DE1619651A1 - Coloring process - Google Patents

Description

PATENT LAWYERS

DR. ING. A. VAN DER WERTH DR. FRANZ LEDERER

HAMBURG-HARBURG 8- MQNCHEN 8

WILSTORFER STR, 32 - TEL. 10411) 7708 61 LUCII.E-GRAHN-3TR. 22 - TEL. (081 (1 44 OS 4ft ~

Monks «the P / J

Applicant; Unilever HoVn. Mueetimiaark 1. Rotterdam, Holland »

Dyeing process

The present invention relates to a dyeing method and a coloring agent, in particular the coloring of keratinous

In the current patent application XS 1194O ₉ I? C / 8m, a process of coloring keratin material is described, where the keratin material is colored by means of a complex cation "which contains the ohromophoric grouping consisting of a five-membered ring". Hing contains a transition metal atom, two adjacent carbon atoms, £,? $! Nitrogen atoms and conjugated double bonds, where the two nitrogen atoms are connected to the Hetellatom. The colored complex cation thus contains the grouping

where Jl is a transition metal "

109828/1862

BATH

It has now been found that a particularly advantageous Group of complex cations sum staining of keratin material within the already ongoing in the above Patent application designated class of cations are those »which between cobalt ions and the group

containing ligsades are formed, where H ¹ and C ^{1 are} ropes of a ¹ heterocyclic ring (sB "a pyridine ring or a® Qhinolinringea)" This group of complex cations was found to have unusually good L AXkalibe bond to "Alkaline solutions of this grain" ™ know plexkationexi Can be kept for a relatively long period of time and therefore you do not need to prepare them just before use

Ligands containing the above grouping can be the general formula

possess, in which H 'and G form part of a heterocyclic ring "R ^ hydrogen, an alkyl group which contains 1 to 4 carbon atoms (e.g. a methyl" - * ethyl or tertiary butyl group), a phenylalkyl group, w i " which the alkyl component toriug & welee contains 1 to 4 carbon atoms, * or a phenyl group ©, Br is one and E * W * »sa * etaff or H ² and & * with the carbon and nitrogen atoms lying there is a heterooyollseed ring, B ₀ Eizi "n pyridine, quinoline barren Ghlnozalinring) form _o When the group R consists of a phenyl group or it contains the Phenylgrupp may contain" substituents sB * _e nitro Asino-, halogen, hydroxy, cyano, alkoxy - or alkyl groups (preferably with 1 bla 4 carbon atoms) «Substituents such as ζ · Β _β the just mentioned kHnn @ m also in the H and O 'aamming heterocyclic ring

109828/1962

- sv.V 1615551

or la that heterocyclic fiing be included, softer formed with the participation of groups R and H ^ can be" .

In the following _table: -? Stir examples cited Mganden, which can form the alkaXibestänüigen RoffiplesJfestionen used Ahren in the novel he <f η The colors of Blskompleacionen which are formed by reaction of these ligands with cobalt (II) ions, just fall are given . The formulas of various of these ligands are given on the attached formula sheets.

-. '.. "'. - Table ''"'-' .. "■ - ■■■■ -

Ligand '''

According to formula I, but under ISreatB the methyl flu by one of the following groups: ^ - I ^ / "λ ^; ^

4-Hitroph0nyl - deep

4-aminophenyl ~

3-Hitrophenyl ■ ':: ■ ._:; .- ^y '; ~ ' 4-cmorphenyl ^: _- ^: -:> - "; ^ ~ ■

terto butyl. ■■■ " - ■ ■■,. ■. / ^ ^: ...--- X- ** ..-

Bensyl -. ■ -.V _- '■■ /. ": ■;.'; ■ V- - _.: "; ** -i

y ^
2 _f 3-ßiaca-1-propene

i- (4-Sitoophenyli- (2pyrdyi} ^ C5-nitrö ^ 2 «pyridyl) -2,3-dia3a-1« »prppen IfI Imrguniörfarbenig 4- (a ^ yridyl} -2- (2-quinolyl) -3 _# ... 4-aiaga-2-butene """;., ^i:::; V _V y '" ■ - Vt

According to formula IV _S but with replacement of the methyl group by one of the groups listed below * -

.- ■ '■■: hydrogen \ ■' ■ "■" ■■■. '.- ^ ^-. *>:

ORlQiHAL IMBPECTisD

4- (4-3? Henyl-2-pyridyl) «2- (2-quinolyl) 3,4-diaza-2-butene

1,3-di (2-quinolyl) -2,3-diaza-1-propene

5-imino-2- (2-pyrldyl) -3, 4 , 6-triaisa-2-hexene

According to Formula VII ₅ , but with the methyl group replaced by one of the groups listed below:

hydrogen
Phenyl

3-nitrophenyl
4-nitrophenyl

5-Iminp-2 ~ (2-ehinolyl) -3 , 4-6-triaza-2-hexene

According to formula VIII _5, however, with replacement of the methyl group by hydrogen

2- (2 ~ pyridyl) -4- (2-quinoxalyl) -3,4-, diaza ^ -ijutene

V pale purple

VI purple

VII yellow

light yellow orange-yellow pale yellow pale yellow

VIII yellow

orange

IX burgundy

According to formula IX, but with replacement of the Methyl group through one of the groups listed below:

hydrogen
4-aminophenyl

burgundy colored violet

The ligands mentioned above can be prepared, _n ZOB by known methods by heating a mixture of the appropriate aldehyde or ketone and a slight stoichiometric excess of the appropriate hydrazine derivatives short period of time in a suitable solvent 2.Bο ethyl alcohol or dimethylformamide, under reflux "An aqueous Solution of the required ». Amount of eiixos cobalt (II) salt, preferably des & obalt (IX) nifct? Ate _r wii * d then added to the Ke & ktionemedluni to form the bite complex

Irami duuren in a purer form received swrffl; don ligcmden mm atm ι an allrohoH

1 0 9,028 / 19Π?

That
become, - dpß

forms and mixes this with an aqueous solution of a cobalt eel _o

The Keratiniaateriäl can with these complex cations through the various methods that are described in the patent application already in progress mentioned at the beginning In view of the good alkali resistance of these complexes, they are not suitable for application Keratin material from aqueous solutions with a pH of 8 to 12 or even higher is particularly suitable «In particular, they can be applied to human hair from solutions with a pH of about 10 to 11 can be applied,

The present invention also relates to compositions suitable for coloring keratin material and especially human hair on the head, and these compositions essentially consist of an aqueous alkaline solution of the above alkali-resistant cobalt-containing complex cations and a surface-active agent and / or a thickening agent *

The surfactant can be an amphoteric or nonionic a _o A'in Examples of amphoteric include those sold under d 'sm Handelsnaiien "Mlranol" surfactants., Nichtionischea examples? surfactants eind fatty ₉ Alkyleao2fyd ~ (^ Äthyleno yd ~ or Propylenosyd - = ») - condensates a hydrophobic base as ss.B _e © ines laagkettigen fat" alcohols ₉ of alkylphenols or lettsäurealkanol »· amidoß, and amino xydt ,, z _e B _o bis (2 ~ hydro ^ ethyl) -alkylamlnoxyd with lauryl or d © r Myrlßtyigruppe as the alkyl group, "the amount of surfactant may vary over a wide range ^ z" B "of O ₉ 25-15 Sewo ^ the composite,

The thickener can be selected from the number of those commonly used in preparations, but it must of course be one that is used with the grain

10 8828/1962

plexcations is compatible _o Examples of suitable nonionic thickeners are derived from cellulose, aB ₀ hydroxyethyl «· and hydroxypropyl cellulose and cellulose ethers, as well as Äthylenoa & konaensate τοη cetyl and stearyl alcoholo The amount of the thickener can vary over a wide range, for example, from 0 ₉ 1 up to 10 wt, # of the composition *

The composition will usually _{contain at least 0 9} % by weight of the cobalt complex as a mixture or a mixture of such salts. The actual amount used will depend on the desired coloring effect. "

^ The composition can, if necessary, be diluted with water _{9 before decomposition.}

It has also been found that the above cobalt-containing Complex cations have relatively good resistance to hydrogen peroxide. «This property makes them suitable for use in hair lightening products «Sol» Before products are formed, just before use, hydrogen peroxide solution is mixed with an alkaline solution Solution one? or more of the above cobalt-containing complex cations mix o

^ To illustrate the proof of good alkali resistance Ility of the cobalt-containing ones used according to the invention Complex running solid selenium listed the following:

Alkaline solutions (pH about 11) of Bi & £ * 4 ■ imino-1- (2-pyridyl) -2.3 _f 5-trlaaa - 1-> pentenf-cobalt nitrate and Bi s - / * 4-imiao - 1 * (2 «ohlnolyl) -2,3» 5 -triaza-1 «pent en] » cob al nitrate (the ligands of the complexes are therefore similar to those of formulas VII and VIII, but the methyl groups are replaced by hydrogen atoms) arranged., The solutions were ^{stored at 15 °} C. and 37 ^° C. for 6 months. Even after this long storage, there was no noticeable change in the color of the solutions

109828/1962

Under alkaline conditions, the Bißkomplexe used in the invention of! Cobalt-resistant and retain their ITST ionic characters Mb is assumed that in these Eomplesen a proton you the secondary ümino "group of the '.PridentatJ & este removed and that the _co-e baltatom to Og ^{4" 4} "* is oxidized"

The following examples explain the invention in more detail «

Example t

A thickened aqueous solution of bis ~ £ ~ 2,4 di- (2 ~ pyridyl) ~ 3 β 4 ~ diaza-2 '' but8nJ ~ _f kobaltnitret was prepared by O _5, 6 Gewichtoteile this complex salt in 99 weight _f A '

share a Hisohung solved what €

1p3 wt “# hydroxyethyl cellulose

2.0 " ⁿ Nonylphenol-9-E0 (1Mol Konylphenol» 9Mole Ethylene Oxide Condensate)

O ₉ 2 "" perfume

0.2 ⁿ "propyl ester of p-hydroxybenzoic acid 96.3""Water

contained "The pH of the solution was mixed with 10 #iger sodium 'hydroxide solution to a value swieehen 11 and 12 is""presented -Sine small blonde hair tress was 10 minutes immersed in the alkaline solution of the complex ₉ ^ rinsed because, gewasoKe» _f again rinsed and dried

The strands of hair had turned a red hue, ([

The complex used in this example was Bi8 ~ £ * 1 · »(e-methyl-Z ^ py ^ ifly!} -3» ^ »pyridyl )« * 2 _t 3 ~ aia8a-1 «propei» liobaltnitrato Xm the rest was that Example 1 repeated. The strand of hair had a red shade of belroramon,

B (Example 1 was repeated with the exception of deaseiip that dae

ppjt was The lock of hair he-fcte βλ JPb

BATH

Example 4

The complex salt used was bis ~ £ 4- (2-pyridyl) ~ 2 ~ (2 ^ hinolyl) -3 »4 ~ dia2! A-2 ~ buten3 ~ cobalt nitrata Ia other Example 1 was repeated. The strand of hair had a purple hue »

Example ft

Example 1 was repeated except that the complex salt used Bi8- £ 4- (4-phenyl ~ 2-pyridyl) ~ 2 »- (2-ohinolyl) -3» 4-diaza-2-butenJ-cobalt nitrate was «The The lock of hair had turned a pale purple hue

Example 6

Example 1 was repeated except that the complex used was used as Bie {'i, 3-cli (2-quinolyl) -2,3-diaj! A-1 * propenj-cobalt nitrate was «The strand of hair had« turned a purple hue ·

Example 7

Example 1 was repeated, with the exception that the complex salt used was Bi- _i f5-imino-2- (2-pyridyl) -3 _> 4 »6- · trifiH5a-2-hexenJ-cobalt nitrate« The lock of hair had a green- get yellow hue «

Example 8

The complex sale used by Bae was bis ~ f5-imino * -2- {2 «ehinolyl) ~ 5f4 # 6-trieusa-2-hexen2-kobaltnitrato Incidentally, that was Example 1 repeated »The strand of hair had got a yellow hue *

Example 9

A thickened aqueous solution of Bis-f2-C 2-pyridyl) -4-C 2 ^ quinoxalyl) -5,4-diaza-2-butene / cobalt nitrate imbereltet »iMem one 0.4 parts of this complex * in §§ »$ weight parts of a mixture dissolved that

2Ö / 1962

1,8 & ew »# hydroxyethyl cellulose 2.0 "" Konylpbenol-9-BO 0.2 "" perfume

\ 0.2 " ⁿ propyl ester of p-hydroxybenaoic acid 95.8 ^tt * water

contained. The pH of the solution was increased with 5.4% monoethanoiamine solution Mne of blonde hair set to a value between 10 and 11 was added to the alkaline solution of the complex immersed for 10 minutes and then rinsed, washed, rinsed and again dried * The lock of hair had a burgundy color Get color «

109129 / tsta

Claims (1)

Munich, July 14, 1967. Claims Method of dyeing keratin material, characterized in that the karatin material is by means of a Somplexkations is colored, which between a Cobalt ion and a ligand forming the grouping ^ "* - Cs = N-HH-GsN- contains, in which N ¹ and 0 form files of a heterocyclic ring « Method gen & S claim 1 * characterized » that the ligand has the general formula be a fact in which H ¹ and C ^{1 form} parts of a heterocyclic ring, H ^{1 is} hydrogen, an alkyl group, a phenylalkyl group or a phenyl group, B ^{2 is} an amino group and R ^{5 is} hydrogen or R ² and R ⁵ cusaasen alt the deewisohen lying hollow * material and nitrogen atoms »· 1η · η h # t» rooyoli »form the top ring. Method according to claim 2, because in the general formula H ¹ and G ^{1 form} parts of a pyridine or ohinoline ring, H ¹ hydrogen _f tin alkyl group it % to 4 carbon atoms or a B # nsyl or Phenyl group means "R ^{2 is} an amino group and R * is waaeeretoff or R ² and R ³ " use the intervening carbon and nitrogen atoms a pyridine, chlorine, or glynoxaline ring BATH ORIGINAL 108138/1902 Method according to one of Claims 1 and 3 characterized in that the Keratinjaaterlsl Treatment with an aqueous alkaline * dea complex cation colored 5. The method according to claim 4, characterized in that that the alkaline solution has a pH of 8 to 12. 6 »Method according to any one of the preceding claims, characterized in ₉ that the keratinous material is human hair» 7. Means of exercising the procedure according to one of the Claims 1 to 6, thereby kemiEeiT-hnet »that it ia essentially from an aqueous alkaline solution the complex cation and a surfactant and / or a thickening agent. 8. Means according to claim 7, characterized gekennzp Ichnet ^ that the Eobalt complete as »Wölitfees ditt returns, in a quantity * οη at least -0, 9. Means according to claim? Or B ₁ net that it contains 0.20 to 15 wt _o ^. # b © rfltoteeaa & li ^ i - means 10 * means according to one of the methods? bie known that it was $ 1 / $ 10 11 "Hair dye aiittal, dftdit ^ ch «Iner wäserigec ^r ümos exists, which da @ kfttion according to» iasm Ä «3T: - # Äsp3pt © li. ©! "% is" 3 -."/'" BATH 1O882JB / 1902 ft * H H I. I. C = ~ Ν = Ν - CH3 H NH I ^J I Il = N, C -NH2 f \? ^H3 N N NH2 IX ^ CH ₃ .JC = N- 109828 / 1.962 8 m 1-01 AT: ' "η 9 3? 8/1 0 6 2