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US3502769A - Hydrogenated terpene polymer storage stabilized toilet preparation - Google Patents

Hydrogenated terpene polymer storage stabilized toilet preparation Download PDF

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Publication number
US3502769A
US3502769A US561701A US3502769DA US3502769A US 3502769 A US3502769 A US 3502769A US 561701 A US561701 A US 561701A US 3502769D A US3502769D A US 3502769DA US 3502769 A US3502769 A US 3502769A
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Prior art keywords
toilet
oil
preparation
vegetable
hair
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US561701A
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Nobukazu Fukuhara
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Shiseido Co Ltd
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Shiseido Co Ltd
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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/31—Hydrocarbons
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • A61K8/8111—Homopolymers or copolymers of aliphatic olefines, e.g. polyethylene, polyisobutene; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/08—Preparations containing skin colorants, e.g. pigments for cheeks, e.g. rouge
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q3/00—Manicure or pedicure preparations
    • A61Q3/02—Nail coatings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners

Definitions

  • a toilet preparation containing a storage stabilizing amount of hydrocarbon which may be a mono-cyclic hydrogenated terpene polymer of the formula (C H and/or a bi-cyclic hydrogenated terpene polymer of the formula (C H17) where n is a whole number of from 2 to 4 and a cosmetic base, such as a cold cream or a cleansing cream base.
  • This invention relates to compositions useful as toilet preparations in general, such as skin toilet preparations, toilet preparations for hair, make-up preparations, etc., the characteristic of which is to have in the said compositions vegetable hydrocarbon compounds obtained by polymerizing and hydrogenating terpenes containing mono, sesqui, di and (or) tri terpenes.
  • a primary object of this invention therefore is the embodiment of various toilet preparations of excellent quality by admixing therein said vegetable hydrocarbon compounds.
  • a toilet preparation requiring adhesive property such as a hair-setting preparation
  • Hydrocarbons such as liquid paraffin, petrolatum, etc., and waxes such as carnauba wax, bees wax, etc.
  • a vegetable oil such as castor oil
  • the product is highly viscous, shapes the hair and renders it glossy, however, it exhibits a bad odor characteristic of the oil, which grows stronger during storage.
  • Mucilaginous substances such as methyl cellulose, gum tragacanth, etc. can temporarily shape the hair, but they lack gloss and on drying change into powdery substance like scurf, so they are not suitable as materials for toilet preparations.
  • This invention makes it the principal point to add the vegetable hydrocarbon compounds obtained by polymerizing and hydrogenating terpenes containing mono, sesqui, di and tri terpene to the preparations.
  • the aforesaid hydrogenated terpenes are produced from alicyclic terpene hydrocarbons,
  • monoeyclic terpenes such as menthadienes (e.g. u-terpinene, 'y-terpinene, a-phellandrene, fl-phell andrene, terpinolene, limonene, etc.) and bi-cyclic terpenes such as the camphenes are first polymerized to form hydrocarbon compounds of the formula (C H wherein n is a positive whole number from 2 to 4. Thatis, the polymers are either dimer, trimers or tetramers.
  • reaction (1) is the main reaction while reaction (2) is a side reaction.
  • reaction (2) is a side reaction.
  • n in the above formula is a positive whole number of from 2 to 4.
  • n has the same significance as above.
  • catalysts which can be used to polymerize the terpenes there are many catalysts which can be used to polymerize the terpenes.
  • a preferred catalyst one which consists of 50% by weight of acid clay and 50% by weight of active clay which had admixed therein 1 to 3% by weight of zinc chloride.
  • the temperature at which the reaction takes place is not particularly critical; however, a temperature of between 170'- 180 C. is preferred when dipentene is the starting materiai.
  • the resultant polymer from the above-reaction is then reduced with hydrogen at a high temperature of pressure and, if desired, a catalyst, e.g. nickel, can be present.
  • a catalyst e.g. nickel
  • the mono, sesqui, di or tri terpenes mentioned above are found vegetable essential oils and possess an aromatic odor, but the compounds represented by Formula I, and mixtures thereef, and Formula II, and mixtures thereof, have excellent quality as the basic materials for toilet preparations.
  • the compounds employed in this invention are colorless transparent liquids of specific gravity above 0.910, far greater than that of any one of the hitherto commonly known oils.
  • the compounds are chemically stable, and hence are suitable for long storage, they also have a moderate fluidity and oily touch, and show much less irritating effect against the skin than any of the hitherto known oils, as proved by patch tests.
  • dipentene dimerized by reacting same in the presence of a catalytic amount of a catalyst composed of 50 parts by weight of acid clay, 50 parts by weight of active clay and 3 parts by weight of zinc chloride at l70180 C.
  • the resultant product is then subjected to reduction with hydrogen at 250 atmospheres and a temperature of 280 C. in the presence of catalytic nickel.
  • This product is the reduced dimer-dipentene which is shown in Equations 1 and 2.
  • This product is designated vegatable hydrocarbon oil dimer in the hereinafter-described examples of practical application of the present invention.
  • trimers and tetramers are as follows:
  • dipentene is polymerized by the action of catalyst, as aforesaid, in the presence of sulfuric acid, (ferric sulfate and aluminum sulfate can also be used) at 181-i90 C. Distillation under reduced pressure gives a distillate boiling at 190280 C./ 4 mm. Reduction with catalyic hydrogen (nickel catalyst) at 250 atmospheres and a temperature of 280 C. gives a viscous liquid boiling at 210280 C./4 mm.
  • catalyst as aforesaid, in the presence of sulfuric acid, (ferric sulfate and aluminum sulfate can also be used) at 181-i90 C. Distillation under reduced pressure gives a distillate boiling at 190280 C./ 4 mm. Reduction with catalyic hydrogen (nickel catalyst) at 250 atmospheres and a temperature of 280 C. gives a viscous liquid boiling at 210280 C./4 mm.
  • This product is designated vegetable hydrocarbon polymer oil in the hereinafter-described examples of practical application of the present invention. Any of the other previously mentioned terpenes may similarly be converted into vegetable hydrocarbon polymer compound for use according to this invention.
  • camphene 100 kilograms of camphene is dissolved in 50 grams of Benzol and dimerized in the presence of the same catalyst as shown in Example 1, such catalyst being added gradually at room temperature.
  • the resultant mixture is agitated for five hours and the resulting heat of reaction is cooled to ambient temperature by water.
  • the Benzol solution is filtered to remove the clay catalyst.
  • the Benzol solution is distilled under reduced pressure to remove unreacted camphene and there remains about 66 grams of viscous liquid which is redistvetted at a temperature of 178 C./15 mm. to obtain a colorless, odorless viscous liquid which is dicamphene.
  • the dicamphene is dissolved in 186* grams of ethanol and platinum black is added as a catalyst and the dicamphene is hydrogenated at 300 atmospheres and a temperature of for four hours.
  • the ethanol solution is separated from the platinum black by filtration and concentrated under reduced pressure.
  • This concentrate is distilled under vacuum and the fraction distilling at l68170 C./l5 mm. is colorless, odorless, viscous liquid and the yield is 40-42%.
  • the hydrocarbon products enumerated hereinbefore are especially useful when used as a component of an emulsified preparation, because the stability of the product is greatly increased by the fact that the specific gravity of the hydrocarbons of this mvention is greater than that of any of the hitherto commonly known oil substances.
  • the highly viscous and adhesive polymers either alone or in admixture, are mixed with a less viscous vegetable hydrocarbon compound dimer, the mixture has an advantage of being capable of addition to the basic materials for various toilet preparations.
  • this mixture is used as the base for a hair-shaping preparation, it gives the preparation not only superior hairshaping power, but also a good glossiness; the preparation is odorless and excels in cleansing quality.
  • the hydrocarbons make it possible to produce a stable hair-shaping emulsion possessing the same degree of hair-shaping power as hair pomade without any fear of the separation of the components on standing, and this is an added advantage because it has been difficult to produce a satisfactory hair-shaping preparation in the form of emulsion using known oily materials.
  • the highly viscous vegetable hydrocarbon polymers have the elfect of strengthening the. film when it is added to the base for film forming preparations, such as hair lacquer and nail enamel.
  • the present invention thus presents the possibility of developing various new toilet articles utilizing the excellent qualities of the vegetable hydrocarbon compounds employed in this invention.
  • Part (A) and part (B) are separately mixed and heated at 70 C., then part (B) is added to part (A). The mixture is stirred, and after the completion of emulsification is cooled while stirring till it becomes creamy.
  • Emulsion (Hand lotion, body lotion, etc.)
  • Part (A) and part (B) are separately mixed and heated to 70 C., then part (A) is added to part (B). The mixture is stirred, and after the completion of emulsification it is cooled down to 35 C. while stirring.
  • Part (A) and part (B) are separately mixed, heated and kept at 65 C., then part (A) is added to part (B). The mixture is stirred until emulsified, and cooled during such stirring till it becomes creamy.
  • Part (A) and part (B) are separately mixed and heated to 70 C., then part (A) is added to part (B).
  • the emulsion is cooled to 35 C. while stirring.
  • the components are mixed and dissolved uniformly.
  • the components are melted and kneader to uniformity. While still warm the mixture is pressed out from an extruder and cut into pieces of suitable length.
  • Hair lacquer Rosin 1.0 Vegetable hydrocarbon polymer oil 1.0 Alcohol a- 98.0
  • the rosin, oil and perfume are dissolved in alcohol to form a clear solution and sealed in an air-tight vessel with propellants such as Freon gas.
  • Nitrocellulose and vegetable hydrocarbon polymer oil are dissolved in a part of the solvents, and after adding plasticizer the mixture is stirred well, then the remaining part of the solvents are added. After complete mixing, it is poured into bottles.
  • perfume and preservatives employed in the foregoing examples are those conventionally used in the cosmetic industry, e.g. oil of rose, sodium benzoate, etc.
  • the terpenes treated in this invention exist in various forms extending from a highly viscous and adhesive liquid to an appropriately fluid oil in accordance with the degree of polymerization of the substance and can be used in any desired measure, the highly viscous oil being suitable for hair preparations and filmforming toilet preparations, while the less viscous oil is suitable for creams in general, emulsions, rouge and makeup preparations.
  • These substances can also be used together in any desired proportions; this makes it possible to apply them extensively for various toilet preparations in general.
  • These substances moreover, show such beautifying effects as are not seen in any of the hitherto known oily materials, and give highly nourishing, nonirritable products with enduring stability.
  • a toilet preparation having enhanced storage stability consisting essentially of a storage enhancing and stabilizing amount of a hydrocarbon selected from the group consisting of a mono-cyclic hydrogenated terpene polymer of the formula (C H and a bi-cyclic hydrogenated terpene polymer of the formula (C H wherein n is a positive whole number of from 2 to 4 in admixture with a base selected from the group consisting of a cold cream base, a cleansing cream base, a rouge base, a hair cream base, and a mascara base;

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
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  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

United States Patent O 3,502,769 HYDROGENATED TERPENE POLYMER STORAGE STABILIZED TOILET PREPARATION Nobukazu Fukuhara, Tokyo, Japan, assignor to Shiseido Co., Ltd., Tokyo, Japan No Drawing. Continuation-impart of application Ser. No. 240,739, Nov. 28, 1962. This application June 30, 1966, Ser. No. 561,701
Claims priority, application Japan, Dec. 13, 1961, 36/ 44,820 Int. Cl. A61k 7/00, 7/06, 9/06 US. Cl. 424-63 6 Claims ABSTRACT OF THE DISCLOSURE A toilet preparation containing a storage stabilizing amount of hydrocarbon which may be a mono-cyclic hydrogenated terpene polymer of the formula (C H and/or a bi-cyclic hydrogenated terpene polymer of the formula (C H17) where n is a whole number of from 2 to 4 and a cosmetic base, such as a cold cream or a cleansing cream base.
The present application is a continuation-in-part application of copending application Ser. No. 240,739, filed on Nov. 28, 1962 and now abandoned.
This invention relates to compositions useful as toilet preparations in general, such as skin toilet preparations, toilet preparations for hair, make-up preparations, etc., the characteristic of which is to have in the said compositions vegetable hydrocarbon compounds obtained by polymerizing and hydrogenating terpenes containing mono, sesqui, di and (or) tri terpenes. A primary object of this invention therefore is the embodiment of various toilet preparations of excellent quality by admixing therein said vegetable hydrocarbon compounds.
It is generally recognized that all kinds of vegetable and animal oils, fats, waxes and hydrocarbons hitherto used as raw materials for toilet preparations, possess, on account of their chemical constitution and various impurities inherently contained therein, various defects such as irritating the skin and the hair, causing the preparation to degenerate quickly, and imparting to the preparation various other undesirable qualities.
Recently, animal and vegetable oils and animal hydrocarbon compounds such as hydrogenated squalene have been used, but the former exhibits a strong offensive odor, deteriorates markedly in storage by putrefaction and oxidation, and irritates the skin, while the latter, which is used as a substitute for petroleum hydrocarbons, shows no refreshing effect on the skin, although it does have the advantage of good stability. Squalene has 30 carbon atoms in its molecular constitution, the number being less than the number of carbon atoms in petroleum hydrocarbons such as liquid parafiin, petrolatum, etc., and is now used extensively as an ingredient of toilet preparations, because it gives a fairly good effect and influence on the skin. This substance, however, is apt to have a bad odor which is characteristic of animal material and also tends to deteriorate on long storage. Moreover, its supply is limited and unreliable.
With respect to a toilet preparation requiring adhesive property, such as a hair-setting preparation, satisfactory results cannot be expected from materials used solely for skin toilet preparations. Hydrocarbons such as liquid paraffin, petrolatum, etc., and waxes such as carnauba wax, bees wax, etc., although employed extensively, when taken alone, do not shape the hair to any extent, la'ck gloss and are difficult to wash. When a vegetable oil such as castor oil is used as the main ingredient of the prep- 3,502,769 Patented Mar. 24, 1970 ice aration, the product is highly viscous, shapes the hair and renders it glossy, however, it exhibits a bad odor characteristic of the oil, which grows stronger during storage. Mucilaginous substances such as methyl cellulose, gum tragacanth, etc. can temporarily shape the hair, but they lack gloss and on drying change into powdery substance like scurf, so they are not suitable as materials for toilet preparations.
This invention, the object of which is to embody new toilet preparations free from the various defects mentioned above, makes it the principal point to add the vegetable hydrocarbon compounds obtained by polymerizing and hydrogenating terpenes containing mono, sesqui, di and tri terpene to the preparations.
The aforesaid hydrogenated terpenes are produced from alicyclic terpene hydrocarbons, For example, monoeyclic terpenes such as menthadienes (e.g. u-terpinene, 'y-terpinene, a-phellandrene, fl-phell andrene, terpinolene, limonene, etc.) and bi-cyclic terpenes such as the camphenes are first polymerized to form hydrocarbon compounds of the formula (C H wherein n is a positive whole number from 2 to 4. Thatis, the polymers are either dimer, trimers or tetramers. The resultant polymers are then completely hydrogenated and, in the case of the menthadienes, form mono-cyclic polymers of the formula (C H wherein n has the same significance as above, and, in the case of the bi-cyclic terpenes, there are formed bi-cyclic polymers of the formula (C H17) wherein n has the same significance.-
' The above detailed reaction, when using di-pentene as the starting material is as follows:
(IE (IE (EH3 3 l a l C H C-C-OH2- CH CHg-C-CHz- OH l I A I H3 0 C H2 0 H3 H i! H Di-pentene Dimer Reduced Dimer (3H (II-l (3H 0 O I /C* /Jl\ /C\ H O CH CH CH2 H O CH2 Di-pentene Dimer 0 H3 CH3 l 5 H O CH H 0 0 H;
Reduced Dimer Of these two reactions, which occur simultaneously, reaction (1) is the main reaction while reaction (2) is a side reaction. Hence, it is apparent that in the case when menthadienes are the starting materials, the final compounds, viz. the vegetable hydrocarbons of this invention, will be of the following formula:
wherein n in the above formula is a positive whole number of from 2 to 4.
When camphene is the starting material the vegetable hydrocarbons of this invention will have the following formula:
H20 t H CH2 H2'o mo-o-om H2 H :1 II
wherein n has the same significance as above.
There are many catalysts which can be used to polymerize the terpenes. Among these may be mentioned an acid clay or active clay having mixed therein a small amount of zinc chloride, aluminum chloride, silica gel, etc. A preferred catalyst one which consists of 50% by weight of acid clay and 50% by weight of active clay which had admixed therein 1 to 3% by weight of zinc chloride. The temperature at which the reaction takes place is not particularly critical; however, a temperature of between 170'- 180 C. is preferred when dipentene is the starting materiai.
The resultant polymer from the above-reaction is then reduced with hydrogen at a high temperature of pressure and, if desired, a catalyst, e.g. nickel, can be present. The resulting compounds, as exemplified by Formulae I and II, are completely hydrogenated.
The mono, sesqui, di or tri terpenes mentioned above are found vegetable essential oils and possess an aromatic odor, but the compounds represented by Formula I, and mixtures thereef, and Formula II, and mixtures thereof, have excellent quality as the basic materials for toilet preparations. The compounds employed in this invention are colorless transparent liquids of specific gravity above 0.910, far greater than that of any one of the hitherto commonly known oils. The compounds are chemically stable, and hence are suitable for long storage, they also have a moderate fluidity and oily touch, and show much less irritating effect against the skin than any of the hitherto known oils, as proved by patch tests. They also have been clinically tested with satisfactory results by applying the preparations containing the substances on allergic patients, and have thus been found to be not only safe when used on sensitive skin but also produce a very desirable effect on skin sanitation by easy assimilation to the skin oil producing a desirable, oily and smooth feeling.
Typical illustrations of the production of the aforesaid polymers of this invention are given below.
100 kilograms of dipentene is dimerized by reacting same in the presence of a catalytic amount of a catalyst composed of 50 parts by weight of acid clay, 50 parts by weight of active clay and 3 parts by weight of zinc chloride at l70180 C. The resultant product is then subjected to reduction with hydrogen at 250 atmospheres and a temperature of 280 C. in the presence of catalytic nickel.
Fractional distillation gives 22 to 25 kilo-grams of distillate boiling at 210-235 C./4 mm.
This product is the reduced dimer-dipentene which is shown in Equations 1 and 2. This product is designated vegatable hydrocarbon oil dimer in the hereinafter-described examples of practical application of the present invention.
The production of the higher polymers vis. the trimers and tetramers, is as follows:
kilograms of dipentene is polymerized by the action of catalyst, as aforesaid, in the presence of sulfuric acid, (ferric sulfate and aluminum sulfate can also be used) at 181-i90 C. Distillation under reduced pressure gives a distillate boiling at 190280 C./ 4 mm. Reduction with catalyic hydrogen (nickel catalyst) at 250 atmospheres and a temperature of 280 C. gives a viscous liquid boiling at 210280 C./4 mm.
This product is designated vegetable hydrocarbon polymer oil in the hereinafter-described examples of practical application of the present invention. Any of the other previously mentioned terpenes may similarly be converted into vegetable hydrocarbon polymer compound for use according to this invention.
A typical illustration of the production of a bi-cyclic terpene is as follows:
100 kilograms of camphene is dissolved in 50 grams of Benzol and dimerized in the presence of the same catalyst as shown in Example 1, such catalyst being added gradually at room temperature.
The resultant mixture is agitated for five hours and the resulting heat of reaction is cooled to ambient temperature by water.
The Benzol solution is filtered to remove the clay catalyst.
The Benzol solution is distilled under reduced pressure to remove unreacted camphene and there remains about 66 grams of viscous liquid which is redistiiled at a temperature of 178 C./15 mm. to obtain a colorless, odorless viscous liquid which is dicamphene.
The dicamphene is dissolved in 186* grams of ethanol and platinum black is added as a catalyst and the dicamphene is hydrogenated at 300 atmospheres and a temperature of for four hours.
The ethanol solution is separated from the platinum black by filtration and concentrated under reduced pressure.
This concentrate is distilled under vacuum and the fraction distilling at l68170 C./l5 mm. is colorless, odorless, viscous liquid and the yield is 40-42%.
The characteristics are:
The formula of the thus-produced dicamphene is as follows:
The hydrocarbon products enumerated hereinbefore are especially useful when used as a component of an emulsified preparation, because the stability of the product is greatly increased by the fact that the specific gravity of the hydrocarbons of this mvention is greater than that of any of the hitherto commonly known oil substances. Further, when the highly viscous and adhesive polymers, either alone or in admixture, are mixed with a less viscous vegetable hydrocarbon compound dimer, the mixture has an advantage of being capable of addition to the basic materials for various toilet preparations. Especially when this mixture is used as the base for a hair-shaping preparation, it gives the preparation not only superior hairshaping power, but also a good glossiness; the preparation is odorless and excels in cleansing quality. The hydrocarbons make it possible to produce a stable hair-shaping emulsion possessing the same degree of hair-shaping power as hair pomade without any fear of the separation of the components on standing, and this is an added advantage because it has been difficult to produce a satisfactory hair-shaping preparation in the form of emulsion using known oily materials. Again, the highly viscous vegetable hydrocarbon polymers have the elfect of strengthening the. film when it is added to the base for film forming preparations, such as hair lacquer and nail enamel. The present invention thus presents the possibility of developing various new toilet articles utilizing the excellent qualities of the vegetable hydrocarbon compounds employed in this invention.
Examples of practical application of this invention are shown below (numbers are percent by weight):
EXAMPLE OF PRACTICAL APPLICATION NO. 1
Cold cream Part (A) Bees wax 11.0 Ceresine 8.0 Lanolin 5.0 Petrolatum 10.0 Vegetable hydrocarbon polymer oil 2.0 Vegetable hydrocarbon oil dimer 37.0 Perfume and preservatives, q.s. Part (B)- Borax 0.8 Distilled water 26.2
Part (A) and part (B) are separately mixed and heated at 70 C., then part (B) is added to part (A). The mixture is stirred, and after the completion of emulsification is cooled while stirring till it becomes creamy.
EXAMPLE OF PRACTICAL APPLICATION NO. 2
Emulsion (Hand lotion, body lotion, etc.)
Part (A) Stearic acid 2.0 Cetyl alcohol 0.5 Glycerin monostearate 5.0 Vegetable hydrocarbon oil dimer 10.0 Perfume and preservatives, q.s.
Part (B) Distilled water 79.5
Glycerin 2.0 Triethanolamine 1.0
Part (A) and part (B) are separately mixed and heated to 70 C., then part (A) is added to part (B). The mixture is stirred, and after the completion of emulsification it is cooled down to 35 C. while stirring.
EXAMPLE OF PRACTICAL APPLICATION NO. 3
Cleansing cream Part (A)- Solid paraffin 10.0 Petrolatum 15.0 Perfume and preservatives, q.s. Vegetable hydrocarbon'oil dimer 40.0 Glycerin monostearate 5.0 Part (B) Distilled Water 24.5 Propylene glycol 5.0 Powder soap 0.5
Part (A) and part (B) are separately mixed, heated and kept at 65 C., then part (A) is added to part (B). The mixture is stirred until emulsified, and cooled during such stirring till it becomes creamy.
6 EXAMPLE OF PRACTICAL APPLICATION NO. 4
Rouge Bees wax 35.0 Carnauba wax 5.0 Lanolin 20.0 Vegetable hydrocarbon oil dimer 30.0 Pigments (rouge) 10.0
Perfume and preservatives, q.s.
All the components are mixed, heated to melting, and after the pigments are uniformly dispersed with homogenizer, poured into molds and quickly cooled to solidify.
EXAMPLE OF PRACTICAL APPLICATION NO. 5
Part (A) and part (B) are separately mixed and heated to 70 C., then part (A) is added to part (B). The emulsion is cooled to 35 C. while stirring.
EXAMPLE OF PRACTICAL APPLICATION NO. 6
Pomade Solid parafiin 5.0 Bees wax 5.0 Petrolatum 60.0 Vegetable hydrocarbon polymer oil 30.0
Perfume and preservatives, q.s.
All the components are mixed together and heated. After melting, the liquid mixture is poured into a vessel and left to solidify.
EXAMPLE OF PRACTICAL APPLICATION NO. 7
Cosmetic Solid paraifin 20.0 Bees wax 30.0 Petrolatum 30.0 Vegetable hydrocarbon oil dimer 15.0 Vegetable hydrocarbon polymer oil 5.0
Perfume and preservatives, q.s.
These substances are mixed together and heated. After melting, the mixture is poured into a suitable mold and left to cool. When it becomes solid, it is taken out of the mold and put in a holder.
EXAMPLE OF PRACTICAL APPLICATION NO. 8
Hair oil Vegetable hydrocarbon polymer oil 10.0 Vegetable hydrocarbon oil dimer 90.0
Perfume and preservatives, q.s.
The components are mixed and dissolved uniformly.
EXAMPLE OF PRACTICAL APPLICATION NO. 9
Mascara Stearic acid 15.0 Triethanolamine 5.0 Bees wax 25.0 Carnauba wax 35.0 Vegetable hydrocarbon polymer oil 10.0 Carbon black 10.0
The components are melted and kneader to uniformity. While still warm the mixture is pressed out from an extruder and cut into pieces of suitable length.
7 EXAMPLE OF PRACTICAL APPLICATION NO. 10
Hair lacquer Rosin 1.0 Vegetable hydrocarbon polymer oil 1.0 Alcohol a- 98.0
Perfume, q.s.
The rosin, oil and perfume are dissolved in alcohol to form a clear solution and sealed in an air-tight vessel with propellants such as Freon gas.
EXAMPLE OF PRACTICAL APPLICATION NO. 11
Nail enamel Nitrocellulose 16.0 Vegetable hydrocarbon polymer oil 2.0 Acetone 47.0 Amyl acetate 16.0 Methyl-ethyl-ketone 8.0 n-Butyl alcohol 2.0 Dibutyl phthalate 1.0 Cyclohexane 8.0
Nitrocellulose and vegetable hydrocarbon polymer oil are dissolved in a part of the solvents, and after adding plasticizer the mixture is stirred well, then the remaining part of the solvents are added. After complete mixing, it is poured into bottles.
The perfume and preservatives employed in the foregoing examples are those conventionally used in the cosmetic industry, e.g. oil of rose, sodium benzoate, etc.
In summing up, the terpenes treated in this invention exist in various forms extending from a highly viscous and adhesive liquid to an appropriately fluid oil in accordance with the degree of polymerization of the substance and can be used in any desired measure, the highly viscous oil being suitable for hair preparations and filmforming toilet preparations, while the less viscous oil is suitable for creams in general, emulsions, rouge and makeup preparations. These substances can also be used together in any desired proportions; this makes it possible to apply them extensively for various toilet preparations in general. These substances, moreover, show such beautifying effects as are not seen in any of the hitherto known oily materials, and give highly nourishing, nonirritable products with enduring stability.
Having thus disclosed the invention what is claimed is:
1. A toilet preparation having enhanced storage stability consisting essentially of a storage enhancing and stabilizing amount of a hydrocarbon selected from the group consisting of a mono-cyclic hydrogenated terpene polymer of the formula (C H and a bi-cyclic hydrogenated terpene polymer of the formula (C H wherein n is a positive whole number of from 2 to 4 in admixture with a base selected from the group consisting of a cold cream base, a cleansing cream base, a rouge base, a hair cream base, and a mascara base;
2. The toilet preparation of claim 1 wherein the cosmetic base is a cold cream base.
3. The toilet preparation of claim 1 wherein the cosmetic base is a cleansing cream base.
4. The toilet preparation of claim 1 wherein the base is a rouge base.
5. The toilet preparation of claim 1 wherein the cosmetic base is a hair cream base.
6. The toilet preparation of claim 1, wherein the cosmetic base is a mascara base.
References Cited UNITED STATES PATENTS 2,249,112 7/1941 Carmody 260666 FOREIGN PATENTS 1,004,174 9/1965 Great Britain.
ALBERT T. MEYERS, Primary Examiner A. P. FAGELSON, Assistant Examiner US. Cl. X.R.
US561701A 1961-12-13 1966-06-30 Hydrogenated terpene polymer storage stabilized toilet preparation Expired - Lifetime US3502769A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
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US4170576A (en) * 1978-07-10 1979-10-09 International Flavors & Fragrances Inc. Uses of mixtures of alpha methyl styrene dimers and terpene dimers in perfumery processes and products
EP0005659A1 (en) * 1978-05-03 1979-11-28 INTERNATIONAL FLAVORS & FRAGRANCES INC. A process for diluting perfumery products with the aid of dimerized alpha methyl styrene and/or dimerized terpenes, a mixture to operate the process, and a perfumery composition so diluted
US4820739A (en) * 1982-06-28 1989-04-11 Lucta, S.A. Fat suppressant
US5019376A (en) * 1989-03-13 1991-05-28 S. C. Johnson & Son, Inc. Sparkling pearlescent personal care compositions
US5723709A (en) * 1994-04-14 1998-03-03 Arizona Chemical Company Terpene dimer compositions and related methods of manufacture
US5762696A (en) * 1996-07-19 1998-06-09 Arizona Chemical Company Terpene dimer varnish and ink formulations and related methods of manufacture
US5847247A (en) * 1994-04-14 1998-12-08 Arizona Chemical Company Terpene-based solvents
EP1122276A3 (en) * 2000-02-01 2002-01-02 Shin-Etsu Chemical Co., Ltd. A novel silicone compound and a makeup containing this compound
EP1122277A3 (en) * 2000-02-04 2002-01-02 Shin-Etsu Chemical Co., Ltd. A novel silicone compound, a powder surface-treated with this compound, and makeup containing this powder
US20070286828A1 (en) * 2004-11-23 2007-12-13 Durlin France Varnish composition based on a solvent exclusively of vegetable origin

Families Citing this family (3)

* Cited by examiner, † Cited by third party
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IT974504B (en) * 1961-12-13 1974-07-10 Shiseido Co Ltd COSMETIC PREPARATION BASED ON VEGETABLE HYDROCARBON COMPOUNDS
US4562214A (en) * 1979-09-10 1985-12-31 Witco Chemical Corporation Personal care emulsion
HU196553B (en) * 1984-11-12 1988-12-28 Tibor Keri Cosmetic composition for skin-regeneration containing extract of green beans

Citations (2)

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Publication number Priority date Publication date Assignee Title
US2249112A (en) * 1937-12-24 1941-07-15 Marie O Carmody Hydrogenation of terpene polymers
GB1004174A (en) * 1961-12-13 1965-09-08 Shiseido Co Ltd Toilet preparations

Patent Citations (2)

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US2249112A (en) * 1937-12-24 1941-07-15 Marie O Carmody Hydrogenation of terpene polymers
GB1004174A (en) * 1961-12-13 1965-09-08 Shiseido Co Ltd Toilet preparations

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0005659A1 (en) * 1978-05-03 1979-11-28 INTERNATIONAL FLAVORS & FRAGRANCES INC. A process for diluting perfumery products with the aid of dimerized alpha methyl styrene and/or dimerized terpenes, a mixture to operate the process, and a perfumery composition so diluted
US4170576A (en) * 1978-07-10 1979-10-09 International Flavors & Fragrances Inc. Uses of mixtures of alpha methyl styrene dimers and terpene dimers in perfumery processes and products
US4820739A (en) * 1982-06-28 1989-04-11 Lucta, S.A. Fat suppressant
US5019376A (en) * 1989-03-13 1991-05-28 S. C. Johnson & Son, Inc. Sparkling pearlescent personal care compositions
US5847247A (en) * 1994-04-14 1998-12-08 Arizona Chemical Company Terpene-based solvents
US5723709A (en) * 1994-04-14 1998-03-03 Arizona Chemical Company Terpene dimer compositions and related methods of manufacture
US5762696A (en) * 1996-07-19 1998-06-09 Arizona Chemical Company Terpene dimer varnish and ink formulations and related methods of manufacture
EP1122276A3 (en) * 2000-02-01 2002-01-02 Shin-Etsu Chemical Co., Ltd. A novel silicone compound and a makeup containing this compound
US6479686B2 (en) 2000-02-01 2002-11-12 Shin-Etsu Chemical Co., Ltd. Silicon compound, and a makeup containing this compound
US6759031B2 (en) 2000-02-01 2004-07-06 Shi-Etsu Chemical Co., Ltd. Silicone compound, and a makeup containing this compound
KR100674559B1 (en) * 2000-02-01 2007-01-26 신에쓰 가가꾸 고교 가부시끼가이샤 New Silicone Compounds and Cosmetics Using the Same
EP1122277A3 (en) * 2000-02-04 2002-01-02 Shin-Etsu Chemical Co., Ltd. A novel silicone compound, a powder surface-treated with this compound, and makeup containing this powder
US6717003B2 (en) 2000-02-04 2004-04-06 Shin-Etsu Chemical Co., Ltd. Silicone compound, a powder surface-treated with this compound, and a makeup containing this powder
US20070286828A1 (en) * 2004-11-23 2007-12-13 Durlin France Varnish composition based on a solvent exclusively of vegetable origin

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DE1492118B2 (en) 1974-07-11
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DE1492118C3 (en) 1975-02-27
DE1492118A1 (en) 1969-07-10

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