Classifications

• • 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
  • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
  • A61K8/41—Amines
  • A61K8/418—Amines containing nitro groups
• • 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
  • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes

Definitions

• This invention relates to novel compounds, dyeing compositions containing the novel compounds, and methods for dyeing keratinaceous material by the use of the nove compounds.
• novel compounds of this invention can be repre- 'sented by the following generic formula:
• R is a hydrocarbon radical free from olefinic and acetylenic .unsaturation having from 1 to about 8 carbon atoms, or a hydroxyalkyl radicalhaving from 1 to 4 carbon atoms; and wherein R is a saturated aliphatic hydrocarbon radical, i.e., alkyl, having from 1 to4 carbon atoms, a hydrozgyalkyl radical having from i to 4 carbon atoms, and R" is hydrogen or hydro x yalkyl having from 1 to 4 carbon atoms, provided that R" is hydroxyalkyl mentioned those wherein: R is a monoliydroxyalkyl having from 1 to 4 carbon atoms and R is an alkyl having from 1 to 4 carbon atoms; R is phenyl and R is an alkyl having from '1 to 4 carbon atoms; R is'a cycloalkyl'having4 to 6 carbon atoms, and particularly 6 carbon atoms and R
• R islan alkyl having from 1 to 4carbon atoms and R is an alkyl having from 1 to 4 carbon atornsyR is phenyl and R is a monohydroxyalkyl having fromx'l to 4 carbon atoms; R is a cycloalkyl having from 4 to 6'carbon atoms, i and particularly 6 carbon atoms and R is a monohydroxyalkyl having from 1 to 4 carbon atoms.
• R' is also hydroxyalkyl and further provided j that at least one of R and 'R' is a hydrocarbon radical.
• the preferred compounds of this invention are those whereinR is ahydrocarbon radical
• propyl isopropyl, butyl, t-butyl, n-hexyl andthelike; cycloalkyl radicals such as those having from 4 to 6 carbon atoms, e.g;, cyclobutyl, cyclopentyl, and cyclohcxyl; the phenyl,"-alkylphenyl or phenalkyl radicals, e.g.,
• benzyl 4-met-hylpl1enyl, 4-ethylphenyl and the like; and lower alkyl substituted cycloalkyl radicals, such as 4- 1-rnethylamino-2-nitro-4-propylaminobenzene; 7'
• i R is a hydroxyalkyl radical
• the alkyl can be methyl, ethyl,
• T hevarious radicals as represented by R'of the generic formula can be alkyl having up-to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, but-yl, t-butyl, andthe tlikeyhydroxyalkyl radicalshaving from I to 4 carbon,
• atoms such as hydroxymethyl, Z-hydroxyethyl, 3-hydroxypropyl, 2,3-dihydroxypropyl and 4-hydroxybutyl.
• hydroxyalkyl is intended to embrace bothmonohydroxy or polyhydroxy substituents, e.g.,- dihydroxy, although it is preferred that when-either R orlR' of generic Formula I is a hydroxyalkyl, it be a monohydro iyalkyl:
• R in Formula I above may be hydrogen or hydroxyall-:yl and has the'value hydroxya'lkyl only when R is also hydroxyalkyl. Moreover, preferably, both R" and R" i are the same hydroxyall ryl group, e.g., hydroxyethyl. t
• the compounds of this inventioni can be produced by reacting a 1-secondaryamino-Z-nitroA-aminobenzene with a reactantor reactants soas to replace at least one of the,
• R can be hydrocarbon radicalsor only one of .R and R 7 need be a hydrocarbon radical.
• the l-secondaryamino-2-nitro 4 alkylaminobenzene compounds of this invention can be produced byreacting'a 1-secondaryamino-2-nitro-4-aminobenzene with an alkylating agent.
• a l-sec'ondaryamino-Z- T nitro-4-aminobenzene e.g., 1 -methy1amino-2-nitro-4-;
• alower alkyl monohydricalcohol about 1,000 parts
• An aqueous solution of a base such as sodium carbonatetabout 30.parts of sodium carbonate, in 180 a parts of water
• a base such as sodium carbonatetabout 30.parts of sodium carbonate
• the mixtureis-then'permitted is then added to the alcoholic solution and the mixtureis-then'permitted to cool to about with a molar excess of sulfuric acid and permitted to remain at a temperature of about 3C. to about 4 C. until thetosyl product is completely dissolved.
• a I-secondaryaminO-Z nitro-4-aminobenzene can be reacted with a halogen substitution product of a'monohydric or polyhydric aliphatic alcohol by refluxing or simply heating above r'oom.
• temperature and in thepresence of an aqueous solution of an acid-binding agent, such as an alkali metal hydroxide, calcium oxide, etc The reaction time can vary from about 4 to 6 hoursQand preferably about 4 hours. ;Generally, molecular proportions of the nitro cornpound and the alcohol reactant are employed.
• the quantity'of the I 'acid binding agent employed is in excess of the theoretical quantity required to neutralize the acid formed, and this excess can var'y from; about 10% to 100%";niore than theory.
• 'The' hydroxyalkyl derivative-of the nitro compound can berecovered by conventional means, such as by boiling toconcentrate the reaction mixture and then salting out by addition; of sodium chloride.
• the precipitate is then filtered.”
• the l-alkylaniino-2-nitr0-4,-tosyl farninobenzene is' then dissolved in r water and sodium hydroxide.
• the solution is cooledto about 1,0? C. and ethylenechlorohydrin about'. 1.25 to.
• the solution is refluxed and an alkylene oxide, e.g., ethylene oxide is bubbled into therefluxing mixture until the mixture has absorbed the desired molar quantity of the alkylene oxide, e.g., .2 moles of ethylene oxide per mole of the nitro compound when it is desired to produce the bis-hydroxyp
• an alkylene oxide e.g., ethylene oxide
• ethylene oxide e.g., ethylene oxide
• the 1-secondaryamino-2-nitro-4-[bis-. (hydroxyalkyl)amino] benzene is thenrecovered by, conalkyl derivative.
• the 1-secondaryamino-2-nitrd4-[bis(hydroxyalkyl)amino]ben zene compounds can be prepared by bydroxyalkylating an appropriate l-secondaryamino-Z-nitro- .'4-aminobenzene in the presence of an aqueous sodium hydroxide solution. 7 p
• One process forthe reduction of the 1-secondaryamino,-2;4-dinitiobenzene to the corre 1 sponding 1l-secondaryamino-Z-nitroa4aminobenzene is by introdueing about 3 moles of hydrogen into a hydrogena tion apparatusmaintained at about 25 to 70 C.
• novel compounds of this invention have utility for dyeing keratinaceous materials and particularly living human hair.
• dyes possess many advantageous properties.
• they havea pronounced atfinity for the hair; they exhibit a good dyeing union with both normal and permanently waved hair, particularly gray hair; they give a wide spectrum of colors, such as that of bluish-red over a violet to a blue and when used in combination with known dyes, they can easily produce various blonde to brown shades; they lose little color upon shampooing; have good lightfastness and rubfastness; they produce bright and lusterous shades; they have good storage stability; and do not stain the scalp.
• a further advantage is that they do not require the use of the conventional peroxide additives, e.g., hydrogen peroxide, for color formation or fixation to the hair.
• the conventional peroxide additives e.g., hydrogen peroxide
• the prior art describes certain nitro derivatives of p-phenylene diamines as hair dyes, the prior art p-phenylene diamines do not have two secondaryamino groups wherein at least one of the secondaryamino groups carries a hydrocarbon radical.
• the compounds of the instant invention have many advantageous properties over the prior art compounds, and particularly in the range of colors produced; good dyetake at pH values of 7 to about 9; uniformly of dyetake between permanent waved parts of the hair and non-permanent waved parts of the hair; the ability to be removed more easily from the hair by special treatments; and improved lightfastness, rubfastness and washfastness.
• the dyeing compositions of this invention comprise neutral or alkaline aqueous solutions of the novel compounds.
• the compositions can also contain the conventional ingredients found in dyeing compositions, such as organic solvents for the dye, thickeners, detergents, gums and the like.
• Alkalizing agents are ordinarily added to the compositions, since the pH of the dyes varies from that of weakly acidic to about neutral.
• the dyeing compositions of this invention can be applied to keratinaceous materials by the conventional techniques used in the art.
• the compositions when applied to living hair on the human head, the compositions can be applied to the hair with a brush, sponge, or other means of contact, such as dipping until the hair is properly saturated with the composition.
• the reaction time or time of contact of the dyeing composition with the hair is not critical and can vary over the wide range used in the hair dyeing art such as periods of about 5 minutes to about 2 hours, and preferably from about minutes to about 60 minutes.
• the dyeing temperature can vary over wide limits as is conventional in the art. Thus, the dyeing temperature can vary from about room temperature, e.g., about C. to above about 60 C. and preferably from about 20 C. to about 45 C.
• the dyeing compositions of this invention can be prepared by the conventional methods used in the hair dyeing art. Thus, they can be prepared by dissolving or dis persing the dye in water of the desired concentration.
• Water miscible organic solvents can be employed to facilitate solution of the dye; in this event, the dye can be dissolved first in the solvent and then diluted with water.
• the organic solvents which can be used there can be mentioned: the lower alkyl monohydric alcohols, such as ethanol or isopropanol; lower aliphatic dihydric alcohols, e.g., propylene glycol; various polyhydric alcohols; ketones; and esters.
• the dispersion of the various ingredients can also be facilitated by addition of a detergent or dispersing agent, such as lauryl or myristyl sulfate or sulfonate.
• a detergent or dispersing agent such as lauryl or myristyl sulfate or sulfonate.
• the water miscible organic solvents employed to facilitate solution of the dye can vary from about 1% to about 30% by weight of the composition, and preferably from about 2% to about 10%.
• the detergent or dispersing agent can vary from about 1% to about 30% by weight of the composition.
• Any water-soluble alkalizing agent that will not interfere (i.e., is compatible) with the dye employed, and will not precipitate the dye or introduce any possibility of toxicity under the conditions of use, or injure the scalp or hide of the pelt, at its ultimate concentration in the composition to be applied to the keratinaceous material, can be used.
• a preliminary test of some selected alkalizing agent can be made to note its compatibility with the dye or to introduce possibility of toxicity or injury.
• Ammonium hydroxide because of its freedom from toxicity over a wide concentration range and its economy is an acceptable alkalizing agent.
• any other compatible ammonia derivative alkalizing agent such as a lower alkanolamine, such as mono-, dior triethanolamine, or alkyl amines or alkylenediamines, such as monoethylamine, diethylamine, propylarnine, dipropylarnine or propylene diamine or a heterocyclic amine, such as morpholine.
• any of these ammonia derivative alkalizing agents as well as ammonium hydroxide may be broadly referred to as an ammonium alkalizan
• any alkaline earth hydroxide for example, calcium hydroxide or magnesium hydroxide, can be used up to the limit of its water stability and at any concentration that fails to produce a precipitate with any of the components of the composition.
• the dissolved alkaline earth hydroxides are preferred over the alkali metal hydroxides, such as sodium hydroxide, or potassium hydroxide, or carbonates, such as sodium carbonate and bicarbonate, any of which can also be used so long as their ultimate concentration in the final dyeing solution is below that which might possibly irritate the scalp, or injure the hide of the fur pelt.
• the quantity of the various ingredients in the dyeing compositions of this invention can vary over a wide range.
• the novel dyes of this invention can be employed in the conventional concentrations used in the dyeing of the various keratinaceous materials.
• tinctorial- 1y effective quantities can vary from less than about 0.01% to greater than about 10% by weight of the aqueous solution.
• concentration of the dye will preferably vary from about 0.05% to about 5% by Weight of the aqueous solution, and particularly from about 0.1% to about 3%.
• Any selected compatible alkalizing agent should be used to give .a pH of about 7 or 7.5 to about 12, and preferably a pH of about 7.5 or 8 to about 11.
• the quantity of the alkalizing agent employed can vary over a wide range depending on the dye and particular alkalizing agent employed.
• the alkalizing agent can vary from less than about 0.1% to about 5% and preferably from about 0.5% to about 2% by weight of the aqueous solution.
• the water content of the composition is ordinarily the major constituent and can vary over a wide range dependent in large measure on the quantity of other additives, such as solvents.
• the dyes of this invention are water dispersible in the usual generic sense as embracing true solutions of the dyes in water or any aqueous medium within the bounds of the invention, as well as stable homogeneous colloidal solutions of them in such aqueou medium.
• the aqueous medium includes the aqueous alkaline medium. It includes also any aqueous medium containing, for example, a sufl'icient amount of a compound, e.g., ethanol employed as a common solvent to enhance the solution of the dye or some other organic material.
• the compositions can be formulated as solutions, gels, emulsions,
• EXAMPLE 1 Preparation .of I-(Z'Jzydroxyethyl) amino-2-nitro-4- methylaminobenzene Sixty parts o-f 1-(2-hydnoxyethyl)arnino-2-nitro-4- aminobenzene were dissolved at 60 C. to 70 C. in 1,000 parts of methanol. An aqueous solution of 30 parts of sodium carbonate in 180 parts of water was then added to the methanolic solution. After cooling the mixture to C., 25 parts of dimethyl sulfate was added dropwise. The mixture wasthen boiled.
• the mixture was permitted to reflux for an additional 0.5 hour and then steam distilled, cooled, and the l-cyclohexylamino-Z-nitro-4-(2'-hydroxyethyl)aminobenzene was extracted from the reaction mixture with ethyl acetate.
• the ethyl acetate extract was heated to evaporate the ethyl acetate to leave the product as bluish-purple crystals.
• dinitroaniline also referred to in this specification as lphenylamino-Z,4-dinitrobenzene
• dinitroaniline also referred to in this specification as lphenylamino-Z,4-dinitrobenzene
• additional 80 ml. of isopropanol 20 grams of a 50% aqueous solution of H 30
• Theternperature of the reaction mixture was brought up to about 65 C. andthen there was introduced into the reactor at a pressure of 50 to 40 psi. about .303 gram (0.15 mole) of hydrogen over a period of 17 minutes.
• the temperature of the reaction mixture at the end of the 17 minute period was 52 -C.
• reaction mixture was permitted to cool, the autoclave was opened and the sulfate salt or" 1-phenylamino-Z-nitro-4-aminobenzene which was produced by the hydrogenation was filtered oil as a precipitate.
• the sulfate salt was subsequently alkalized and separated to obtain the l-phenylamino-2-nitro-4- aminobenzene as red crystals.
• N-(2-hydroxyethyl)2,4-dinitroaniline also referred to in this specification as 1-(2'-hydroxyethyl)amino-2,4-dinitrobenzene, in 150 ml. of ethanol.
• This reaction mixture was hydrogenated at a pressure of 50 to p.s.i. and a temperature of 60 C. After absorption by the reaction mixture of 0.3 mole of hydrogen, the apparatus was permitted to cool.
• the yellow hydrochloric acid salt of 1-(2-hydroxyethyl)amino-Z-nitro-4-aminobenzene was separated from the catalyst by dissolving in hot water.
• the free base 1-(2hydroxyethyDamino-Z-nitro-4- of monoethanolamine, l gram of triethanolamine, 1 gram.
• T0 EXAMPLE 12 By employing the procedure and composition, including the various quantities of ingredients except for the substitution of the following dyes .in place of the lmethylamino 2-nitro-4-(2'hydroxyethyl)aminobenzene of Example 11 there are produced the following colors on gray hair: l-(2'-hydroxyethyl)amino-2-nitro-4-methylaminobenzene produces a blue color; l-methylamino- Z-nitro-4-methylaminobenzene produces a reddish purple color; 1 methylamino-2-nitro-4-[bis(2'-hydroxyethyl) amino1benzene produces a blue color; l-phenylamino-Z- nitro-4-(2-hydroxyethyl) aminobenzene produces a violet color; and 1-cyclohexylarnino-2-nitro-4-(2-hydroxyethyl) aminobenzene produces a violet color.
• the mixture was then cooled and 100 grams of sodium chloride was added to the mixture to salt out the l-methylarnino- 2-nitro-4-[bis(2'-hydroxyethyl)amino1benzene as blue crytals. The mixture was then filtered to recover this glycol derivative.
• aminobenzene was obtained by neutralizing the salt with 1 then applied to gray hair. After about 20 minutes, the aminobenzene was obtained by neutralizing the salt with 1 then applied to gray hair. After about 20 minutes, the aminobenzene was obtained by neutralizing the salt with 1 then applied to gray hair. After about 20 minutes, the aminobenzene was obtained by neutralizing the salt with 1 then applied to gray hair. After about 20 minutes, the aminobenzene was obtained by neutralizing the salt with 1 then applied to gray hair. After about 20 minutes, the
• R is a member selected from the group cnsisting of non-olefinic and non-acetylenic hydrocarbon and havingv from 1 to vabout 8 carbon atoms, and hydroxyalkyl having from 1 to 4 carbon atoms; and R' is a member selected from the group consisting of saturated aliphatic hydrocarbon having from l to 4 carbon atoms and hydroxyalkyl having from 1 to 4 carbon atoms and 'R is selected from the group consisting of hydrogen and hydroxyalkyl having from 1 to 4 carbon atoms, provided that R is hydroxyalkyl only when R is also hydroxyalkyl and further provided that at least one of R and R is hydrocarbon; and a suflicient quantity of an alkalizing agent to give the aqueous solution a pH of about 7.5 to about 12.
• composition of claim 1 wherein both R and 'R of the formula are alkyl having from ,1 m4 carbon
• R represents monohydroxyalkyl having from 1 to 4' carbon atoms and R is hydrogen.
• composition of claim l whereinlR of the formula represents alkyl having from 1 to 4 carbon atoms and R and R are the same hydroxyalkyl 5.
• composition of claim 1 wherein R -off-the formula represents alkyl having from 1 to 4 carbon atoms and R and R" represent the same hydroxyethyl.
• composition of claim 1 wherein R is monohydroxyalkylhaving from 1 to 6 carbon atoms; R is an alkyl having from 1 to 4 carbon atoms and R is hydrogen; p
• a hair dyeing composition for living human hair comprising an aqueous solution containing from about 0.1% to about 3% by weight of a p-phenylene diamine represented by the following formula:
• JI-lTl-R ' from the group consisting of saturated aliphatic hydrocarbon having from 1 to 4 carbon atoms and hydroxyalkyl having from 1 to 4 carbon atoms and R is selected from the group consisting of hydrogen and hydroxyalkyl having from 1 to 4 carbon atoms, provided that R is hydroxyalkyl only when R is also hydroxyalkyl and fur- 'ther provided that at least one of R and R is hydrocarbon;
• composition of claim 11 wherein the p-phenyl- ,ene diamine is 1-methylamino-2-nitro-4-(2-hydroxyethyl) aminobenzene v 13.
• the composition of claim 11 wherein the p-phenylene diamine is 1-(2-hydroX yethyl)-2-nitro-4-methylaminobenzene.
• composition of claim 1 1 wherein the p phenyl- ,ene diamine is 1-methylamino-2-nitro 4-methylaminobenzene.
• 7 15 The composition ofclaim 11 wherein the p-phenylene diamine is 'l-phenylamino-2-nitro-4-(2-hydroxyethyl) aminoben'z ene.
• composition of claim ;11 wherein the p-phenylene diamine is 1-methylamino-2-nitro-4-[bis(2-hydroxyethyl)amino]benzene.f f I s 1 17.
• the composition of claim 11 wherein the p-phenylene diamine is 1-cyc1ohexylamino-2-nitro-4-(2-hydroxyhexyl and R is monohydroxyalkyl having'from'I to 4 7 carbon atoms and R is hydrogen.
• aqueous solution varies from about 8 to about 11.
• a hair dyeing composition for living human hair 3 B a r-R I sis-ting of nori-olefinic and'non acetylenic hydrocarbon having from 1 to about 8 carbon atoms, and hydroxy-;
• R is a member selected fro'm the group consisting of saturated aliphatic hydrocarbon having from 1' to 4 carbon'atoms and hy-f' droxyalkyl having from 1 to 4 carbon atoms and R" is selected from the'group consisting' oflahydrogen andhydroxyalkyl having from 111014 carbon atoms, proethyl) aminobenzene.
• a proc'essfor dyeing living human hair which comprises applying thereto a tinctorially effective quantity of an aqueous solution; containing a p-phenylene diamine 7 V 1 derivative represented by the following formula: 9.
• the composition of claiml wherein the pH of the w a Y wherein R is a member selected from ,thegroupco nsist- 3 ing of non-olefinic and non acetylenic hydrocarbon'havwherein R is a member selected from tthe group con-V ing from'l to 8 carbon atoms; and hydroxya'lkyl having from l te carbon atoms;' Rziis a member selectedfro'm the group consisting of; saturatedaliphat-ic hydrocarbon I having from 1 to 4 carbon atoms and hydroxyallgylhavmg from 1 to 4 carbon atoms and R. is" selected from the group consisting of hydrogen and hydroxyalkyl havf,
• R is hydroxyallgyl-only when R is 'alsoj hydroXyalkyl and fur- 7 there provided that at least one of R and R is hydrocarbon; and a suflicient quantity of an alkalizing agent to I impart'apH of from aqueous I solutipn.
• R and R are alkyl having from 1 to 4 carbon atoms; and a suflicient quantity of an alkalizing agent to impart a pH of about 7.5 to about 12 to said aqueous solution.
• R is alkyl having from 1 to 4 carbon atoms and R is monohydroxyalkyl having from 1 to 4 carbon atoms; and a sufficient quantity of an alkalizing agent to impart a pH of about 7.5 to about 12 to the said aqueous solution.
• a process for dyeing living human hair which comprises applying thereto a tinctorially elfective quantity of an aqueous solution containing a p-phenylene diamine derivative represented by the following formula:
• R is alkyl having from 1 to 4 carbon atoms and R and R are the same hydroxyalkyl having from 1 to 4 carbon atoms; and a sufi'icient quantity of an alkalizing agent to impart a pH of about 7.5 to about 12 to the said aqueous solution.v a
• R is alkyl having from 1 to 4 carbon atoms; and a suflicient quantity of an alkalizing agent to impart a pH of about 7.5 to about 12 to the said aqueous solution.
• R is monohydroxyalkyl having from 1 to 4 car- 1 diamine derivative bon atoms and R is alkyl having from 1 to 4 carbon atoms; and a sufficient quantity of an alkalizing agentto impart a pH of about 7.5 to about 12 to the said aqueous solution.
• a process for dyeing living'human hair which comprises applying thereto a tinctorially effective quantity of an aqueous solution containing a p-phenylene diamine derivative represented by the following formula:
• R is monohydroxyalkyl having from 1 to 4 carbon atoms; and a sufiicient quantity of an alkalizing agent to impart a pH of about 7.5 to about 12 to'the said aqueous solution.
• a process for dyeing living human hair which comprises applying thereto an aqueous solution containing from about 0.05% to about 5% by weight of p-phenylene diamine derivative having the formula:
• R is a member selected from the group consisting of non-olefinic and non-acetylenic hydrocarbon and having from 1 to about 8 carbon atoms, and hydroxyalkyl having from 1 to 4 carbon atoms;
• R is a member selected selected from the group consisting of hydrogen and hydroxyalkyl having from 1 to 4 carbon atoms, provided that R" is hydroxyalkyl only when R is also hydroxy alkyl and further provided that at least one of R and R is hydrocarbon; and a suflicient quantity ofan ammonium alkalizant to impart a pH of about 8 to about 11 to said aqueous solution; and wherein the Said aqueous solution is at a temperatureof about 20 C. to about 45 C.
• R is a member selected from the group consisting of non-olefinic and non-acetylenic hydrocarbonv having from 1 to 8 carbon atoms, and hydroxyalkyl having from 1 to 4 carbon atoms; R is a-member selected :from the diamine derivative is 1-(2"hydroxyet hyl)amino-Z-nitro- References Cited by the Examiner FOREIGN PATENTS 741,334 11/55 Great Britain.

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Citations (1)

• 0
  • FR FR1310072D patent/FR1310072A/fr not_active Expired
• 1964
  • 1964-06-12 US US374562A patent/US3168442A/en not_active Expired - Lifetime
• 1965
  • 1965-01-08 FR FR1232A patent/FR85850E/fr not_active Expired

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