T2; ES2151483T3; NO943414D0; FI944316A; CA2131330C; MX9301506A; CA2131330A1; AU3919493A; MA22824A1; JPH07504704A

Description

OPI DATE 21/10/93 APPLN. ID 39194/93 I II III I IIIlI 11 111 IIIII AOJP DATE 23/12/93 PCT NUMBER PCT/US93/02335 iI II 1 1ii AU9339194

,PCT)

(51) International Patent Classification 5 (11) International Publication Number: WO 93/19148 CllD 1/722, 1/83 Al (43) International Publication Date: 30 September 1993 (30.09.93) (21) International Application Number: PCT/US93 02335 (74) Agents: REED, David et al.; The Procter Gamble Company, 5299 Spring Grove Avenue, Cincinnati, OH (22) International Filing Date: 15 March 1993 (15.03.93) 45202 (US).

Priority data: (81) Designated States: AU, BB, BG, BR, CA, CZ. Fl. HU, JP, 92870045.9 17 March 1992(17.03.92) EP KP, KR, LK, MG, MN, MW, NO, NZ, PL, RO, RU, (34) Countries for which the regional SD, SK, UA, US, European patent (AT, BE, CH, DE, or international application DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), wasfiled: BE et al. OAPI patent (BF, BJ, CF, CG, CI, CM, GA. GN, ML.

MR, SN, TD, TG).

(71) Applicant (for all designated States except US): THE PROC- TER GAMBLE COMPANY [US/US]; One Procter Published Gamble Plaza, Cincinnati, OH 45202 With international search report.

(72) Inventors; and Inventors/Applicants (for US only) DE WAELE, Johan, Karel, Emma (BE/BE]; Meerweg 33, B-1980 Zemst (BE), SCOTT, Louise, Gail (GB/BE]; Stijn Streuvelslaan 9, B.

1933 Sterrebeek (BE), 67366B (54)Title: COMPOSITIONS AND METHOD FOR DILUTE CLEANING OF HARD SURFACES (57) Abstract The present invention encormpasses hard surface cleaning compositions comprising highly ethoxylated nonionic surfact.

ants, possibly in mixture with anionic surfactants, The present invention also encompasses a method of cleaning a hard surface wherein said compositions are diluted in water and applied to said hard surface, The present invention also encompasses the diluted cleaning composition obtained in the method according to the present invention, i COMPOSITIONS AND METHOD FOR DILUTE CLEANING OF HARD SURFACES Technical field The present invention relates to the cleaning of hard surfaces. Hard surface cleaning compositions comprising at least one highly ethoxylated nonionic surfactant and possibly an anionic surfactant, are diluted before use, exhibiting outstanding dilute cleaning performance.

Background Hard surface cleaning compositions are well known in the art. It is known to use various surfactants in these compositions, including ethoxylated nonionic surfactants. Ethoxylated nonionic surfactants which are typically us',d in such compositions are lower ethoxylates, i.e. with a degree of ethoxylation of 5 to 7.

Compositions which can be used in diluted form are also known in the art. In such compositions, the technical problem lies in sustaining upon dilution an 20 efficient cleaning performance. Such compositions for dilute cleaning are described for instance in copending European Patent 503219. In these compositions, the dilute cleaning performance is obtained by using alkanolamines.

It would therefore be desirable to provide hard surface cleaning compositions which can be effectively used in diluted form.

This may be achieved by formulating hard surface cleanin, compositions comprising at least one highly ethoxylated nonionic surfactant, preferably with at least one anionic surfactant. These compositions unexpectedly exhibit outstanding cleaning performance upon dilution, compared to the same I, compositions without said nonionic surfactant while the cleaning performance of 2 the neat, i.e. undiluted compositions is similar, regardless of the presence of said nonionic surfactant.

In other words, it has now been found that hard surface cleaning compositions comprising said highly ethoxylated nonionic surfactant exhibit outstanding cleaning performance when used both neat and diluted.

Surprisingly, said compositions comprise a highly ethoxylated nonionic surfactant, yet they are especially effective on greasy soils. Such greasy soils are commonly brought by cooking with oils and fatty foods, and by simple contact with human skin, thus they are present on most surfaces, particularly in bathrooms and kitchens. The compositions according to the present invention are suitable for use on all such surfaces.

This invention is also particularly useful as it allows to formulate compositions with reduced levels of other ingredients, which yet retain optimal cleaning :performance, due to said highly ethoxylated nonionic surfactant; also, the user needs less product to achieve the same task, This advantage is particularly valuable in terms of environmental compatibility.

Compositions comprising highly ethoxylated fatty alcohols are described in US 595369 (abstract), These compositions are designed for the cleaning of metallic surfaces in weaving machines.

Throughout the description and claims of this specification, the word "comprise" and variations of the word, such as "comprising" and "comprises", is not intended to exclude other additives or components or integers.

Summary of the Invention The present invention provides a composition for the cleaning of hard surfaces ~comprising from 0.5% to 30% by weight of the total composition of at least one 1-s s nonionic surfactant, wherein said nonionic surfactant is of the formula RO-

(CH

2

CH

2 0)NH wherein R is a C8 to C22 alkyl chain or a C8 to C28 alkyl benzene chain, and n is an integer of from 21 to 65, or mixtures thereof.

The present invention also provides a composition for the cleaning of hard surfaces comprising from 0.5% to 30% by weight of the total composition of a mixture comprising at least one anionic surfactant and at least one nonionic surfactant, wherein said nonionic surfactant is of the formula RO-(CH 2 CH0)H wherein R is a C8 to C22 alkyl chain or a C8 to C28 alkyl benzene chain, and n is an integer of from 10 to 65, or mixtures thereof.

The present invention also provides the diluted compositions obtained by diluting the above compositions in water. Said diluted compositions comprises from 0.001% to 3.5% by weight of the total composition of said nonionic surfactant or said mixture of anionic surfactant and nonionic surfactant.

The present invention also provides a method of cleaning hard surfaces wherein a composition comprising at least one nonionic surfactant of the formula RO-

(CH

2 CH20)nH wherein R is a C8 to C22 alkyl chain or a C8 to C28 alkyl benzene chain, and n is an integer of from 10 to 65, or mixtures thereof, is diluted in water and applied to said hard surface, Detailed description of the invention The Compositions according to the invention comprise, as an essential ingredient, a highly ethoxylated nonionic surfactant. The highly ethoxylated nonionic surfactants to be used in the compositions according to the present invention are carefully selected, and belong to the group according to the formula RO-

(CH

2

CH

2 0)nH, wherein R is a C8 to C22 alkyl chain or a C8 to C28 alkyl benzene chain, and n is an integer WO 93/19148 PCT/US93/02335 4 of from 10 to 65, or mixtures thereof. Indeed, it is unforeseeably only those ethoxylated alcohols with such a high degree of ethoxylation which allow to obtain the observed cleaning benefits in diluted form, especially on greasy soils. Accordingly, the preferred nonionic surfactants for use in the compositions according to the present invention are those according to the above formula where n is from 11 to more preferably 18 to 35, most preferably 21 to 30. The preferred R chains for use herein are the C 8 to C 22 alkyl chains, Suitable chemical processes for preparing the highly ethoxylated nonionic surfactants for use herein have been extensively described in the art, Suitable highly ethoxylated nonic-ic surfactants for use herein are also commercially available, for instance in the series commercialized under the trade name LUTENSOL R from BASF or DOBANOL R from SHELL. A preferred highly ethoxylated alcohol for use herein is LUTENSOL R A030 (R is a mixture of C1 3 and C 15 alkyl chains, and n is 30). It is also possible to use mixtures of such highly ethoxylated nonionic surfactants, with different R groups and different ethoxylation degrees.

The compositions according to the present invention may additionally comprise an anionic surfactant. The prior art extensively describes anionic surfactants, including alkyl benzene sulfates and sulfonates, paraffin sulfonates, sulfonates of fatty acids and of fatty acid esters, all of which are suitable for use herein. Said anionic surfactants can also be used in the form of their salts, including sodium, potassium, ammonium and triethanolammonium salts. The preferred anionic surfactants for use in the compositions according to the present invention are paraffin sulfonates, preferably in the form of their sodium salt.

When the compositions according to the present invention comprise both said highly ethoxylated nonionic surfactant and said anionic surfactant, these are preferably present in a weight ratio of said anionic surfactant to said nonionic surfactant of from 0.2 to 5, more preferably to In one embodiment of the present invention, a hard surface cleaning composition according to the present invention comprises from 0.5 to preferably from 1 to 15 by weight of the total composition of WO 93/19148 PC/US93/02335 at least one nonionic surfactant of the formula RO-(CH 2 CH20)nH wherein R is a C 8 to C 22 alkyl chain or a C8 to C 28 alkyl benzene chain, and n is an integer of from 21 to 65, or mixtures thereof.

In a second embodiment of the present invention, a hard surface cleaning composition according to the present invention comprises from 0.5 to preferably from 1 to 15 by weight of the total composition of a mixture comprising at least one anionic surfactant and at least one nonionic surfactant, wherein said nonionic surfactant is of the formula

RO-(CH

2 CH20)nH wherein R is a C8 to C 2 2 alkyl chain or a Cg to C28 alkyl benzene chain, and n is an integer of from 10 to 65, or mixtures thereof.

The diluted compositions according to the present invention, which are obtainable by diluting the compositions described hereinabove, comprise from 0.001 to 3.5 by weight of the total composition of the mixture described hereinabove, preferably from 0,01 to 0,3 The hard surface cleaning compositions according to the present invention may further comprise additional surfactants, including other nonionic surfactants, amphoteric and zwitterionic surfactants and mixtures thereof. Typical of these are lower ethoxylated nonionic surfactants (e.g with an ethoxylation degree of about amine oxides, betaines, sulphobetaines and the like, which are well-known in the detergency art.

The compositions according to the present invention may further comprise an alkanolamine, or mixtures thereof, in amounts ranging from 0,1% to by weight of the total composition, preferably from 0.5% to most preferably from 0.8% to At such levels, the alkanolamine has a buffering effect in the undiluted product, as well as an unexpected boosting effect on the cleaning performance of the diluted compositions.

Suitable alkanolamines for use in the compositions according to the present include monoalkanolamines, dialkanolamines, trialkanolamines, alkylalkanolamines, dialkylalkanolamines and alkoxyalkanolamines.

Preferred alkanolamines to be used according to the present invention include monoethanolamine, triethanolamine, aminoethylpropanediol, 2- WO 93/19148 PCT/US93/02335 6 aminomethyl propanol, and ethoxyethanolamine. Particularly preferred are monoethanolamine, triethanolamine and ethoxyethanolamine.

The compositions according to the present invention may further comprise builders. Suitable builders for use herein include nitrilotriacetates (NTA), polycarboxylaces, citrates, water-soluble phosphates such as tripolyphosphate and sodium ortho-and pyro-phosphates, silicates, ethylene diamine tetraacetate (EDTA), amino-polyphosphonates (DEQUEST), ether carboxylate builders such as in EP-A-286 167, phosphates, iminodiacetic acid derivatives such as described in EP-A-317 542, EP-262 112 and EP-A- 399 133, and mixtures thereof. Preferred builders/sequestrants for use herein are selected from Tetrapotassium pyrophosphate, citric acid and sodium carbonate. The hard surface cleaning compositions according to the present invention may comprise up to 15% by weight of the total composition of a builder, preferably from 1% to The compositions according to the present invention may further comprise solvents, Suitable solvents for use herein include propylene glycol derivatives such as n-butoxypropanol or n- butoxypropoxypropanol, watersoluble CARBITOL R solvents or water-soluble CELLOSOLVE R solvents; water-soluble CARBITOL R solvents are compounds of the 2-(2alkoxyethoxy)ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl; a preferred water-soluble carbitol is 2-(2butoxyethoxy)ethanol also known as butyl carbitol. Water-soluble CELLOSOLVE R solvents are compounds of the 2-alkoxyethoxy ethanol class, with 2-butoxyethoxyethanol being preferred, Other suitable solvents include benzyl alcohol, and diols such as 2-ethyl-l, 3-hexanediol and 2,2,4-trimethyl-l,3-pentanediol and mixtures thereof. Preferred solvents for use herein are n-butoxypropoxypropanol, BUTYL CARBITOL R and mixtures thereof, The compositions according to the present invention comprise up to 15 by weight of the total composition of a solvent, preferably from 3% to The compositions according to the present invention may also comprise minor ingredients to provide aesthetic or additional product performance benefits. Typical minor ingredients include perfumes, dyes, optical brighteners, soil suspending agents, detersive enzymes, gel-control WO 93/19148 PCT/US93/02335 7 agents, thickeners, freeze-thaw stabilizers, bactericides, preservatives, and the like.

In the method for the cleaning of hard surfaces according to the present invention, a hard surface cleaning composition comprising at least one nonionic surfactant of the formula RO-(CH 2 CH20)nH wherein R is a C 8 to

C

22 alkyl chain or a C 8 to C 28 alkyl benzene chain, and n is an integer of from 10 to 65, or mixtures thereof, is diluted in water and applied to said surface. In a preferred method according to the present inventit- :id composition further comprises an anionic surfactant as described hereinbefcre.

In a preferred method according to the present invention, said composition is diluted into 10 to 200 times its weight of water, more preferably 50 to 150 times, before it is applied to said hard surface.

The different embodiments of the present invention are further illustrated by the following examples Examples The following compositions were the listed proportions: made by mixing the listed ingredients in Ingredients: Sodium paraffin sulfonate Alcohol ethoxylate 30EO (1) Alcohol ethoxylate 12EO (2) Alcohol ethoxylate 7EO (3) Alcohol benzene ethoxylate 10EO (4) Citric acid Butylcarbitol R n-butoxypropoxypropanol Triethanolamine water minors Compositions #1 #2 #3 Weight 3 3 3 2 3 1 3 2 3 7 2 1 100% 1 up to WO 93/19148 PCT/US93/02335 Compositions #6 #7 Weight 3 Ingredients: Sodium paraffin sulfonate Sodium alkyl sulfate Sodium alcohol ethoxylate sulfate Alcohol ethoxylate 30EO (1) Alcohol ethoxylate 12EO (2) Alcohol ethoxylate 7EO (3) Citric acid Tetrapotassium pyrophosphate Butylcarbitol R n-butoxypropoxypropanol Triethanolamine Monoethanolamine Ethoxyethanolamine water minors 3 4 4 6 1 2 up to 100% In the examples hereinabove, is a highly ethoxylated nonionic surfactant wherein R is a mixture of C 13 and C 15 alkyl chains and n is is a highly ethoxylated nonionic surfactant wherein R is a mixture of C 13 and C 15 alkyl chains and n is 12. is a lower ethoxylated nonionic surfactant wherein n is 7. is a highly ethoxylated nonionic surfactant wherein R is a mixture of C 19 and C 2 1 alkyl benzene chains and n is Compositions 1-8 described hereinabove can be used neat or diluted. In a method according to the present invention, these compositions are diluted in 65 times their weight of water and applied to a hard surface.

Claims

1. A hard surface cleaning composition consisting essentially of: from 0.5% to 30% by weight of the total composition of at least one nonionic surfactant, wherein said nonionic surfactant is of the formula RO- (CH 2 CH 2 0)nH wherein R is a Cg to C22 alkyl chain or a Cg to C28 alkyl benzene chain, and n is an integer of from 21 to 65 or mixtures thereof; (ii) from 0.1% to 10% by weight of an alkanolamine, selected from monoalkanolamines, dialkanolamines, tralkanolamines, alkylakanolamines, dialkylakanolamin3s, alkoxyalkanolamines or mixtures thereof; (iii) up to 15% by weight of a builder; (iv) up to 15% by weight of a solvent selected from propylene glycol derivatives, 2-(2-akloxyethoxy)ethanol derivatives, benzyl alcohol, diols and mixtures thereof; optional minor ingredients selected from perfumes, dyes, optical brighteners, soil suspending agents, detersive enzymes, gel-control agents, thickeners, freeze-thaw stabilisers, bactericides and preservatives; and (vi) water.

2. A hard surface cleaning composition consisting essentially of: from 0.5% to 30% by weight of the total composition of at least one anionic surfactant and at least cie noninnic surfactant, wherein sa!d nonionic surfactant is of the formula RO-(CH 2 CH 2 0)nH wherein R is a C8 to C, alkyl chain or a Ca to 0 Ca alkyl benzene chain, and n is an integer of from 10 to 65, or mixtures thereof; (ii) from 0.1% to 10% by weight of an alkanolamine, selected from monoalkanolamines, dialkanolamines, tralkanolamines, alkylakanolamines, dialkylakanolamines, alkoxyalkanolamines or mixtures thereof; (iii) up to 15% by weight of a builder; (iv) up to 15% by weight of a solvent selected from propylene glycol derivatives, 2-(2-akloxyethoxy)ethanol derivatives, benzyl alcohol, diols and mixtures thereof; optional minor ingredients selected from perfumes, dyes, optical A4 brighteners, soil suspending agents, detersive enzymes, gel-control agents, P 61% A thickeners, freeze-thaw stabilisers, bactericidet and preprvatives; and "VtS Oitt (vi) water.

3. A composition according to claim 2, wherein said anionic surfactant and said nonionic surfactant are present in a weight ratio of said anionic surfactant to said nonionic surfactant of from 0.2 to

4. A composition according to either claim 2 or 3, wherein said anionic surfactant and said nonionic surfactant are present in a weight ratio of said anionic surfactant to said nonionic surfactant of from 0.5 to A composition according to any one of claims 2 to 4, wherein said anionic surfactant is a paraffin sulfonate in the form of its sodium salt.

6. A composition according to any one of claims 2 to 5, wherein n is an integer of from 11 to

7. A composition according to any one of claims 2 to 6, wherein n is an integer of from 18 to

8. A composition according to any of the preceding claims, wherein n is an integer of from 21 to

9. A composition according to any of the preceding claims, wherein R is a C 8 to C22 alkyl chain, A diluted hard surface cleaning composition obtainable by diluting in water a composition according to any of the preceding claims, comprising from 0.001% to by weight of the total composition of said nonionic surfactant or said mixture of anionic surfactant and nonionic surfactant.

11. A diluted hard surface cleaning composition obtainable by diluting in water, a composition according to any of te preceding claims, comprising from 0.01% to 0.3% by weight of the total composition of said nonionic surfactant or s.aJ mixture of anionic surfactant and nonionic surfactant.

12. A method for cleaning of a hard surface where a composition consisting essentially of: g* from 0.5% to 30% by weight of the total composition of at least one nonionic surfactant, wherein said nonionic surfactant is of the formula RO- (CH 2 CH 2 0)nH wherein R is a Ca to C22 alkyl chain or a Ca to C23 alkyl benzene chain, and n is an integer of from 21 to 65 or mixtures thereof; 11 (ii) from 0.1% to 10% by weight of an alkanolamine, selected from monoalkanolamines, dialkanolamines, tralkanolamines, alkylakanolamines, d,alkylakanolamines, alkoxyalkanolamines or mixtures thereof; (iii) up to 15% by weight of a builder; (iv) up to 15% by weight of a solvent selected from propylene glycol derivatives, 2-(2-akloxyethoxy)ethanol derivatives, bonzyl alcohol, diols and mixtures thereof; optional minor ingredients selected from perfumes, dyes, optical brighteners, soil suspending agents, detersive enzymes, gel-control agents, thickeners, freeze-thaw stabilisers, bactericides and preservatives; and (vi) water is diluted in water and applied to said hard surface is diluted in water and applid to said hard surface,

13. A method for cleaning of a hard surface according to claim 12 wherein the composition further includes an anionic surfactant.

14. A method according to either claims 12 or 13, wherein said composition is diluted into 10 to 200 times its weight of water before it is applied to said hard surface. A hard surface cleaning composition as hereinbefore described with reference to any one of the examples. DATED: 25 September, 1996 PHILLIPS ORMONDE FITZPATRICK Attorneys for: THE PROCTER GAMBLE COMPANY *se t a oe M)C C WIvvoo~ull~oITA EV]UJtP~14DOO INTERNATIONAL SEARCH REPORT Inwernaionl apphcaton No, PCTIUS93/rJ35 A, CLASSIFICATION OF SUBJECT MATTER :C11I) 1/722, 1/83 US CL :2521174.21,170,171,550,551,554, DIG, 10, DIG. 14 According to International Patent Classification (IPC) or to both national ciastification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) U.S. Documentation searched other than minimum documentation to the extent that such documents ar included in the rld. searched Electronic data base consulted during the international search (name of data base and, where practicable, search terms used) DOCUMENTS CONSIDERED TO BE RELEVANT CxtegoryU CiLaikon of document, with indication. where appropriate, of the relevant passages Relevant to claim No, X US,A, 4,492,646 (WELCH) 1-3,9 08 JANUARY 1985 Se abstract; column 2, lines 30-52 and examples VI X USIA, 4,615,819 (LENG ET AL) 2,3,9 and 07 OCTOBER 1986 See abstrfact and example 18 X USA, 4,671,894 (LAMB ET AL) 2,3,9 and 09 JUNE 1987 See abstract and example I SFurther documents are listed in the continuation or Box C, See patent family annex, Spcl a ofcitd of do w Waur atwoa pqbtlsbd ateft a te mbuoWaOc1 rndis -lOcltY date nd not acosfloa A bs sPPbSaabot Acitd o uWadomnid thI OA docmnatdetak lbe gwenlmm ofd w4n .r thicb is tco0idnt d prn of tiwory unMetyin Ibe m'icnii to be pai of pa naUh r es-acs 'X docmcra of parciAut owie csehkd invasizm cnnox b t"Loct dlocumew PuUMW an D or ah -r te inkroadial fifs c ocmie nove at cf ot be waicrd ito ,volve sa mnvutv.V dotwmnxh whoy vw doubs on pnicayy cki) a wof lm w *baa ibs doctagaizu a ke slow Cited to ts.tbtsh lb. pubtacawos de ato w4w citic at other socaaj rasom (IM spenifis) *Y doctames of panicukt rakvwuwd ti chinMe ktcenoo c9ano b4 omansit to sia'ot, so nw4 augv C whb ds docnat i don-woa refeams to 4 onJ dhclonav, axbliioa at odwr tnobload with"a or t os othciuch doctnenl, uc" "mbaWaos am b abvlw to0 pamos aLkilsina b LA .r docc~am puht6 prior 6*dK6wrmioolf& d"kP 6w** dftw m4 wamber of dn wm p U fmiNay Ilbe prkmoc daw tehkwd Date of the actual completion of the international search Dateopf 3 tX a tt 9 3 ermational search report '6 APRIL 1993 Name and mailing addr-ss of the ISA/US Athorized officer Am u-o ett Commiujoner of Patnts and Trademic&i 84X PCr BRADLEY A. SWOPEb'0=':* NGC'C- Washingon. D.C. 20231 MRRW DMVCZO3 Pacatmile No. NOT APPLICABLE Telephone No. t703) 308.2521 Form PCT/ISAJ2IO Cecond sheet)(July I992)* INTERNATIONAL SEARCH REPORT bItcrnational application No. PCT/US93/023I35 Box I Observations where certain cLaims were found untsearchable (Coutinuati, of itemn 1 of first sheet) This international report has not been established in respect of certain claim under Article 17(2)(a) for the following reasons: Claims Nos.: Jbecause they rosate t6 subject matter not required to be searched by this Authority, namely: 2. flClaims Nos,; because they relate to parts of the international application that do not comply with the prescribed requirements to suct an extent that no meaningful international search can be carried out, specifically: 3. 7X Claims Nos.: 4-8 and I I because they are dependent claims and are not dmWie in accordance with the second andi third scnti.ces of Rule 6,4(a). Box If Observations where unity or invention is lacking (Continuation of item 2 of first sheet) This International Searching Authot,,y found multiple inventions in this international application, as follows,, As all required additiznal search fees were timely paid by the applicant, thi international search report covers all searchable claims. 2. F As all searchable claims could be searched without effort justifying an additional fee, this Authority did not invitk, payment of any additional fee, 3. F As only some of the required additional search fees were timely paid by the Applicant, this international search report covers only those claims for which fees were paid, specifica~ly claims Nos.- 4. F1No recoired Additional search fees were timely paid by the applicant. Consequently, is international search report is restricted to the invention first mentioned in the claims; it is covrv by claims Nos.: Remark on Protest EThe additional search fees were accompanied by the Applicant's protest. No protest Accompanied the payment of additional search fees. Form PCTlISAJ2IO (Continuation Of frst sht)UIY 1992)*