Gels of nonpolar liquids with N-acyl amino acids and derivatives thereof as gelling agents

• US 3,969,087 A
• Filed: 02/12/1975
• Issued: 07/13/1976
• Est. Priority Date: 08/07/1974
• Status: Expired due to Term

• Current Assignee: Ajinomoto Company Limited (Ajinomoto Co., Inc.)
• Original Assignee: Ajinomoto Company Limited (Ajinomoto Co., Inc.)
• Inventors: Saito, Tadaomi, Takehara, Masahiro, Honna, Masao, Ninagawa, Sadayoshi, Takesada, Masahiko, Matsuzawa, Yoshimasa
• Primary Examiner(s): Miller, Edward A.
• Application Number:
  US05/549,488
• Time in Patent Office: 517 Days
• Field of Search: 44/7 C, 44/7 D, 252/316
• US Class Current: 44/270
• CPC Class Codes: A23D 9/007 characterised by ingredients other than fatty acid triglycerides
• CPC Class Codes: A61K 8/042 Gels
• CPC Class Codes: A61K 8/44 Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
• CPC Class Codes: A61K 9/0014 Skin, i.e. galenical aspects of topical compositions non-active ingredients are additionally classified in A61K47/00; A61K9/0009, A61K9/0021, A61K9/7015, A61K9/7023 take precedence; cosmetic preparations A61K8/00, A61Q; preparations for wound dressings or bandages A61L26/00
• CPC Class Codes: A61Q 19/00 Preparations for care of the skin
• CPC Class Codes: A61Q 5/12 Preparations containing hair conditioners
• CPC Class Codes: B01J 19/06 Solidifying liquids making microcapsules B01J13/02
• CPC Class Codes: C08K 5/17 Amines; Quaternary ammonium compounds
• CPC Class Codes: C09D 7/43 Thickening agents
• CPC Class Codes: C10L 1/224 Amides; Imides carboxylic acid amides, imides C10L1/221, C10L1/2227 take precedence
• CPC Class Codes: C10L 1/2412 sulfur bond to an aromatic radical
• CPC Class Codes: C10L 7/02 liquid fuels lubricating compositions C10M

Abstract

A wide variety of non-polar organic liquids are converted into gels by homogeneously admixing the non-polar organic liquids with a small amount of certain N-acyl amino acids or derivatives of N-acyl amino acids such as esters, amides and amine salts of the N-acyl amino acids.

Claims

1. A process for preparing a gel, which comprises:

homogeneously admixing a non-polar organic liquid having a dielectric constant of less than about 20 and having a solubility less than 10% by weight in water with an effective gel forming amount of at least one compound containing an N-acylamino acid component having the formula;

##EQU7## wherein RCO is a C₂ to C₃₀ aliphatic acyl group or an aralkylacyl group;

Z is selected from the group consisting of hydroxy, -NH₂, -OR₁, -NHR₂, ##EQU8## and -0^-R₅ NH₃ ⁺ wherein R₁, R₂, R₃, R₄ and R₅ are selected from the group consisting of C₁ to C₃₀ aliphatic hydrocarbon groups and aralkyl groups;

X is selected from the group consisting of hydrogen and methyl; and

Y is selected from the group consisting of ##EQU9## wherein R₆ is C₁ to C₄ alkyl, benzyl, phenyl, --CH₂ OH, ##EQU10## --CH₂ SH, --CH₂ CH₂ --S-CH₃ or -- (CH₂)_p --COZ and p is a positive integer of 1 or 2 and Z is the same as above, --(CH₂)_m NHCOR, wherein m is a positive integer of 3 or 4 and COR is the same as above and --(CH₂)_n --, wherein n is a positive integer of 1 to 6;

with the proviso that when Z is --OR₁, ##EQU11## where R₆ is --(CH₂)_m NHCOR and that at least one of R, R₁, R₂, R₃, R₄ and R₅ is a C₅ to C₃₀ aliphatic hydrocarbon group; and

allowing the mixture to stand until gel formation occurs.

2. The process of claim 1, wherein said homogeneous admixing is conducted at temperatures ranging from room temperature up to the boiling point of said non-polar organic liquid.

3. The process of claim 1, wherein said compound containing an N-acylamino acid component is admixed with said non-polar organic liquid in the form of very fine powdered particles or as a solution.

4. The process of claim 1, wherein the effective gel forming amount of said compound containing an N-acylamino acid component added to said non-polar organic liquid is 0.05% to 20% by weight.

5. A process for preparing a gel, which comprises:

mixing a non-polar organic liquid having a dielectric constant of less than about 20 and having a solubility less than 10% by weight in water with 0.05 - 20% by weight based on said non-polar organic liquid of a compound containing an N-acylamino acid component having the formula (I), ##EQU12## wherein RCO is a C₂ to C₃₀ aliphatic acyl group or an aralkyl acyl group;

Z is selected from the group consisting of hydroxy, --NH₂, --OR₁, --NHR₂, ##EQU13## and --O^-R₅ NH₃ ⁺, wherein R₁, R₂, R₃, R₄ and R₅ are selected from the group consisting of C₁ to C₃₀ aliphatic hydrocarbon radicals and aralkyl radicals;

X is selected from the group consisting of hydrogen and methyl;

Y is selected from the group consisting of ##EQU14## wherein R₆ is C₁ to C₄ alkyl, benzyl, phenyl, --CH₂ OH, ##EQU15## --CH₂ SH, --CH₂ CH₂ --S--CH₃ or --(CH

     2)_p --COZ and p is a positive integer of 1 or 2 and Z is the same as above, --(CH₂)_m NHCOR, wherein m is a positive integer of 3 or 4 and COR is the same as above, and --(CH₂)_n --, wherein n is a positive integer of 1 to 6, with the proviso that when Z is -OR₁, ##EQU16## wherein R₆ is --(CH₂)_m NHCOR and that at least one of R, R₁, R₂, R₃, R₄ and R₅ is a C₆ to C₃₀ aliphatic hydrocarbon group;

heating the mixture to effect solution;

cooling the resulting solution to room temperature; and

thereafter;

allowing said cooled solution to stand until gel formation occurs.

6. The process of claim 5, wherein said non-polar organic liquid is a liquid hydrocarbon.

7. The process of claim 6, wherein said liquid hydrocarbon is selected from the group consisting of gasoline, naphthas, kerosine, gas oil, heavy oil, crude oil, spindle oil, turbine oil, liquid paraffin, benzene, oxlene, toluene, hexane, heptane, octane and cyclohexane.

8. The process of claim 5, wherein said non-polar organic liquid is a fatty oil.

9. The process of claim 8, wherein said fatty oil is selected from the group consisting of corn oil, soybean oil, olive oil, rape seed oil and cotton seed oil.

10. The process of claim 5, wherein said non-polar organic liquid is an ester.

11. The process of claim 10, wherein said ester is selected from the group consisting of butyl acetate, diethyl phthalate, dioctyl phthalate, dioctyl sebacate and tricresyl phosphate.

12. The process of claim 5, wherein said non-polar organic liquid is a ketone selected from the group consisting of methyl isobutyl ketone and diisobutyl ketone.

13. The process of claim 5, wherein said non-polar organic liquid is a normally liquid polyoxyalkylene monoalkyl ether.

14. The process of claim 13, wherein said polyoxyalkylene monoalkyl ether is polyoxyethylene monolauryl ether containing 4 to 6 oxyethylene units or polyoxypropylene monoalkyl ethers wherein the alkyl group has 4 to 12 carbon atoms and the number of oxypropylene units is 10 to 50.

15. The process of claim 5, wherein said non-polar organic liquid is a normally liquid polyoxyalkylene glycol fatty acid ester.

16. The process of claim 15, wherein said polyoxyalkylene glycol fatty acid ester is polyoxyethylene lauric or oleic acid ester containing 4 to 6 oxyethylene units.

17. A process for preparing a gel, which comprises:

homogeneously admixing a non-polar organic liquid having a dielectric constant of less than about 20 and having a solubility less than 10% by weight in water with 0.05% to 20% by weight of at least one compound containing an N-acylamino acid component having the formula ##EQU17## wherein RCO is a C₅ to C₃₀ aliphatic acyl, and Y is selected from the group consisting of ##EQU18## wherein R₆ is a C₁ to C₄ alkyl and --(CH₂).sub. m NHCOR, wherein m is a positive integer of 3 or 4 and COR is the same as above; and

allowing the mixture to stand until gel formation occurs.

18. The process of claim 17, wherein said compound containing an N-acylamino acid component is selected from the group consisting of N-lauroylalanine, N.sup.α

, N.sup.δ

-dicaproyl ornithine, N.sup.α

,N.sup.δ

-dicapryloyl orinthine, N.sup.α

,N.sup.δ

-dilauroylornithine, N.sup.α

,N.sup.ε

-dicocoylornithine, N.sup.α

,N.sup.ε

-dicaproyllysine and N.sup.α

,N.sup.ε

-dicapryloyllysine.

19. A process for preparing a gel, which comprises:

homogeneously admixing a non-polar organic liquid having a dielectric constant of less than 20 and having a solubility less than 10% by weight in water with 0.05% to 20% by weight of a compound containing N-acylamino acid component having the formula ##EQU19## wherein RCO is a C₂ to C₃₀ aliphatic acyl group or an aralkylacyl group;

R₁ is a C₁ to C₃₀ aliphatic hydrocarbon group or an aralkyl; and

##EQU20## wherein R₆ is --(CH₂)_m NHCOR, m is a positive integer of 3 or 4 and RCO is the same as above, with the proviso that at least one of R and R₁ is a C₅ to C₃₀ aliphatic hydrocarbon group; and

allowing the mixture to stand until gel formation occurs.

20. The process of claim 19, wherein said compound containing an N-acylamino acid component is an N.sup.α

,N.sup.δ

-dicapryloylornithine alkyl ester, wherein said alkyl group has 6 to 18 carbon atoms;

N.sup.α

,N.sup.δ

-dilauroylornithine alkyl ester, wherein said alkyl group has 6 to 18 carbon atoms;

N.sup.α

,N.sup.δ

-dicocoylornithine alkyl ester, wherein said alkyl group has 6 to 18 carbon atoms;

N.sup.α

,N.sup.δ

-distearoylornithine alkyl ester, wherein said alkyl group has 6 to 18 carbon atoms;

N.sup.α

,N.sup.δ

-ditallowylornithinealkyl ester, wherein said alkyl group has 6 to 18 carbon atoms;

N.sup.α

,N.sup.ε

-dicapryloyllysine alkyl ester, wherein said alkyl group has 6 to 18 carbon atoms;

N.sup.α

,N.sup.ε

-dilauroyllysine alkyl ester, wherein said alkyl group has 6 to 18 carbon atoms;

N.sup.α

,N.sup.ε

-dicocoyllysine alkyl ester, wherein said alkyl group has 6 to 18 carbon atoms;

N.sup.α

,N.sup.ε

-distearoyllysine alkyl ester, wherein said alkyl group has 6 to 18 carbon atoms or N.sup.α

,N.sup.ε

-ditallowyllysine alkyl ester, wherein said alkyl group has 6 to 18 carbon atoms.

21. A process for preparing a gel, which comprises:

homogeneously admixing a non-polar organic liquid having a dielectric constant of less than 20 and having a solubility less than 10% by weight in water with 0.05% to 20% by weight of a compound containing an N-acylamino acid component having the formula ##EQU21## wherein RCO is a C₂ to C₃₀ aliphatic acyl group or an aralkyl acyl group;

Z is --NH₂, --NHR₂ or ##EQU22## wherein R₂, R₃ and R₄ are selected from the group consisting of C₁ to C₃₀ aliphatic hydrocarbon groups and aralkyl groups; and

##EQU23## wherein R₆ is C₁ to C₄ alkyl, benzyl, --CH₂ CH₂ --S--CH₃, or --(CH₂)_p -COZ wherein p is a positive integer of 1 or 2 and Z is the same as above;

--(CH₂)_m NHCOR, wherein m is a positive integer of 3 or 4 and COR is the same as above and --(CH₂)_n --, wherein n is a positive integer of 1 to 6, with the proviso that at least one of R, R₂, R₃, and R₄ is a C₅ to C₃₀ aliphatic hydrocarbon group; and

allowing the mixture to stand until gel formation occurs.

22. The process of claim 21, wherein said compound containing an N-acylamino acid component is N-acetyl glutamic acid-α

,γ

-dialkyl amide, wherein said alkyl group has 12 to 18 carbon atoms;

N-capryloylglutamic acid-α

,γ

-diamide, N-caprylyl glutamic acid-α

,γ

-dialkylamide, wherein said alkyl group has 1 to 18 carbon atoms;

N-lauroylglutamic acid-α

,γ

-diamide, N-lauroylglutamic acid-α

,γ

-dialkylamide, wherein said alkyl group has 1 to 18 carbon atoms;

N-cocoylglutamic acid-α

,γ

-diamide, N-cocoylglutamic acid-α

,γ

-dialkylamide, wherein said alkyl group has 1 to 18 carbon atoms;

N-stearoylglutamic acid-α

,γ

-diamide, N-stearoylglutamic acid-α

,γ

-dialkylamide, wherein said alkyl group has 1 to 18 carbon atoms;

N-tallowylglutamic acid-α

,γ

-diamide, N-(tallowyl)glutamic acid-α

,γ

-dialkylamide, wherein said alkyl group has 1 to 18 carbon atoms;

N.sup.α

,N.sup.ε

-diacetyllysine alkylamide, wherein said alkyl group has 12 to 18 carbon atoms;

N.sup.α

,N.sup.ε

-dicapryloyllysine amide, N.sup.α

,N.sup.ε

-dicapryloyllysine alkylamide, wherein said alkyl group has 1 to 18 carbon atoms;

N.sup.α

,N.sup.ε

-dilauroyllysine amide, N.sup.α

,N.sup.ε

-dilauroyllysine alkylamide, wherein said alkyl group has 1 to 18 carbon atoms;

N.sup.α

,N.sup.ε

-dicocoyllysine amide, N.sup.α

,N.sup.ε

-dicocoyllysine alkylamide, wherein said alkyl group has 1 to 18 carbon atoms;

N.sup.α

,N.sup.ε

-distearoyllysine amide, N.sup.α

,N.sup.ε

-distearoyllysine alkylamide, wherein said alkyl group has 1 to 18 carbon atoms;

or N.sup.α

,N.sup.ε

-di(tallowyl)lysine amide, N.sup.α

,N.sup.ε

-di(tallowyl)lysine alkylamide, wherein said alkyl group has 1 to 18 carbon atoms.

23. A process for preparing a gel, which comprises:

homogeneously admixing a non-polar organic liquid having a dielectric constant of less than 20 and having a solubility less than 10% by weight in water with 0.05% to 20% by weight of a compound containing an N-acylamino acid component having the formula ##EQU24## wherein RCO is a C₂ to C₃₀ aliphatic acyl group or an aralkyl acyl group;

R₅ is a C₁ to C₃₀ aliphatic hydrocarbon group or an aralkyl; and

Y ##EQU25## wherein R₆ is selected from the group consisting of C₁ to C₄ alkyl, benzyl or --(CH₂)_m NHCOR, and m is a positive integer of 3 or 4 and COR is the same as above, with the proviso that at least one of R and R₅ is a C₅ to C₃₀ aliphatic hydrocarbon group; and

allowing the mixture to stand until gel formation occurs.

24. The process of claim 23, wherein said compound containing an N-acylamino acid component is an N.sup.α

,N.sup.δ

-dicapryloyllysine alkylamine salt, wherein said alkylamine has 8 to 18 carbon atoms;

an N.sup.α

,N.sup.ε

-dilauroyllysine alkylamine salt, wherein said alkylamine has 4 to 18 carbon atoms;

an N.sup.α

,N.sup.ε

-dicocoyllysine alkylamine salt, wherein said alkylamine has 4 to 18 carbon atoms;

an N.sup.α

,N.sup.ε

-distearoyllysine alkylamine salt, wherein said alkylamine has 4 to 18 carbon atoms;

an N.sup.α

,N.sup.ε

-ditallowyllysine alkylamine salt, wherein said alkylamine has 4 to 18 carbon atoms;

an N.sup.α

,N.sup.ε

-dicapryloylornithine alkylamine salt, wherein said alkylamine has 8 to 18 carbon atoms;

an N.sup.α

,N.sup.δ

-dilauroylornithine alkylamine salt, wherein said alkylamine has 4 to 18 carbon atoms;

an N.sup.α

,N.sup.δ

-dicocoylornithine alkylamine salt, wherein said alkylamine has 4 to 18 carbon atoms;

an N.sup.α

,N.sup.δ

distearoylornithine alkylamine salt, wherein said alkylamine has 4 to 18 carbon atoms;

an N.sup.α

,N.sup.δ

-ditallowylornithine alkylamine salt, wherein said alkylamine has 4 to 18 carbon atoms;

an N-lauroylphenylalanine alkylamine salt, wherein said alkylamine has 8 to 18 carbon atoms;

an N-cocoylphenylalanine alkylamine salt, wherein said alkylamine has 8 to 18 carbon atoms;

an N-stearoylphenylalanine alkylamine salt, wherein said alkylamine has 8 to 18 carbon atoms, or an N-tallowylphenylalanine alkylamine salt, wherein said alkylamine has 8 to 18 carbon atoms.

25. A gel, consisting essentially of:

a homogeneous mixture of a non-polar organic liquid having a dielectric constant of less than 20 and having a solubility less than 10% by weight in water and 0.05% to 20% by weight of at least one compound containing an N-acylamino acid component having the formula ##EQU26## wherein RCO is a C₂ to C₃₀ aliphatic acyl group or an aralkyl acyl group;

Z is hydroxy, --NH₂, --OR₁, --NHR₂, ##EQU27## or --O^-R₅ NH₃ ⁺, wherein R₁, R₂, R₃, R₄ and R₅ is a C₂ to C₃₀ aliphatic hydrocarbon group and aralkyl groups;

X is hydrogen or methyl; and

##EQU28## wherein R₆ is C₁ to C₄ alkyl, benzyl, phenyl, --CH₂ OH, ##EQU29## --CH₂ SH, --CH₂ CH₂ --S--CH₃ or --(CH₂)_p COZ; and

p is a positive integer of 1 or 2, and Z is the same as above;

--(CH₂)_m NHCOR, wherein m is a positive integer of 3 or 4 and COR is the same as above, or --(CH₂)_n --, wherein n is a positive integer of 1 to 6, with the proviso that when Z is --OR₁, ##EQU30## wherein R₆ is --(CH₂)_m NHCOR and that at least one of R, R₁, R₂, R₃, R₄ and R₅ is a C₅ to C₃₀ aliphatic hydrocarbon group.

26. The gel of claim 25, wherein said non-polar organic liquid is selected from the group consisting of gasoline, naphthas, kerosine, gas oil, heavy oil, crude oil, spindle oil, turbine oil, liquid paraffin, benzene, xylene, toluene, hexane, heptane, octane, cyclohexane, corn oil, soybean oil, olive oil, rapeseed oil, cotton seed oil, butyl acetate, diethyl phthalate, dioctyl phthalate, dioctyl sebacate, tricresyl phosphate, methyl isobutyl ketone, diisobutyl ketone, liquid polyoxyethylene, monolauryl ether, liquid polyoxyethylene monostearyl ether, liquid polyoxypropylene monobutyl ether, liquid polyoxypropylene monolauryl ether, liquid polyoxypropylene monostearyl ether, liquid polyoxyethylene glycol lauric acid ester, liquid polyoxypropylene glycol oleic acid ester and mixtures thereof.

27. A gel, consisting essentially of a homogeneous mixture of a non-polar organic liquid having a dielectric constant of less than 20 and having a solubility less than 10% by weight in water, and 0.05% - 20% by weight of at least one compound having the formula ##EQU31## wherein RCO is C₅ to C₃₀ aliphatic acyl, and ##EQU32## wherein R₆ is C₁ to C₄ alkyl or --(CH₂)_m NHCOR, wherein m is a positive integer of 3 or 4 and COR is the same as above.

28. A gel, consisting essentially of:

a homogeneous mixture of a non-polar organic liquid having a dielectric constant of less than 20 and having a solubility less than 10% by weight in water and 0.05% to 20% by weight of at least one cmpound having the formula ##EQU33## wherein RCO is a C₂ to C₃₀ aliphatic acyl group or an aralkyl acyl group;

R₁ is a C₁ to C₃₀ aliphatic hydrocarbon group or an aralkyl group, and ##EQU34## wherein R₆ is --(CH₂)_m NHCOR, wherein m is a positive integer of 3 or 4 and RCO is the same as above, with the proviso that at least one of R and R₁ is a C₅ to C₃₀ aliphatic hydrocarbon group.

29. A gel, consisting essentially of:

a homogeneous mixture of a non-polar organic liquid having a dielectric constant of less than 20 and having a solubility less than 10% by weight in water and 0.05% to 20% by weight of at least one compound having the formula ##EQU35## wherein RCO is a C₂ to C₃₀ aliphatic acyl group or an aralkyl acyl group;

Z is --NH₂ or --NHR₂, wherein R₂ is a C₁ to C₃₀ aliphatic hydrocarbon group or aralkyl group; and

##EQU36## wherein R₆ is C₁ to C₄ alkyl, benzyl, --CH₂ CH₂ --S--CH₃ or --(CH₂)_p --COZ, wherein p is a positive integer of 1 or 2 and Z is the same as above, or --(CH₂)_m COR, wherein m is a positive integer of 3 or 4 and COR is the same as above, with the proviso that at least one of R and R₂ is a C₅ to C₃₀ aliphatic hydrocarbon group.

30. A gel, consisting essentially of:

a homogeneous mixture of a non-polar organic liquid having a dielectric constant of less than 20 and having a solubility less than 10% by weight in water, and 0.05% to 20% by weight of at least one compound having the formula ##EQU37## wherein RCO is C₂ to C₃₀ aliphatic acyl;

R₅ is a C₁ to C₃₀ aliphatic hydrocarbon group or an aralkyl group; and

Y is C₁ to C₄ alkyl, benzyl or --(CH₂)_m NHCOR, wherein m is a positive integer of 3 or 4 and COR is the same as above, with the proviso that at least one of R and R₅ is a C₅ to C₃₀ aliphatic hydrocarbon group.