AU699995B2 - Lipophilic solid cosmetic composition comprising acidic dye - Google Patents

Description

'4 WO 95117884 PCT/US94/14288 LIPOPHILIC SOLID COSMETIC COMPOSITION COMPRISING ACIDIC DYE [TECHNICAL FIELD] o1 The present invention relates to a lipophilic solid cosmetic composition having good stainability, long-lasting effect, and good color stability, for example, cosmetic compositions suitable for lipsticks, eye shadows, blushers, and foundations.

[CONVENTIONAL TECHNOLOGY] is Coloring agents such as pigments and dyes are used in lipophilic solid cosmetic compositions mainly used for the purpose of make-up; for example, lipsticks, eye shadows, blushers, and foundations; in order to provide color to the skin. The coloring agents used here should not only provide an alluring color, but also meet general characteristics required for making a cosmetic composition. Namely, such characteristics are; homogeneity in appearance, good stainability upon application, and long-lasting effect with stable color after application.

GB Patent 1,173,743 discloses that it is useful to contain a oil-insoluble dye or a combination of oil-insoluble dye and oil-soluble dye in a cosmetic.

Further, lipsticks and lipophilic cosmetics containing the combination of oil-base dye or the combination of oil-base dye and acidic dye is disclosed in the art.

IP Laid-open patent S63-119405 discloses a transparent solid cosmetic having good transparency, stability in appearance, and superior usage and dye solubility characterized in comprising 12-hydroxystearic acid, polyhydric alcohol ester of rosin, and a partial ester of polyhydric alcohol and branched fatty acid, or ester of polyhydric alcohol and unsaturated fatty acid.

JP Laid-open patent H1-90110 discloses a transparent solid cosmetic having good transparency, stability in appearance, and superior usage and dye solubility characterized in comprising polyamide resin, pentaerythritot rosin ester, and a partial ester of polyglycerin and branched fatty acid, or an ester of polyglycerin and unsaturated fatty acid.

JP Laid-open patent H1-287011 discloses an emulsified lipstick having a brilliant color comprising water-soluble mineral clay, water, and fluorescent-type dye.

S]P Laid-open patent H3-86808 discloses a lipstick having superior utility characteristic such as Sgood coming out of color, spreadability, attachment, long-lasting effect, and good appearance as 1.

I i i-i-

S

S

4.

S

S.

*554 Se ft

S

S

II

well as stability, comprising 13-21% solid hydrocarbon, 15-60% ester compound made of oxy acid and fatty alcohol, 20-65% liquid or paste-type hydrocarbon, and oil-base dye.

JP Laid-open patent H3-90013 discloses a lipstick having superior utility characteristic such as good coming out of color, spreadability, attachment, longlasting effect, and good appearance as well as stability, comprising 13-21% solid hydrocarbon, 15-60% ester compound made of polyhydric alcohol and fatty alcohol, 20-65% liquid or paste-type hydrocarbon, and oil-base dye.

JP Laid-open patent H3-236307 discloses a lipophilic cosmetic which does 10 not sweat, and has a high chroma color characterized in comprising 0.01-30 wt% of a gamma-alumina having a certain relative surface area, and 0.01-10wt% oilbase dye.

It would be desirable to provide a lipophilic solid cosmetic composition having good stainability, long-lasting effect, and good color stability.

15 It would further be desirable to provide a lipophilic solid cosmetic composition having the same effects as said with a small amount of dye.

It would yet further be desirable to provide a lipophilic solid cosmetic composition having improved homogeneity of appearance over a wide range of shades.

However, acidic dyes tend to decolor as it is exposed to humidity in the atmosphere, which causes changing of coloring itself. It is not preferable for a make-up cosmetic such as lipstick to decolor. Thus, conventionally, lipophilic cosmetics including acidic dye such as lipsticks tended to be used for dark shades, for decoloring of such shades would not be so obvious.

Here, by comprising an acidic dye with water-soluble organic acid, a lipophilic solid cosmetic composition having good stainability, long-lasting effect, and good color stability, namely, less decoloring over time, was obtained.

Meanwhile, it is desirable to provide the best coloring effects with small amount of dye in consideration of safety. Dyes are also generally known to be difficult to homogeneously include in lipophilic solid cosmetic compositions because of its tendency to separate from the other lipophilic components, and thus, are desired to be included at its minimum.

II

k r..

C(WNHiREfVTctAlHLECtWicovOOC i c Here, by further comprising an oil-base dye, a lipophilic solid cosmetic composition having good stainability, long-lasting effect, and good color stability, and further with improved homogeneity of appearance was obtained over a wide range of shades with a small total amount of dye.

[DETAIL DESCRIPTION OF THE INVENTION] The present invention relates to a lipophilic solid cosmetic composition comprising by weight: 0.01-1% acidic dye; and 0.01-0.5% water soluble organic acid having one or more functional groups; and further, preferably 0.01-2% oil-base dye.

10 The present invention also provides a lipstick composition comprising by weight: a) 0.01-1% acidic dye; b) 0.01-0.5% water soluble organic acid having one or more functional groups; c) 0.01-2% oil-base dye; 15 d) 0.1-5% solvent; e) 60-98% lipophilic material; and f) 0-39% pigment; wherein said water soluble organic acid is introduced into the composition as a solution of said solvent.

C C 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.

NcV RA, WO 95/17884 PCT/US94/14288 3 The cosmetic composition of the present invention comprises 0.01-1 wt%, preferably 0.01-0.25 wt% of an acidic dye. The acidic dyes used in the present invention are those which are safe enough to be used in cosmetics, such as D&C Red #28 (Red #104-(1) according to Japanese Ministry of Health and Welfare Regulations; hereinafter D&C Red #6 (Red #201 s according to MHW Regulations), FD&C Yellow #5 (Yellow #4 according to MHW Regulations), and FD&C Yellow #6 (Yellow #5 according to MHW Regulations). Acidic dyes can be included in the cosmetic composition as-is, or as a mixture with fatty acid ester.

The cosmetic composition of the present invention comprises 0.01-0.5 wt%, preferably 0.05-0.1 wt% of a water-soluble organic acid having one or more functional groups. Examples of watero1 soluble organic acids are citric acid, anhydrous citric acid, lactic acid, tartaric acid, and malic acid.

Although acidic dyes are generally known to decolor, the stainability and stability of color over time are improved by combining them with organic acid. Such effects can be seen with a small amount of organic acid, but can be significantly seen when the organic acid is included at a level is of at least 0.5 times weight of the acidic dye.

The cosmetic composition of the present invention can further comprise 0.01-2 wt%, preferably 0.01-0.5 wt% of an oil-base dye. The oil-base dyes used in the present invention are those which are safe enough to be used in cosmetics, such as D&C Red #21 (Red #223 according to MHW Regulations), D&C Red #27 (Red #218 according to MHW Regulations), and D&C Orange (Orange #201 according to MHW Regulations). In the present invention, by including an oilbase dye, the same level of stainability can be obtained by using less amount of dye in total as compared to that when only acidic dye is included. It is desirable that due is included at the minimum level in view of safety to the skin and product stability. Further, with the combination of dyes, the variety of shades are widened. As was the case for acidic dyes, oil-base dyes can be included in the cosmetic composition as-is, or as a mixture with fatty acid ester.

Solvent In the present invention, organic acid can be incorporated to the cosmetic composition by dissolving it into 0.1-5 wt%, preferably 0.5-3 most preferably 0.7-1.5 wt% to cosmetic composition of a solvent. Solvents are selected from the group consisting of water, monohydric alcohol having 1 to 6 carbons, and polyhydric alcohol. Examples of solvents are water, ethanol, isopropanol, glycerin, diglycerin, triglycerin, ethylene glycol diethylene glycol, propylene glycol, dipropylene glycol, 1,3 butylene glycol, and 1,4 butylene glycol. By incorporating the organic acid as a solution of solvent, the organic acid can be dispersed homogeneously in the cosmetic composition, and thus it is preferable from a process point of view. It is also found that some combinations of dye and solvent improve stability of color. Further, as some polyhydric alcohols have good attachment to the skin, the combination of these with dye improve the stainability.

r o WO 95/17884 PCT/US94/14288 4 The type of solvent is selected in consideration with solubility with other components in the cosmetic composition, and also with the needs of the desired product.

Optional Components The lipophilic solid cosmetic compositions of the present invention can further comprise the s following components as usually included in cosmetic compositions, in addition to those already disclosed herein.

Typically, the cosmetic compositions of the present invention contain 30-98 wt%, for lipsticks 60-98 wt%, preferably 80-95 wt% lipophilic material, and 0-65wt%, for lipsticks 0-39wt%, preferably 2-20 wt% pigment.

to Litiophilic Material The lipophilic material used in the present invention can be selected from the group consisting from solid lipophilic material, liquid oil, oil gelling agent, and mixtures thereof. These components are selected by the one skilled in the art according to the desired cosmetic composition to be made. Preferably, for cosmetic compositions containing more than about s1 pigment such as foundations, eye shadows, and blushers, the mixture of solid lipophilic material, liquid oil, and oil gelling agent is included.

Solid Lipophilic Material The solid lipophilic material act as a solidifying agent in the cosmetic composition. It can assist in the formation of the solid structure of the composition. The solid is a low-melting organic compound or mixture of high molecular weight substances, and is solid or paste at room temperature. The solids can be waxes, hydrocarbons, fatty acids, fatty alcohols, natural fats, or esters, but not limited thereof.

Natural, mineral and synthetic waxes can be used herein. Non-limiting examples of natural waxes of animal origin are beeswax, spermaceti, lanolin, shellac wax, or of vegetable origin, such as carnauba, candelilla, bay berry, sugarcane wax, and of mineral origin, such as ozokerite, ceresin, montan, paraffin, microcrystalline, vaseline, petroleum and petrolatum wax. Nonlimiting examples of synthetic waxes are polyol ether-esters such as carbowax and hydrocarbontype waxes, silicone waxes and polyethylene wax. Synthetic triglycerides in wax form such as esters of linear fatty acids are also useful. The most preferred waxes are ozokerite, ceresin, lanolin, microcrystalline, carnauba, beeswax, and paraffin waxes.

The fatty acids used herein can be saturated, unsaturated, linear, or branched. Non-limiting examples are lauric, myristic, palmitic, stearic and behenic acids.

Non-limiting examples of fatty alcohols used herein are octyl, decyl, lauryl, myristyl, cetyl, stearyl, and behenyl alcohols.

Non-limiting examples of the natural fats useful herein are cocoa butter, palm oil, Japan wax, hydrogenated vegetable oil, hydrogenated castor oil, and cholesterol.

WO 95/17884 PCTIUS94/14288 Non-limiting examples of the esters useful herein are myristyl myristrate, myristyl palmitate, myristyl stearate, cetyl palmitate, cetyl stearate, cetyl lactate, stearyl lactate, cholesterol stearate, cholesterol oleate, cholesterol palmitate, cholesterol laurate, cholesterol myristate, cholesterol lineolate, and cholesterol ricinoleate.

s Liquid Oils The liquid oils act as emollients, and imparts tackiness, and drag properties to the cosmetic.

Liquid oils are material that freely flow at room temperature. Liquid oils can also be volatile.

Said liquid oils can be hydrocarbon oils, natural oils, fatty alcohols, fatty acid esters, and silicone oils, but not limited thereof.

to Non-limiting examples of the hydrocarbons useful in the present invention are liquid paraffin, squalane, liquid petrolatum, mineral oil, and liquid polybutenes.

The natural oils used herein typically are mixtures of saturated and unsaturated fatty acids. Nonlimiting examples of natural oils derived from plants include almond oil, olive oil, sesame oil, safflower oil, avocado oil, cottonseed oil, jojoba oil, castor bean oil, castor oil, rapeseed oil, soybean oil, palm kernel oil, and coconut oil. Non-limiting examples of natural oils derived from animal sources are mink oil and egg yolk oil.

Non-limiting examples of fatty alcohols useful in the present invention are isostearyl alcohol, lanolin alcohol, oleyl alcohol, hexadecyl alcohol, octyldodecanol alcohol, linoleyl alcohol, linolenyl alcohol, and arachidyl alcohol.

Fatty acids useful in the present invention can be natural or synthetic, saturated, unsaturated, linear, or branched. Non-limiting examples of fatty acids useful in the present invention are adipic, caprylic, capric, isostearic, linoleic, ricinoleic, oleic, elaidic and erucic acids.

Non-limiting examples of the fatty acid esters useful in the present invention are cetyl ricinoleate, cetyl oleate, cetyl octanoate, cetyl acetate, glyceryl trioctanoate, isopropyl lanolate, isopropyl linoleate, isopropyl myristate, isopropyl palmitate, isopropyl oleate, isopropyl stearate, ethyl lactate, ethyl glutamate, ethyl laurate, ethyl linoleate, ethyl methacrylate, ethyl myristate, ethyl palmitate, diisopropyl adipate, octyl dodecyl myristate, octyl palmitate, octyl isopelargonate, octyl dodecyl lactate, tridecyl isononanoate, isotridecyl isononanoate, hexadecyl stearate, oleyl oleate, isononyl isononanoate, isostearyl myristate, dipenta-erythrytol ester, neopentyl glycol dioctanoate, and di(capryl/capric acid) propylene glycol. Other suitable esters include triglycerides such as caprylic triglycerides, cqpric triglyceride, isostearic triglyceride, adipic triglyceride.

Non-volatile and volatile, straight, branched, and cyclic silicone oils such as dimethicone, phenyl dimethicones, and cyclomethicones are also useful.

Oil Gelling Agents The oil gelling agents are included for gelatinizing or viscosity controlling of the formulation.

Non-limiting examples of oil gelling agents useful in the present invention are condensation I i WO 95/17884 PCTUS94/14288 6 products of benzaldehydes and polyhydric alcohols having at least 5 bases such as dibenzylidene xylitol, paratribenzylidene sorbitol, metal soaps such as calcium stearate, calcium palmitate, lithium salt of 2-ethyl hexane, alminium salt of 1,2,hydroxystearate, amide, ester, and amide derivatives of N-acylamino acids such as lauroyl glutamate dibutylamide, lauroyl glutamate s stearamide, dicaproyl lysine lauroylamide, dicaproyl lysine lauroylamine salt, dicaproyl lysine lauryl ester, dicaproyl lysine lauroyl phenylalanine laurylamide; dextrine fatty acid esters, and 1,2-hydroxystearic acid.

Pigments Non-limiting examples of pigments useful in the present invention are talc, mica, clay, kaolin, to zinc oxide, nylon powder, ultramarine, pearl pigments (bismuth oxychloride, guanine), iron oxide, titanium oxide, titanated mica, calcium carbonate, tar pigments, and other organic pigments. Pigments which are surface treated with silicones and its derivatives, metal soaps, fluorine compounds and its derivatives, lecithin and its derivatives, amino acids and its salts, etc.

can also be used.

The pigments can also be dispersed in an oily medium such as those disclosed above under liquid oils prior to use in the making process. Pigments can be purchased pre-dispersed in an oily medium like castor oil, or as dry powders which subsequently are dispersed in a chosen medium by the formulator.

i- ~_I WO 95/17884 PCT/US94/14288 7 Other Optional Components The compositions made by the process of the present invention can optionally contain components in addition to those already disclosed herein, so long as the lipophilic solid cosmetic composition as a whole has a common pH in the range of 4-7.

Optional components include antioxidants, preservatives, antiinflammatory agents, astringents, pH buffers, perfumes, ultraviolet and infrared screening agents, nonionic surfactants such as fatty acid esters and polyoxyalkylene fatty acid esters, amphoteric and anionic surfactants such as lecithins and phosphates, vitamins, and skin conditioning agents.

Antioxidants and preservatives can be, and usually will be formulated in the composition of the io present invention to make products attractive to the consumer. Useful antioxidants and preservatives are tocopherol, dibutylhydroxy toluene, methylparaben, and propylparaben. These components are typically present at levels not more than 1 respectively.

Useful skin conditioning agents are beta-glycyrrhetic acid and its derivatives, vegetation extracts, allantoin, collagen, and extract and treated elastin fibers.

i WO 95/17884 PCT1US94114288 WO 95/17884 PCTIUS94/14288 4.

*4*4 Oe* *4M4**

V.

4 0a 4* VII 44 4 4

[EXAMPLES]

The following examples illustrate the compositions of the present invention, but are not intended to be limiting thereof. All percentages and ratios are based on weight unless otherw~ise specified.

Table 1 Component Amount Example 1 Example 2 Example 3 D&C Red #28 (Red #104-(1) according to 0.100 0.100 0.100 MHW Regulations)______ Anhydrous citric acid 0.075 0.075 D&C Red #27 (Red #218 according to MHW 0.100 0.100 0.100 1,3 buty ene glycol 1.425 Ethyl alcohol 1.425 Distilled water 1.425 Ceresin 4.000 4.000 4.000 NMicrocrystalline wax Moo0 2.000 2Moo Candelilla wax 5.000___ 5.000 5.000 Paraffin wax 3Moo 3.000 3.000 Castor oil 20.000 20.000 20.000 Liquid Paafi 15.000 15.000 15.000 Purified lanolin 10.000 10.000 10.000 Liqiuid lanolin 10.000 10.000 10.000 Glyety tiocanote21.300 21.300 21.300 Rdpigment (RW #202 according to MHW 150150 1.50 Red pigment (Red #201 according to MHW 050050050 Yellow pigment (Yellow #4 Aluminum lake 1.0100100 according to MHW Regulation)_______ Titanium oxide 3M0o 3.000 3.000 Iron oxide 2.000 2.000 2.000 Total 100.000 100.000 100.000 WO 95/17884 PCT/US94/14288 9 The lipsticks as shown as Examples 1-3 in Table 1 can be prepared by a suitable process to one skilled in the art. As a preferred process, the following can be used. Acidic dye, oil-base dye, and pigment are mixed with a certain amount of castor oil respectively. Anhydrous citric acid is dissolved in the solvent to make a 5% solution. The dye mixture, pigment mixture, and organic s acid solution thus obtained are mixed with the other components which had been melted and dissolved at 100-120 0 C. The finally obtained mixture is poured into a mold to obtain a stick-type lipstick.

Claims (11)

1. A lipophilic solid cosmetic composition comprising by weight: a) 0.01-1% acidic dye; and b) 0.01-0.5% water soluble organic acid having one or more functional groups.

2. The lipophilic solid cosmetic composition according to Claim 1 further comprising by weight 0.01-2% oil-base dye.

3. The lipophilic solid cosmetic compositipn according to Claim 1 or 2 wherein said water soluble organic acid is selected from the group consisting of citric acid, anhydrous citric acid, lactic acid, tartaric acid, malic acid, and mixtures thereof.

4. The lipophilic solid cosmetic composition according to Claim or 2 wherein said water soluble organic acid is included at a level of at least 0.5 times weight of said acidic dye.

5. The lipophilic solid cosmetic composition according to Claim 1 or 2 wherein said water soluble organic acid is introduced into the composition as a solution of 0.1-5% by weight to composition of a solvent, wherein said solvent is selected from the group consisting of water, monohydric alcohol of 1 to 6 carbons, polyhydric alcohols, and mixtures thereof.

6. A lipstick composition comprising by weight: a) 0.01-1% acidic dye; b) 0.01-0.5% water soluble organic acid having one or more functional groups; c) 0.01-2% oil-base dye; 0.1-5% solvent; e) 60-98% lipophilic material; and f) 0-39% pigment; wherein said water soluble organic acid is introduced into the composition as a solution of said solvent.

7. The lipophilic solid cosmetic composition according to Claim I or 2 i*cin (i) said water soluble organic acid is selected from the group consisti orf citric acid, anhydrous citric acid, lactic acid, tartaric acid, malic acid, and mixtures 11 thereof, and (ii) said water soluble organic acid is included at a level of at least times weight of said acidic dye.

8. The lipophilic solid cosmetic composition according to Claim 1 or 2 wherein (i) said water soluble organic acid is selected from the group consisting of citric acid, anhydrous citric acid, lactic acid, tartaric acid, malic acid, and mixtures thereof, and (ii) said water soluble organic acid is introduced into the composition as a solution of 0.1-5% by weight to composition of a solvent, wherein said solvent is selected from the group consisting of water, monohydric alcohol of 1 to 6 carbons, polyhydric alcohols, and mixtures thereof

9, The lipophilic solid cosmetic composition according to Claim 1 or 2 wherein (i) said water soluble organic acid is selected from the group consisting of citric acid, anhydrous citric acid, lactic acid, tartaric acid, malic acid, and mixtures thereof, (ii) said water soluble organic acid is included at a level of at least 'times weight of said aciaic dye, and (iii) said water soluble organic acid is S1.. introduced into the composition as a solution of 0.1-5% by weight to composition of a solvent, wherein said solvent is selected from the group consisting of water, monohydric alcohol of 1 to 6 carbons, polyhydric alcohols, and mixtures thereof.

10. A lipophilic solid cosmetic composition according to claim 1 0uW substantially as herein described with reference to any one of the Examples. DATED: 15th May, 1996 PHILLIPS ORMONDE FITZPATRICK Attorneys for: THE PROCTER GAMBLE COMPANY •O LIFrsll~-~-'-a~- IL~CC INTERNATIONAL SEARCH REPORT International application No. PCT/US94/14288 A. CLASSIFICATION OF SUBJECT MATTER IPC(6) A61K 9/127, 7/027 US CL :424/450, 64 According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) U.S. 424/450, 64 Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched APS: Search terms: 'acidic dye?, lipstick Electronic data base consulted during the international search (name of data base and, where practicable, search terms used) NONE C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. Y US, A, 4,438,140 (GUILLON) 20 March 1984, see Abstract; 1-3, 6 columns 2-4 and claims. Y US, A, 4,952,245 (IWANO) 28 August 1990, see Abstract; 1-3, 6 column 1, line 29 and Example

11. Y US, A, 4,305,961 (TSUTSUMI) 15 December 1981, see 1-3, 6 column 3, lines 57-60 and claims. Y US, A, 5,171,572 (SUGANUMA) 15 December 1992, see 1-3, 6 column 8, lines 54-57. D Further documents are listed in the continuation of Box C. O See patent family annex. Special categories of cited documents: later document published afer the intenational riling date or priority date and not in conflict with the application but cited to undertand the documentdefhng the general state of the a s which i not considerd principle or theory underlying the invention to be part of particular relevance earlier document published on or after the international iling date conXdeud novel or relevance; th invenion can e not be document which may throw doubts on priority claim(s) or which is when the document i taken alone cited to blh the publication dte of another citation or other docent of ptcur evance; the claimed invention cannot be specL reoa (r ipcified) documaen of particular reevace; tbe claimed invention annot be s a n conaidered to involve an inventive Itep when the document is document referring to an oral disclosure, ue, exhibition or other combined with one or more other such documents, ch combination means being obviou to a person skilled in the art document ps'i hed prior to the intemationl filing date but later than document mmber of the same patet family the priority date claimed Date of the actual completion of the international search Date of mailing of the international search report 21 FEBRUARY 1995 0 3 APR 1995 Name and mailing address of the ISA/US Authofi d officer Commissioner of Patents and Trademarks Box PCT Washington, D.C. 20231 Facsimile No. (703) 305-3230 Telephone No. 03) 308-2351 Form PCT/ISA/210 (second sheet)(July 1992)* i 1 ~ma~e~8sA~~p~-; INTERNATIONAL SEARCH REPORT International application No. PCT/US94/14288 Box I Observations where certain claims were found unsearchable (Continuation of item 1 of first sheet) This international report has not been established in respect of certain claims under Article 17(2)(a) for the following reasons: I. l Claims Nos.: because they relate to subject matter not required to be searched by this Authority, namely: 2. Claims Nos.: because they relate to parts of the international application that do not comply with the prescribed requirements to such an extent that no meaningful international search can be carried out, specifically: 3. Claims Nos.: 4 because they are dependent claims and are not drafted in accordance with the second and third sentences of Rule 6.4(a). Box II Observations where unity of invention is lacking (Continuation of item 2 of first sheet) This International Searching Authority found multiple inventions in this international application, as follows: 1. F] As all required additional search fees were timely paid by the applicant, this international search report covers all searchable claims. 2. O As all searchable claims could be searched without effort justifying an additional fee, this Authority did not invite payment of any additional fee. 3. O 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, specifically claims Nos.: 4. No required additional search fees were timely paid by the applicant. Consequently, this international search report is restricted to the invention first mentioned in the claims; it is covered by claims Nos.: Remark on Protest D The additional search fees were accompanied by the applicant's protest. EO No protest accompanied the payment of additional search fees. Form PCT/ISA/210 (continuation of first shet(l))(July 1992)*