阅读说明：本技术 含有有机c1-c6烷氧基硅烷的毛发处理试剂的制备方法 (Process for preparing hair treatment agents containing organic C1-C6 alkoxysilanes ) 是由 T·莱希纳 C·罗尔 A·瓦尔特 C-P·蒂西斯 于 2020-01-08 设计创作，主要内容包括：本发明涉及一种制备用于处理角蛋白材料特别是人类毛发的试剂的方法,包括下述步骤：(1)一种或多种有机C-(1)-C-(6)烷氧基硅烷与水在20-70℃温度下的反应,(2)在20-70℃温度下从反应混合物中完全或部分除去通过步骤(1)中的反应释放的C-(1)-C-(6)醇,(3)任选地添加一种或多种化妆品成分,和(4)将制剂填充到包装单元中。(The invention relates to a method for producing an agent for treating keratin materials, in particular human hair, comprising the following steps: (1) one or more organic C 1 ‑C 6 Reaction of alkoxysilanes with water at temperatures of 20 to 70 ℃, (2) complete or partial removal of the C liberated by the reaction in step (1) from the reaction mixture at temperatures of 20 to 70 ℃ 1 ‑C 6 Alcohol, (3) optionally adding one or more cosmetic ingredients, and (4) filling the formulation into a packaging unit.)

1. a process for preparing an agent for treating keratin materials, in particular human hair, comprising the following steps:

(1) one or more organic C₁-C₆Reacting alkoxy silane with water at the temperature of 20-70 ℃,

(2) partially or completely removing C released by the reaction in step (1) from the reaction mixture at a temperature of 20-70 deg.C₁-C₆The alcohol is added into the mixture of the alcohol,

(3) optionally adding one or more cosmetic ingredients, and

(4) the formulation is filled into a packaging unit.

2. The process according to claim 1, wherein in step (1), one or more organic C's of formula (I) and/or (II)₁-C₆The reaction of the alkoxysilane with water is carried out,

R₁R₂N-L-Si(OR₃)_a(R₄)_b (I)

wherein

-R₁、R₂Independently represent a hydrogen atom or C₁-C₆An alkyl group, a carboxyl group,

l is a linear or branched divalent C₁-C₂₀An alkylene group or a substituted alkylene group,

-R₃、R₄independently of one another represent C₁-C₆An alkyl group, a carboxyl group,

-a, represents an integer from 1 to 3, and

b represents an integer of 3-a, and

(R₅O)_c(R₆)_dSi-(A)_e-[NR₇-(A')]_f-[O-(A”)]_g-[NR₈-(A”')]_h-Si(R₆')_d'(OR₅')_c' (II),

wherein

-R₅、R₅'、R₅”、R₆、R₆' and R₆"independently represents C₁-C₆An alkyl group, a carboxyl group,

-A, A ', A ", A'" and A "" independently represent a divalent C, linear or branched₁-C₂₀An alkylene group or a substituted alkylene group,

-R₇and R₈Independently represents a hydrogen atom, C₁-C₆Alkyl, hydroxy C₁-C₆Alkyl radical, C₂-C₆Alkenyl, amino C₁-C₆Alkyl or a group of the formula (III),

-(A””)-Si(R₆”)_d”(OR₅”)_c” (III),

-c, represents an integer from 1 to 3,

-d represents an integer from 3 to c,

-c' represents an integer from 1 to 3,

-d 'represents an integer from 3 to c',

-c' represents an integer from 1 to 3,

-d "represents an integer from 3 to c",

-e represents 0 or 1,

-f represents 0 or 1,

-g represents 0 or 1,

-h represents 0 or 1,

-with the proviso that at least one of e, f, g and h is not 0.

3. The process according to any one of claims 1 or 2, characterized in that in step (1), one or more organic C's of formula (IV)₁-C₆Alkoxysilane with waterThe reaction is carried out in the presence of a catalyst,

R₉Si(OR₁₀)_k(R₁₁)_m (IV),

wherein

-R₉Is represented by C₁-C₁₂An alkyl group, a carboxyl group,

-R₁₀is represented by C₁-C₆An alkyl group, a carboxyl group,

-R₁₁is represented by C₁-C₆An alkyl group, a carboxyl group,

-k is an integer from 1 to 3, and

-m represents an integer 3-k.

4. A method according to any one of claims 1 to 3, characterized in that

(1) One or more organic C₁-C₆The reaction of the alkoxysilanes with water in the reaction vessel or reactor is preferably carried out in a double-walled reactor, a reactor with an external heat exchanger, a tubular reactor, a reactor with a thin-film evaporator, a reactor with a falling-film evaporator and/or a reactor with an additional condenser.

5. The method according to any one of claims 1 to 4, wherein

(1) The organic C₁-C₆Reaction of the alkoxysilane with an amount equivalent of 0.10 to 0.80 species of water (S-W), preferably an amount equivalent of 0.15 to 0.70, more preferably 0.20 to 0.60, and most preferably 0.25 to 0.50 species of water,

wherein the amount equivalent of water is calculated according to the following formula

Wherein

Amount of S-W-substance equivalent of water

mol (water) — the molar amount of water used

mol (silane) ═ C used in the reaction₁-C₆Total molar amount of alkoxysilane

n (alkoxy) ═ per C₁-C₆C of alkoxy silane₁-C₆The number of alkoxy groups.

6. The method according to any one of claims 1 to 5, wherein

(1) One or more organic C₁-C₆The alkoxysilane is reacted with water at a temperature of 20 to 65 ℃, preferably 20 to 60 ℃, more preferably 20 to 55 ℃, still more preferably 20 ℃ to 50 ℃ and most preferably 20 to 45 ℃.

7. The method according to any one of claims 1 to 6, wherein the reaction mixture is heated to a temperature sufficient to cause the reaction mixture to form a solid phase

(2) Removing C liberated by the reaction in step (1) from the reaction mixture at a temperature of 20-65 ℃, preferably 20-60 ℃, more preferably 20-55 ℃, still more preferably 20-50 ℃ and most preferably 20-45 ℃₁-C₆An alcohol.

8. The method according to any one of claims 1 to 7, characterized in that

(2) Removing C liberated by the reaction in step (1) from the reaction mixture by distillation at a pressure of from 10 to 900mbar, more preferably from 10 to 800mbar, still more preferably from 10 to 600mbar and most preferably from 10 to 300mbar₁-C₆An alcohol.

9. The method according to any one of claims 1 to 8, wherein C is removed in step (2)₁-C₆Before the alcohol, a solvent having a boiling point of 20 to 90 ℃, preferably 30 to 85 ℃ and most preferably 40 to 80 ℃ at normal pressure (1013hPa) is added.

10. The method according to any one of claims 1 to 9, characterized in that

(3) Adding one or more cosmetic ingredients selected from the group consisting of solvents, polymers, surface active compounds, coloring compounds, lipid components, pH adjusting agents, fragrances, preservatives, plant extracts and protein hydrolysates.

11. The method according to any one of claims 1 to 10, characterized in that

(3) Adding one or more cosmetic ingredients selected from the group consisting of hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and/or decamethylcyclopentasiloxane.

12. The method according to any one of claims 1 to 11, characterized in that

(4) The formulation is filled into a bottle, tube, jug, box, sachet, aerosol pressure vessel, non-aerosol pressure vessel, can or pail.

13. The process according to any one of claims 1 to 12, characterized in that the pH of the reaction mixture in step (1), (2), (3) and/or (4) after dilution with distilled water in a weight ratio of 1:1 is from 7.0 to 12.0, preferably from 7.5 to 11.5, more preferably from 8.5 to 11.0 and most preferably from 9.0 to 11.0.

14. The method of any one of claims 1 to 13, comprising the following sequence of steps:

(1) one or more organic C₁-C₆Reacting alkoxy silane with water at the temperature of 20-70 ℃,

(2) removing C liberated by the reaction in step (1) from the reaction mixture at a temperature of 20-70 ℃₁-C₆The alcohol is added into the mixture of the alcohol,

(3) adding one or more cosmetic ingredients, and

(4) filling the formulation into a packaging unit.

15. The method of any one of claims 1 to 14, comprising the following sequence of steps:

(1) one or more organic C₁-C₆Reacting alkoxy silane with water at the temperature of 20-70 ℃,

(3) adding one or more cosmetic ingredients to the mixture,

(2) removing C liberated by the reaction in step (1) from the reaction mixture at a temperature of 20-70 ℃₁-C₆Alcohol, and

(4) filling the formulation into a packaging unit.

16. Process according to any one of claims 1 to 15, characterized in that an agent for colouring the keratin materials, for retaining the keratin materials or for modifying the shape of the keratin materials is prepared.

17. Multicomponent packaging unit (kit of parts) for dyeing keratin materials, in particular human hair, which is produced separately

-a first packaging unit containing a cosmetic preparation (a), and

-a second packaging unit containing a cosmetic preparation (B),

wherein

-the cosmetic preparation (a) in the first packaging unit is prepared by the method of claims 1 to 16, and

-the cosmetic preparation (B) comprises at least one colorant compound selected from the group consisting of pigments, direct dyes and/or oxidative dye precursors.

Examples

In a reaction vessel, 20.0g of 3-aminopropyltriethoxysilane (C)₉H₂₃NO₃Si-221.37 g/mol) and 50.0g of methyltrimethoxysilane (C)₄H₁₂O₃Si 136.22 g/mol).

20.0g of 3-aminopropyltriethoxysilane (0.0903 moles of hydrolysable alkoxy groups per molecule)

50.0g of methyltrimethoxysilane 0.367 mol (3 hydrolyzable alkoxy groups per molecule)

Then, 10.0g of water (18.015g/mol) was added with stirring.

10.0g water-0.555 mol

The amount of substance corresponds to 0.40 mole of water/[ (3 × 0.090 mole) + (3 × 0.367 mole) ]

In this reaction, C used₁-C₆The alkoxysilane is reacted with an amount equivalent of 0.40 species of water.

In order to produce particularly high-performance keratin treating agents, it has been found that it is essential to maintain a specific temperature range in step (1).

In this context, it was found that a minimum temperature of 20 ℃ in step (1) is necessary to allow the hydrolysis to proceed at a sufficiently high rate and to ensure effective reaction control.

On the other hand, however, heating of the reaction mixture to a temperature above 70 ℃ must be avoided anyway. If the production is carried out at too high a temperature, undesirable or excessive polymerization or condensation reactions may occur at this point, resulting in failure to form a film attached to the keratin material upon subsequent application of the agent. Thus, when using reagents produced at too high a temperature during the dyeing process, it is no longer possible to obtain sufficiently high color intensities.

For these reasons, one or more C in step (1) of the process₁-C₆The reaction of the organoalkoxysilane with water must be carried out at a temperature of from 20 to 70 ℃.

The temperature ranges given here are C₁-C₆Alkoxysilanes andthe temperature to which the mixture of water must be adjusted. The temperature may be measured, for example, by a calibrated thermometer that extends into the mixture. Preferably, one or more organic C₁-C₆The reaction of the alkoxysilane with water takes place at a temperature of from 20 to 65 ℃, preferably from 20 to 60 ℃, more preferably from 20 to 55 ℃, still more preferably from 20 ℃ to 50 ℃ and most preferably from 20 to 45 ℃.

In another very particularly preferred embodiment, the method according to the invention is characterized in that:

(1) one or more organic C₁-C₆The alkoxysilane is reacted with water at a temperature of 20 to 65 ℃, preferably 20 to 60 ℃, more preferably 20 to 55 ℃, still more preferably 20 ℃ to 50 ℃ and most preferably 20 to 45 ℃.

The temperature range and the preferred temperature range according to the invention can be adjusted by adjusting the temperature of the reaction vessel or reactor. For example, the reaction vessel or reactor may be surrounded from the outside by a temperature control bath, which may be, for example, a water bath or a silicon oil bath.

If the reaction is carried out in a double-walled reactor, the temperature-controlled liquid may also pass through a space formed by two walls enclosing the reaction chamber.

It may further be preferred that there is no active heating of the reaction mixture and that any increase in temperature above ambient temperature is caused solely by the exotherm of the hydrolysis in step (1). If the exothermic reaction process heats the reaction mixture in step (1) too much, it must be cooled again.

Organic C₁-C₆The reaction of the alkoxysilane with water is preferably carried out at normal pressure, i.e.at a pressure of 1013mbar (1013 hPa).

_{1 6}Removing the C-C alcohol released in step (1) from the reaction mixture.

Step (2) of the process according to the invention is characterized in that the C liberated by the reaction in step (1) is partially or completely removed from the reaction mixture at a temperature of 20 to 70 ℃₁-C₆An alcohol.

As described above, C₁-C₆Hydrolysis of alkoxysilanesLiberation of the corresponding C₁-C₆The alcohol, which can now be removed from the reaction mixture in step (2), is thus removed from the reaction equilibrium.

C only in step (1)₁-C₆The alcohols can only be removed from the reaction mixture after their release, step (2) of the process preferably taking place after step (1). Here, C₁-C₆The removal of the alcohol may be carried out directly after the hydrolysis in step (1). Alternatively, however, the cosmetic ingredient may be added first (corresponding to step (3) of the method according to the invention), and C may be carried out subsequently₁-C₆Removal of alcohol (step (2)).

Alternatively, in various embodiments, step (2) may be performed simultaneously with the hydrolysis in step (1). In this embodiment, C₁-C₆The removal of alcohol has already started before the addition of water, at the beginning of the addition or after 5-20 wt.% of the planned total amount of water has been added (i.e. at the beginning of the distillation-optionally under reduced pressure).

Due to removal of C₁-C₆Alcohol, the reaction equilibrium is shifted in favour of the condensation reaction, in which the (partially) hydrolysed C₁-C₆The Si-OH groups on the alkoxysilanes can be reacted with other Si-OH groups or with other C groups₁-C₆The alkoxysilane groups react with elimination of water.

Such a reaction can be carried out, for example, according to the following scheme:

partially hydrolyzed and fully hydrolyzed C₁-C₆The alkoxysilanes can be reacted in condensation reactions with C which has not yet been reacted, partially or completely hydrolyzed₁-C₆The alkoxysilane is condensed.

In the above exemplary reaction scheme, condensation to dimers is shown, but condensation to oligomers with multiple silane atoms is also possible and preferred.

The extent of the condensation reaction is determined in part by the amount of water added in step (1). Preferably, the amount of water is such that the condensation is a partial condensation, with "partial condensation" or "partial condensation" in this context meaning that not all condensable groups of the silanes present react with one another and the organosilicon compounds obtained therefore still have on average at least one hydrolyzable/condensable group per molecule.

Furthermore, it has been found that C is removed from the reaction mixture in step (2)₁-C₆The temperature of the alcohol may also be an important influencing factor with respect to the performance of subsequent hair treatment products.

In this context, it is suspected that overheating temperatures above 70 ℃ move the condensation towards high molecular weight products which are too large to be deposited as a closed and durable film on the keratin material during subsequent keratin processing. Thus, C is removed from the reaction mixture₁-C₆In the case of alcohols, a temperature range of 20 to 70 ℃ must be maintained.

The method according to the invention comprises the complete and partial removal of the released C₁-C₆An alcohol. Due to the difficulty of achieving complete removal of all C₁-C₆Alcohol (C)₁-C₆A small residue of alcohol will remain in the reaction mixture at all times), thus partially removing C)₁-C₆Alcohols are preferred.

When C released by the reaction in step (1) is removed from the reaction mixture₁-C₆In the case of alcohol, it is particularly preferable to maintain the temperature in the range of 20 to 65 ℃, preferably 20 to 60 ℃, more preferably 20 to 55 ℃, still more preferably 20 to 50 ℃ and most preferably 20 to 45 ℃.

In step (2), the specified temperature range again refers to the removal of C from the reaction mixture₁-C₆Alkoxysilane the temperature to which the reaction mixture has to be adjusted. The temperature can also be measured, for example, by a calibrated thermometer that extends into the mixture.

In another very particularly preferred embodiment, the method according to the invention is characterized in that:

(2) at 20-65 deg.C, preferably 20-60 deg.C, more preferably 2Removing C liberated by the reaction in step (1) from the reaction mixture at a temperature of from 0 to 55 ℃, still more preferably from 20 ℃ to 50 ℃ and most preferably from 20 to 45 ℃₁-C₆An alcohol.

Very particular preference is given, in the case of one embodiment, to a process for preparing an agent for treating keratin materials, in particular human hair, comprising the following steps:

(1) one or more organic C₁-C₆Reacting alkoxy silane with water at the temperature of 20-65 ℃,

(2) completely or partially removing C released by the reaction in step (1) from the reaction mixture at a temperature of 20-65 ℃₁-C₆The alcohol is added into the mixture of the alcohol,

(3) optionally adding one or more cosmetic ingredients, and

(4) the formulation is filled into a packaging unit.

Very particular preference is given, in the case of one embodiment, to a process for preparing an agent for treating keratin materials, in particular human hair, comprising the following steps:

(1) one or more organic C₁-C₆Reacting alkoxy silane with water at the temperature of 20-60 ℃,

(2) completely or partially removing C liberated by the reaction in step (1) from the reaction mixture at a temperature of 20 to 60 DEG C₁-C₆The alcohol is added into the mixture of the alcohol,

(3) optionally adding one or more cosmetic ingredients, and

(4) the formulation is filled into a packaging unit.

Very particular preference is given, in the case of one embodiment, to a process for preparing an agent for treating keratin materials, in particular human hair, comprising the following steps:

(1) one or more organic C₁-C₆Reacting alkoxy silane with water at the temperature of 20-55 ℃,

(2) completely or partially removing C released by the reaction in step (1) from the reaction mixture at a temperature of 20-55 DEG C₁-C₆The alcohol is added into the mixture of the alcohol,

(3) optionally adding one or more cosmetic ingredients, and

(4) the formulation is filled into a packaging unit.

Very particular preference is given, in the case of one embodiment, to a process for preparing an agent for treating keratin materials, in particular human hair, comprising the following steps:

(1) one or more organic C₁-C₆Reacting alkoxy silane with water at the temperature of 20-50 ℃,

(2) completely or partially removing C released by the reaction in step (1) from the reaction mixture at a temperature of 20-50 DEG C₁-C₆The alcohol is added into the mixture of the alcohol,

(3) optionally adding one or more cosmetic ingredients, and

(4) the formulation is filled into a packaging unit.

Very particular preference is given, in the case of one embodiment, to a process for preparing an agent for treating keratin materials, in particular human hair, comprising the following steps:

(1) one or more organic C₁-C₆Reacting alkoxy silane with water at the temperature of 20-45 ℃,

(2) completely or partially removing C released by the reaction in step (1) from the reaction mixture at a temperature of 20-45 DEG C₁-C₆The alcohol is added into the mixture of the alcohol,

(3) optionally adding one or more cosmetic ingredients, and

(4) the formulation is filled into a packaging unit.

In step (2) of the process, the adjustment of the temperature range according to the invention and the preferred temperature range can be carried out, for example, by heating or cooling the reaction vessel or reactor, for example, by placing the reaction vessel in a heating jacket, or by externally surrounding the reaction vessel with a temperature-controlled bath, which can be, for example, a water bath or a silicone oil bath.

If the reaction is carried out in a double-walled reactor, the temperature-controlled liquid may also pass through a space formed by two walls enclosing the reaction chamber.

In the methodIn step (2), the C released is removed to ensure the most complete removal without exceeding the necessary temperature range₁-C₆Alcohol, preferably C is removed under reduced pressure (compared to atmospheric pressure)₁-C₆An alcohol. In this context, it has been demonstrated that C is distilled from the reaction mixture using a distillation unit₁-C₆Alcohols are particularly advantageous. In the course of this distillation, a pressure of from 10 to 900mbar, more preferably from 10 to 800mbar, still more preferably from 10 to 600mbar and most preferably from 10 to 300mbar is preferably set.

Vacuum distillation is a common chemical process and standard commercially available vacuum pumps and distillation equipment can be used. The distillation apparatus may be in the form of a reaction vessel or an attachment to a reactor.

In another very particularly preferred embodiment, the method according to the invention is characterized in that:

(2) c liberated by the reaction in step (1) is removed from the reaction mixture by distillation at a pressure of from 10 to 900mbar, more preferably from 10 to 800mbar, still more preferably from 10 to 600mbar and most preferably from 10 to 300mbar₁-C₆An alcohol.

After vacuum distillation, the volatile alcohol and, if necessary, distilled water may be condensed and collected in the receiver as a liquid distillate. The distillation can optionally be carried out with cooling of the evaporated alcohol/water by means of a cooler. The reduced pressure may be generated by conventional methods known in the art, typically using a vacuum pump.

As already mentioned, it is very preferred to use C with methoxysilane or ethoxysilane groups in the process according to the invention₁-C₆Alkoxysilanes, di-and tri-methoxy-and-ethoxysilanes, particularly preferably trimethoxy-or triethoxysilanes. These have the advantage that methanol and ethanol are liberated during hydrolysis and condensation, respectively, which, owing to their boiling points, can be easily removed from the reaction mixture by vacuum distillation.

In order to fine-tune the necessary temperature range, a method known as "boiling cooling" may also be used in step (2) of the method according to the invention.

In boiling cooling, the C of the solvent in step (2) having a boiling point of 20-90 ℃, preferably 30-85 ℃ and most preferably 40-80 ℃ at atmospheric pressure (1013hPa)₁-C₆Alcohol is added to the reaction mixture before removal. This added solvent may also be referred to as "low boiling point".

The low boiling point of the addition starts to boil at a maximum of 90 ℃ (in vacuo, the boiling temperature decreases accordingly). If light boilers are still present in the reaction mixture, the reaction mixture is kept at the boiling temperature of the light boilers.

In a further very particularly preferred embodiment, the process according to the invention is characterized in that C in step (2)₁-C₆Before the alcohol is removed, a solvent having a boiling point of 20 to 90 ℃, preferably 30 to 85 ℃ and very particularly preferably 40 to 80 ℃ at atmospheric pressure (1013hPa) is added.

Suitable solvents include:

dichloromethane with a boiling point of 40 ℃ (1013mbar)

Methanol with a boiling point of 65 ℃ (1013mbar)

Tetrahydrofuran with a boiling point of 65.8 ℃ (1013mbar)

Ethanol with a boiling point of 78 ℃ (1013mbar)

Isopropanol with a boiling point of 82 ℃ (1013mbar)

Acetonitrile with a boiling point of 82 ℃ (1013mbar)

Particularly suitable solvents are methanol, ethanol and isopropanol.

In various embodiments, the vacuum distillation of step (2) is conducted with production of a product containing less than 5 wt.%, preferably less than 2 wt.%, more preferably less than 1 wt.% of alcohol (from the hydrolysis reaction). After vacuum distillation, the water content of the product is less than 5.0 wt.%, even more preferably less than 1.0 wt.%, and most preferably less than 0.5 wt.%.

Adding one or more cosmetic ingredients in step (3).

As optional step (3), the process according to the invention comprises the addition of one or more cosmetic ingredients.

Cosmetics optionally used in step (3)The ingredient may be any suitable ingredient to impart other beneficial properties to the product. For example, in step (3) of the process, the solvent, the thickening or film-forming polymer, the surfactant compound selected from nonionic, cationic, anionic or zwitterionic/amphoteric surfactants, the colorant compound selected from pigments, direct dyes, oxidative dye precursors, C₈-C₃₀Fatty components of fatty alcohols, hydrocarbon compounds, fatty acid esters, acids and bases belonging to pH regulators, perfumes, preservatives, plant extracts and protein hydrolysates.

In another very particularly preferred embodiment, the method according to the invention is characterized in that:

(3) adding one or more cosmetic ingredients selected from the group consisting of solvents, polymers, surface active compounds, coloring compounds, lipid components, pH adjusting agents, fragrances, preservatives, plant extracts and protein hydrolysates.

The choice of these other substances will be made by the expert according to the desired properties of the reagent. With regard to the other optional components and the amounts used of these components, reference is explicitly made to the relevant manual known to the expert.

In this context, it has proven particularly preferred to use cosmetic ingredients in step (3), which further improve the stability, in particular the storage stability, of the keratin treatment agent. Herein, it has been shown that the addition of (3) one or more cosmetic ingredients selected from the group consisting of hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and/or decamethylcyclopentasiloxane is particularly advantageous in improving the stability of the composition.

In another very particularly preferred embodiment, the method according to the invention is characterized in that:

(3) adding one or more cosmetic ingredients selected from the group consisting of hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and/or decamethylcyclopentasiloxane.

Hexamethyldisiloxane has CAS number 107-46-0 and is commercially available, for example, from Sigma-Aldrich.

Octamethyltrisiloxane has CAS number 107-51-7, also commercially available from Sigma-Aldrich.

Decamethyltetrasiloxane has CAS number 141-62-8, also commercially available from Sigma-Aldrich.

Hexamethylcyclotrisiloxane has the CAS number 541-05-9.

Octamethylcyclotetrasiloxane has CAS number 556-67-2.

The CAS number for decamethylcyclopentasiloxane is 541-02-6.

Filling the formulation into a packaging unit (4)

In step (4) of the process according to the invention, the formulation obtained after steps (1) and (2) and optionally after step (3) optionally present is filled into a packaging unit.

The packaging unit may be a final package from which the user removes the reagents for treating the keratin materials. Suitable final packages include bottles, tubes, jars, boxes, sachets, aerosol pressure containers, non-aerosol pressure containers. In this regard, these final packages may contain an amount of keratin treating agent sufficient for one or (if desired) multiple applications. Preferably filled in an amount sufficient for a single application.

Further, however, the formulation in step (4) may also be filled into an intermediate package, which may be a can or a tub (hobbock), for example. Filling into an intermediate package is particularly suitable if the reaction vessel or reactor in which the process according to the invention is carried out is physically separated from the filling device which fills into the final package.

In another very particularly preferred embodiment, the method according to the invention is characterized in that:

(4) the formulation is filled into a bottle, tube, jug, box, sachet, aerosol pressure vessel, non-aerosol pressure vessel, can or pail.

The packaging unit may be a standard container commonly used in cosmetics.

The pH of the formulation in the method

In further experiments, it has been found that the reaction mixture also has a pH value which influences the condensation reaction during steps (1) to (4) of the process according to the invention. It was found that the basic pH stopped the condensation especially at the oligomer stage. The more acidic the reaction mixture, the more condensation appears to occur and the higher the molecular weight of the siloxane formed during condensation. Therefore, it is preferred that the pH of the reaction mixture in step (1), (2), (3) and/or (4) is from 7.0 to 12.0, preferably from 7.5 to 11.5, more preferably from 8.5 to 11.0, most preferably from 9.0 to 11.0.

The water content of the composition is preferably at most 10.0% by weight, and particularly preferably set lower. Especially in the case of compositions with very low water content, the measurement of the pH value (by means of a combination electrode or by means of a pH paper by means of a glass electrode) using the usual methods known from the prior art may prove difficult. For this purpose, the pH according to the invention is the pH obtained after mixing or diluting the preparation with distilled water in a weight ratio of 1: 1.

The corresponding pH value is thus measured after, for example, 50g of the composition according to the invention has been mixed with 50g of distilled water.

In another very particularly preferred embodiment, the process according to the invention is characterized in that the pH of the reaction mixture in steps (1), (2), (3) and/or (4) after dilution with distilled water in a weight ratio of 1:1 is from 7.0 to 12.0, preferably from 7.5 to 11.5, more preferably from 8.5 to 11.0 and very particularly preferably from 9.0 to 11.0.

In another very particularly preferred embodiment, the process according to the invention is characterized in that the pH of the reaction mixture in steps (1), (2), (3) and (4) after dilution with distilled water in a weight ratio of 1:1 is from 7.0 to 12.0, preferably from 7.5 to 11.5, more preferably from 8.5 to 11.0 and most preferably from 9.0 to 11.0.

To adjust this basic pH, it may be necessary to add an alkalizing agent and/or acidifying agent to the reaction mixture. The pH value for the purposes of the present invention is the pH value measured at a temperature of 22 ℃.

For example, ammonia, alkanolamines, and/or basic amino acids may be used as the alkalizing agent.

The alkanolamine may be selected from the group consisting of C having at least one hydroxyl group₂-C₆Primary amines of the alkyl precursors. Preferred alkanolamines are selected from the group consisting of: 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropan-1, 2-diol, 2-amino-2-methylpropan-1, 3-diol.

For the purposes of the present invention, amino acids are those which contain in their structure at least one protonatable amino group and at least one-COOH or-SO₃An organic compound of H group. Preferred amino acids are aminocarboxylic acids, in particular α - (alpha) -aminocarboxylic acids and ω -aminocarboxylic acids, of which α -aminocarboxylic acids are particularly preferred.

According to the invention, basic amino acids are those whose isoelectric point pI is greater than 7.0.

The basic alpha-amino carboxylic acids contain at least one asymmetric carbon atom. In the context of the present invention, the two possible enantiomers can equally be used as specific compounds or mixtures thereof, in particular as racemates. However, it is particularly advantageous to use the naturally preferred isomeric forms, usually in the L-configuration.

The basic amino acid is preferably selected from the group consisting of: arginine, lysine, ornithine and histidine, with arginine and lysine being particularly preferred. In a further particularly preferred embodiment, the agent according to the invention is therefore characterized in that the basifying agent is a basic amino acid selected from the group consisting of: arginine, lysine, ornithine and/or histidine.

In addition, inorganic alkalizers may also be used. The inorganic alkalizing agents which can be used according to the invention are preferably selected from the following group: sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate, and potassium carbonate.

Particularly preferred alkalizing agents are ammonia, 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol, 3-aminopropane-1, 2-diol, 2-amino-2-methylpropan-1, 3-diol, 2-aminobutan-1-ol, Arginine, lysine, ornithine, histidine, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate, potassium phosphate, sodium silicate, sodium metasilicate, potassium silicate, sodium carbonate, and potassium carbonate.

In addition to the alkalinizing agents mentioned above, experts are also familiar with the usual acidifying agents for fine-tuning the pH. Preferred acidulants according to the invention are pleasurable acids such as citric, acetic, malic or tartaric acid, as well as dilute inorganic acids.

Sequence of method steps

The process according to the invention is characterized in that it comprises steps (1), (2), (3) and (4), step (3) being an optional step. Some embodiments are suitable with respect to the order of the method steps.

In one embodiment, a process comprising the following sequence of steps is preferred:

(1) one or more organic C₁-C₆Reacting alkoxy silane with water at the temperature of 20-70 ℃,

(2) partially or completely removing C released by the reaction in step (1) from the reaction mixture at a temperature of 20-70 deg.C₁-C₆The alcohol is added into the mixture of the alcohol,

(3) adding one or more cosmetic ingredients, and

(4) the formulation is filled into a packaging unit.

The process starts with step (1), followed by step (2), followed by step (3), followed by step (4), i.e. the partial or complete removal of C in step (2)₁-C₆After the alcohol, one or more cosmetic ingredients, which may be, for example, solvents, pigments, thickening polymers, and the like, are added to the reaction mixture. The formulation is then filled into a packaging unit.

In a further embodiment, it may likewise be preferred to remove C in step (2)₂-C₆The alcohol is preceded by the addition of one or more cosmetic ingredients (3).

In another embodiment, a process comprising the following sequence of steps is preferred:

(1) one or more organic C₁-C₆Reacting alkoxy silane with water at the temperature of 20-70 ℃,

(3) adding one or more cosmetic ingredients to the mixture,

(2) removing C liberated by the reaction in step (1) from the reaction mixture at a temperature of 20-70 DEG C₁-C₆Alcohol, and

(4) the formulation is filled into a packaging unit.

Agent for the treatment of keratin materials

The above described process allows the preparation of prehydrolyzed or condensed silane blends which perform very well when applied to keratinous materials.

In principle, the keratin treating agents produced by this process can be used for a variety of purposes, for example as agents for coloring keratin materials, as agents for caring for keratin materials or as agents for changing the shape of keratin materials.

In another very particularly preferred embodiment, the method according to the invention is characterized in that an agent for colouring the keratin materials, for holding the keratin materials or for changing the shape of the keratin materials is prepared.

It is clear that the reagents prepared show particularly good suitability for use in the dyeing process.

In another embodiment, which is clearly very particularly preferred, the process according to the invention is characterized in that an agent for colouring keratin materials is prepared.

When used in a dyeing process, at least one colorant compound may be added to the composition, for example in step (3), wherein the colorant compound may be selected from the group consisting of pigments, direct dyes and/or oxidative dye precursors. An agent for colouring keratin materials is obtained which contains, in addition to the prehydrolyzed/condensed C1-C6 alkoxysilane, one or more colouring compounds.

However, it is also preferred that the hair colorant is provided to the user as part of a multi-component packaging unit.

Therefore, a second object of the present invention is a multicomponent packaging unit (kit of parts) for the coloring of keratin materials, in particular human hair, which is prepared separately

-a first packaging unit containing a cosmetic preparation (a) and

-a second packaging unit containing a cosmetic preparation (B),

wherein

The cosmetic preparation (a) in the first packaging unit has been produced by the method already disclosed in detail in the description of the first subject of the invention, and

-the cosmetic formulation (B) comprises at least one colorant compound selected from the group consisting of pigments, direct dyes and/or oxidative dye precursors.

Coloring compound

When the reagent prepared by the method according to the present invention is used in a dyeing method, one or more colorant compounds may be used. One or more colorant compounds may be added to the reaction mixture as a cosmetic ingredient in step (3) of the process, or provided to the user as an ingredient of separately prepared formulation (B).

The coloring compound or compounds may preferably be selected from pigments, direct dyes, oxidation dyes, photochromic dyes and thermochromic dyes, particularly preferably from pigments and/or direct dyes.

Pigments within the scope of the present invention are colouring compounds having a solubility in water at 25 ℃ of less than 0.5g/L, preferably less than 0.1g/L, even more preferably less than 0.05 g/L. Water solubility can be determined, for example, by the following method: 0.5g of pigment was weighed and placed in a beaker. A stirrer (still-fish) was added. Then, one liter of distilled water was added. While stirring on a magnetic stirrer, the mixture was heated to 25 ℃ for 1 hour. If after this period the undissolved components of the pigment remain visible in the mixture, the solubility of the pigment is less than 0.5 g/L. If the pigment-water mixture cannot be visually evaluated due to the high concentration of the possibly finely dispersed pigment, the mixture is filtered. If a portion of the undissolved pigment remains on the filter paper, the solubility of the pigment is less than 0.5 g/L.

Suitable coloring pigments may be of inorganic and/or organic origin.

In a preferred embodiment, the agent according to the invention is characterized in that it contains (b) at least one coloring compound selected from the group of inorganic and/or organic pigments.

Preferred colour pigments are selected from synthetic or natural inorganic pigments. Inorganic colour pigments of natural origin can be made, for example, from chalk, ocher, umber, smectite, charred Terra di Siena or graphite. In addition, black pigments such as black iron oxide, colored pigments such as ultramarine blue or red iron oxide, and fluorescent or phosphorescent pigments may be used as the inorganic colored pigments.

Particularly suitable are non-ferrous metal oxides, hydroxides and oxide hydrates, mixed-phase pigments, sulfur-containing silicates, metal sulfides, double metal cyanides, metal sulfates, chromates and/or molybdates. Preferred color pigments are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI 77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, pigment blue 29), hydrated chromium oxide (CI 77289), iron blue (ferric ferrocyanide, CI 77510) and/or carmine (cochineal).

Colored pearlescent pigments are also particularly preferred colorants from the group of pigments according to the invention. These are usually mica-and/or mica-based and may be coated with one or more metal oxides. Mica belongs to the group of phyllosilicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and nacrite. To produce pearlescent pigments in combination with metal oxides, mica, mainly muscovite or phlogopite, is coated with metal oxides.

As an alternative to natural mica, synthetic mica coated with one or more metal oxides may also be used as a pearlescent pigment. Particularly preferred pearlescent pigments are based on natural or synthetic mica (mica) and are coated with one or more of the above-mentioned metal oxides. The color of the respective pigment can be changed by changing the layer thickness of the one or more metal oxides.

In a further preferred embodiment, the agent according to the invention is characterized in that it comprises (b) at least one colorant compound selected from the group of pigments selected from the group of: non-ferrous metal oxides, metal hydroxides, metal oxide hydrates, silicates, metal sulfides, composite metal cyanides, metal sulfates, bronze pigments and/or mica-based colorant compounds coated with at least one metal oxide and/or metal oxychloride.

In a further preferred embodiment, the composition according to the invention is characterized in that it comprises (b) at least one colorant compound selected from mica-or mica-based pigments reacted with one or more metal oxides selected from the group consisting of: titanium dioxide (CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492), red and/or brown iron oxide (CI 77491, CI 77499), manganese violet (Cl 77742), ultramarine (sodium aluminum sulfosilicate, CI 77007, pigment blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288), and/or iron blue (ferric ferrocyanide, CI 77510).

Examples of particularly suitable color pigments are available from Merck under the trade name Merck Andcommercially available under the trade name of SensoryAndcommercially available under the trade name Eckart Cosmetic ColorsCommercially available and under the trade name from SunstarAre commercially available.

A particularly preferred trade name isThe color pigments of (a) are, for example:

colorona hopper, Merck, mica, CI 77491 (iron oxides)

Colorona session Orange, merck corporation, mica, CI 77491 (iron oxide), alumina

Colorona Patina Silver, Merck, mica, CI 77499 (iron oxide), CI 77891 (titanium dioxide)

Colorona RY, Merck, CI 77891 (titanium dioxide), mica, CI 75470 (Carr Red)

Colorona organic Beige, Merck, mica, CI 77891 (titanium dioxide), CI 77491 (iron oxides)

Colorona Dark Blue, Merck, mica, titanium dioxide, iron ferrocyanide

Colorona Chameleon, Merck, CI 77491 (iron oxide), mica

Colorona Aborigine Amber, Merck, mica, CI 77499 (iron oxide), CI 77891 (titanium dioxide)

Colorona Blackstar Blue, Merck, CI 77499 (iron oxide), mica

Colorona Patagonian Purple, Merck, mica, CI 77491 (iron oxide), CI 77891 (titanium dioxide), CI 77510 (iron ferrocyanide)

Colorona Red Brown, Merck, mica, CI 77491 (iron oxide), CI 77891 (titanium dioxide)

Colorona Russet, Merck, CI 77491 (titanium dioxide), mica, CI 77891 (iron oxides)

Colorona Imperial Red, Merck, mica, titanium dioxide (CI 77891), D & C Red No. 30 (CI 73360)

Colorona Majestic Green, Merck, CI 77891 (titanium dioxide), mica, CI 77288 (chromium oxide Green)

Colorona Light Blue, Merck, mica, titanium dioxide (CI 77891), iron ferrocyanide (CI 77510)

Colorona Red Gold, Merck, mica, CI 77891 (titanium dioxide), CI 77491 (iron oxide)

Colorona Gold Plus MP 25, Merck, mica, titanium dioxide (CI 77891), iron oxide (CI 77491)

Colorona Camine Red, Merck, mica, titanium dioxide, Carhong

Colorona Blackstar Green, Merck, mica, CI 77499 (iron oxide)

Colorona Bordeaux, Merck, mica, CI 77491 (iron oxides)

Colorona Bronze, Merck company, mica, CI 77491 (iron oxides)

Colorona Bronze, Merck company, mica, CI 77491 (iron oxides)

Colorona Fine Gold MP 20, Merck, mica, CI 77891 (titanium dioxide), CI 77491 (iron oxides)

Colorona Sienna Fine, Merck, CI 77491 (iron oxide), mica

Colorona Sienna, Merck, mica, CI 77491 (iron oxides)

Colorona Precious Gold, Merck, mica, CI 77891 (titanium dioxide), silica, CI 77491 (iron oxide), tin oxide

Colorona Sun Gold Sparkle MP 29, Merck, mica, titanium dioxide, iron oxide, mica, CI 77891, CI 77491(EU)

Colorona Mica Black, Merck, CI 77499 (iron oxide), Mica, CI 77891 (titanium dioxide)

Colorona Bright Gold, Merck, mica, CI 77891 (titanium dioxide), CI 77491 (iron oxides)

Colorona Blackstar Gold, Merck, mica, CI 77499 (iron oxide)

Another particularly preferred trade name isThe color pigments of (a) are, for example:

xirona Golden Sky, Merck, silica, CI 77891 (titanium dioxide), tin oxide

Xirona Caribbean Blue, Merck, mica, CI 77891 (titanium dioxide), silica, tin oxide

Xirona Kiwi Rose, Merck, silica, CI 77891 (titanium dioxide), tin oxide

Xirona Magic Mauve, Merck, silica, CI 77891 (titanium dioxide), tin oxide.

Further, a particularly preferred trade name isThe color pigments of (a) are, for example:

unipure Red LC 381EM, sensor, CI 77491 (iron oxide), silica

Unipure Black LC 989EM, sensor, CI 77499 (iron oxide), silica

Unipure Yellow LC 182EM, sensor, CI 77492 (iron oxide), silica

In another embodiment, the agent according to the invention may also contain (b) one or more colouring compounds selected from the group of organic pigments.

The organic pigments according to the invention are correspondingly insoluble organic dyes or colored paints, which can be selected, for example, from the following groups: nitroso, nitro-azo, xanthene, anthraquinone, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketo-pyrrolopyrrole, indigo, thioindigo, dioxazine and/or triarylmethane compounds.

Examples of particularly suitable organic pigments are carmine, quinacridone, phthalocyanine, sorghum, blue pigments with color index numbers CI 42090, CI 6980, CI 69855, CI 73000, CI 74100, CI 74160, yellow pigments with color index numbers CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigments with color index numbers CI 61565, CI 61570, CI 74260, green pigments with color index numbers CI 11725, CI 15510, orange pigment of CI 45370, CI 71105, red pigment with color index CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and/or CI 75470.

In another particularly preferred embodiment, the agent according to the invention is characterized in that it contains (b) at least one colorant compound selected from the group of organic pigments selected from the following group: carmine, quinacridone, phthalocyanine, sorghum, blue pigment with color index number Cl 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160, yellow pigment with color index number CI 11680, CI 11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005, green pigment with color index number CI 61565, CI 61570, CI 74260, orange pigment with color index number CI 11725, CI 15510, CI 45370, CI 71105, red pigment with color index number CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 50, CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 75 73915 and/or CI 75470.

The organic pigment may also be a colored coating. In the sense of the present invention, the term colored paint means a particle comprising a layer of absorbing dye, the unit of the particle and the dye being insoluble under the conditions described above. The particles may for example be an inorganic matrix, which may be aluminium, silica, calcium borosilicate, calcium aluminoborosilicate or even aluminium.

For example, alizarin color varnish may be used.

The use of pigments in the agents according to the invention is particularly preferred because of their excellent light and temperature resistance. It is also preferred if the pigments used have a certain particle size. This particle size leads on the one hand to a homogeneous distribution of the pigments in the polymer film formed and on the other hand to the avoidance of a rough hair feel or skin sensation after application of the cosmetic product. Thus, according to the invention, it is advantageous for the average particle size D of at least one pigment₅₀Is 1.0-50 μm, preferably 5.0-45 μm, preferably 10-40 μm, 14-30 μm. Average particle size D₅₀For example, it can be measured by Dynamic Light Scattering (DLS) method.

The pigment(s) (b) may be used in amounts of from 0.001 to 20% by weight, in each case from 0.05 to 5% by weight, based in each case on the total weight of the agent according to the invention.

As colouring compounds (b), the agents according to the invention may also contain one or more direct dyes. Direct acting dyes are dyes that are attracted directly to hair and do not require an oxidation process to develop color. Direct dyes are usually nitrophenyldiamines, nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes or indophenols.

Direct dyes within the meaning of the present invention have a solubility in water (760mmHg) at 25 ℃ of more than 0.5g/L and are therefore not considered pigments. Preferably, the solubility of the direct dyes within the meaning of the present invention in water (760mmHg) at 25 ℃ is greater than 1.0 g/L. In particular, the solubility of the direct dyes within the meaning of the present invention in water (760mmHg) at 25 ℃ is greater than 1.5 g/L.

Direct dyes can be divided into anionic direct dyes, cationic direct dyes and nonionic direct dyes.

In a further preferred embodiment, the agent according to the invention is characterized in that it contains at least one anionic direct dye, cationic direct dye and/or nonionic direct dye as coloring compound (b).

In a further preferred embodiment, the agent according to the invention is characterized in that it contains (b) at least one anionic direct dye, cationic direct dye and/or nonionic direct dye.

Suitable cationic direct dyes include basic blue 7, basic blue 26, basic violet 2 and basic violet 14, basic yellow 57, basic red 76, basic blue 16, basic blue 347 (cationic blue 347/Dystar), HC blue No. 16, basic blue 99, basic brown 16, basic brown 17, basic yellow 57, basic yellow 87, basic orange 31, basic red 51, basic red 76.

As nonionic direct dyes, nonionic nitro and quinone dyes and neutral azo dyes can be used. Suitable nonionic direct dyes are those listed under the following international names or trade names HC yellow 2, HC yellow 4, HC yellow 5, HC yellow 6, HC yellow 12, HC orange 1, disperse orange 3, HC red 1, HC red 3, HC red 10, HC red 11, HC red 13, HC red BN, HC blue 2, HC blue 11, HC blue 12, disperse blue 3, HC violet 1, disperse violet 4, disperse black 9 known compound designations, and 1, 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1, 4-bis- (2-hydroxyethyl) -amino-2-nitrobenzene, 3-nitro-4- (2-hydroxyethyl) -aminophenol, 2- (2-hydroxyethyl) amino-4, 6-dinitrophenol, 4- [ (2-hydroxyethyl) amino) -3-nitro-1-methylbenzene, 1-amino-4- (2-hydroxyethyl) -amino-5-chloro-2-nitrobenzene, 4-amino-3-nitrophenol, 1- (2' -ureidoethyl) amino-4-nitrobenzene, 2- [ (4-amino-2-nitrophenyl) amino ] benzoic acid, 6-nitro-1, 2,3, 4-tetrahydroquinoxaline, 2-hydroxy-1, 4-naphthoquinone, picric acid and salts thereof, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-4-nitrophenol.

Anionic direct dyes are also known as acid dyes. The acid dye has at least one carboxylic acid group (-COOH) and/or one sulfonic acid group (-SO)₃H) Of (4) a direct dye. Depending on the pH value, the protonated form (-COOH, -SO) of the carboxylic or sulfonic acid group₃H) In their deprotonated form (-COO present)^-、-SO₃ ^-) And (4) balancing. The proportion of protonated forms increases as pH decreases. If the direct dyes are used in the form of their salts, the carboxylic or sulfonic acid groups are present in deprotonated form and are neutralized with the corresponding stoichiometric equivalent of a cation to maintain electrical neutrality. The acid dyes of the present invention can also be used in the form of their sodium salts and/or their potassium salts.

Acid dyes within the meaning of the present invention have a solubility in water (760mmHg) at 25 ℃ of more than 0.5g/L and are therefore not considered pigments. Preferably, the acid dyes within the meaning of the present invention have a solubility in water (760mmHg) at 25 ℃ of more than 1.0 g/L.

Alkaline earth metal salts (such as calcium and magnesium salts) or aluminum salts of acid dyes typically have a lower solubility than the corresponding alkali metal salts. If the solubility of these salts is below 0.5g/L (25 ℃, 760mmHg), they do not fall within the definition of direct dyes.

An essential feature of acid dyes is their ability to form anionic charges, whereby the carboxylic or sulfonic acid groups responsible for this are usually linked to different chromophoric systems. Suitable chromophoric systems can be found, for example, in the structures of nitrophenyldiamines, nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes, oxazine dyes and/or indophenol dyes.

For example, one or more compounds selected from the group consisting of: acid yellow 1(D & C yellow 7, limonin A, Ext.D & C yellow No. 7, Japanese yellow 403, CI 10316, COLIPA N ° B001), acid yellow 3(COLIPA N °: C54, D & C yellow N ° 10, quinoline yellow, E104, food yellow 13), acid yellow 9(CI 13015), acid yellow 17(CI 18965), acid yellow 23(COLIPA N ℃ 29, Covacap Jaune W1100 (LCW), Sicovit Tartrazine 85E 102(BASF), Tartrazine, food yellow 4, Japanese yellow 4, FD & C yellow No. 5), acid yellow 36(CI 18665), acid yellow 121(CI 90), acid orange 6 (142CI 70), acid orange 7 (2-naphthol orange, orange II, CI 15510, D & C orange 4, COLIPA N ℃ 015), acid orange 10 (C.I.16230; G sodium salt, acid orange 13011 (T45370), acid orange 7 (2-naphthol orange 20120; TSCI 14620; TSCI 201; TSCI 14620; acid orange 13020; TSCI 201; acid orange 13020; acid orange 201; acid orange 13020; acid orange # 1; acid orange 13020; acid orange # 1; japanese brown 201; d & C brown No. 1), acid red 14(c.i.14720), acid red 18(E124, red 18; CI 16255), acid red 27 (E123, CI 16185, C-Rot 46, Echtrot D, FD & C Red No. 2, food red 9, naphthol Red S), acid Red 33 (Red 33, cherry Red, D & C Red 33, CI 17200), acid Red 35(CI C.I.18065), acid Red 51(CI 45430, tetraiodofluorescein B (Pyrosin B), tetraiodofluorescein (tetraiodofluorescein), eosin J, tetraiodofluorescein (deosin)), acid Red 52(CI 45100, food Red 106, Sun rhodamine B, acid rhodamine B, Red n.106, acid Red 73(CI 27290), acid Red 87 (eosin, CI 45380), acid Red 92 (COLON ℃ 53, CI 45410), acid Red 95(CI 45425, erythrosine, Simaced erythrosine Y), acid Red 184 (Ja 15685), acid Red 43, Exro ℃.43, acid Red 730 (CI C.I.6043, 60730), COLIPA n deg.C 063), acid Violet 49(CI 42640), acid Violet 50(CI 50325), acid blue 1 (patent blue, CI 42045), acid blue 3 (patent blue V, CI 42051), acid blue 7(CI 42080), acid blue 104(CI 42735), acid blue 9 (E133, patent blue AE, Amidoblau AE, food color Brilliant blue A, CI 42090, C.I. food blue 2), acid blue 62(CI 62045), acid blue 74 (E132, CI 73015), acid blue 80(CI 61585), acid green 3(CI 42085, food green 1), acid green 5(CI 42095), acid green 9(C.I.42100), acid green 22(C.I.42170), acid green 25(CI 61570, Japanese green 201, D & C green 5), acid green 50 (acid Brilliant green BS, C.I.44090, acid Brilliant green BS, E142), acid black 1 (Black n deg.B 401, naphthalene black 10B 401, naphthalene black amide 10B 10, naphthalene blue 401, naphthalene blue 10B 401, naphthalene blue 10 (CI 42085, E133, C42085, C1, C4, C1, C4, C1, C1, C4, C1, C4, C4, C4, C4, C, CI 20470, COLIPA n ° B15), acid black 52(CI 15711), food yellow 8(CI 14270), food blue 5, D & C yellow 8, D & C green 5, D & C orange 10, D & C orange 11, D & C red 21, D & C red 27, D & C red 33, D & C violet 2, and/or D & C brown 1.

For example, the water solubility of anionic direct dyes can be determined in the following manner. 0.1g of anionic direct dye was added to the beaker. Add stir-fish. Then 100ml of water was added. While stirring, the mixture was heated to 25 ℃ on a magnetic stirrer. Stirring for 60 minutes. The aqueous mixture was then visually evaluated. If undissolved residues are still present, the amount of water is increased-for example in 10ml portions. Water was added until the dye amount was completely dissolved. If the dye-water mixture cannot be visually evaluated due to the high strength of the dye, the mixture is filtered. If a portion of the undissolved dye remains on the filter paper, the solubility test is repeated with a higher amount of water. If 0.1g of the anionic direct dye is dissolved in 100ml of water at 25 ℃, the solubility of the dye is 1.0 g/L.

Acid yellow 1 is known as 8-hydroxy-5, 7-dinitro-2-naphthalenesulfonic acid disodium salt and has a solubility in water of at least 40g/L (25 ℃).

Acid yellow 3 is a mixture of the sodium salts of mono-and disulfonic acids of 2- (2-quinolyl) -1H-indene-1, 3(2H) -dione and has a water solubility of 20g/L (25 ℃).

Acid yellow 9 is the disodium salt of 8-hydroxy-5, 7-dinitro-2-naphthalenesulfonic acid, having a solubility in water higher than 40g/L (25 ℃).

Acid yellow 23 is the trisodium salt of 4, 5-dihydro-5-oxo-1- (4-sulfophenyl) -4- ((4-sulfophenyl) azo) -1H-pyrazole-3-carboxylic acid and is highly soluble in water at 25 ℃.

Acid orange 7 is the sodium salt of 4- [ (2-hydroxy-1-naphthyl) azo ] benzenesulfonic acid. The water solubility of the water-soluble polymer is more than 7g/L (25 ℃).

Acid Red 18 is the trisodium salt of 7-hydroxy-8- [ (E) - (4-sulfo-1-naphthyl) -diazenyl ] -1, 3-naphthalenedisulfonic acid and has a very high water solubility of more than 20% by weight.

Acid Red 33 is the disodium salt of 5-amino-4-hydroxy-3- (phenylazo) -naphthalene-2, 7-disulfonic acid having a solubility in water of 2.5g/L (25 ℃ C.).

Acid Red 92 is the disodium salt of 3,4,5, 6-tetrachloro-2- (1,4,5, 8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl) benzoic acid, whose solubility in water is expressed as greater than 10g/L (25 ℃).

Acid blue 9 is the disodium salt of 2- ({4- [ N-ethyl (3-sulfobenzyl) amino ] phenyl } {4- [ (N-ethyl (3-sulfobenzyl) imino ] -2, 5-cyclohexadien-1-ylidene } methyl) benzenesulfonic acid and has a solubility in water of greater than 20% by weight (25 ℃).

Thermochromic dyes may also be used. Thermochromic colour refers to the property of a material to change its colour reversibly or irreversibly with a change in temperature. This can be done by varying the intensity and/or wavelength maxima.

Finally, photochromic dyes may also be used. Photochromism relates to the property of a material to change its color reversibly or irreversibly upon irradiation with light, in particular ultraviolet light. This can be done by varying the intensity and/or wavelength maxima.

The same applies in respect of other preferred embodiments of the multicomponent packaging unit according to the invention to the method according to the invention.

Examples

1. Preparation of silane blends

1.1. Preparation of silane blend 1 (inventive)

A reactor having a heatable/coolable housing and a capacity of 10 liters was filled with 4.67kg of methyltrimethoxysilane. Then, 1.33kg of (3-aminopropyl) triethoxysilane was added with stirring. The mixture was stirred at 30 ℃. Subsequently, 670ml of water (distilled) were added dropwise with vigorous stirring, and the temperature of the reaction mixture was kept at 30 ℃ with external cooling. After the water addition was complete, stirring was continued for another 10 minutes. A vacuum of 280mbar is then applied, the reaction mixture is heated to a temperature of 44 ℃ and the ethanol and methanol liberated during the reaction are distilled off. The distilled alcohol was collected in a cooled receiver. Under the selected reaction conditions, the distillation was continued until no more alcohol was condensed in the receiver. The reaction mixture was then allowed to cool to room temperature. Then, 3.33kg of hexamethyldisiloxane was added dropwise to the thus-obtained mixture while stirring. Stirring was continued for 10 minutes, the silane blend 1 was poured into a bucket, and the bucket was tightly closed.

1.2. Preparation of silane blend 2 (comparative example)

A reactor having a heatable/coolable housing and a capacity of 10 liters was filled with 4.67kg of methyltrimethoxysilane. Then, 1.33kg of (3-aminopropyl) triethoxysilane was added with stirring. The mixture was stirred at 30 ℃. Subsequently 670ml of water (distilled) are added rapidly with vigorous stirring. The addition was carried out without external temperature control and the reaction mixture was heated to 75 ℃. After the water addition was complete, stirring was continued until the reaction mixture was cooled to 44 ℃. A vacuum of 280mbar is then applied and the reaction mixture is maintained at a temperature of 44 ℃. The ethanol and methanol released during the reaction were distilled off. The distilled alcohol was collected in a cooled receiver. Under the selected reaction conditions, the distillation was continued until no more alcohol was condensed in the receiver. The reaction mixture was then allowed to cool to room temperature. Then, 3.33kg of hexamethyldisiloxane was added dropwise to the thus-obtained mixture while stirring. Stirring was continued for 10 minutes, the silane blend 2 was poured into a bucket, and the bucket was tightly closed.

1.3. Preparation of silane blend 3 (comparative example)

A reactor having a heatable/coolable housing and a capacity of 10 liters was filled with 4.67kg of methyltrimethoxysilane. Then, 1.33kg of (3-aminopropyl) triethoxysilane was added with stirring. The mixture was stirred at 30 ℃. Subsequently, 670ml of water (distilled) were added dropwise with vigorous stirring, and the temperature of the reaction mixture was kept at 30 ℃ with external cooling. After the water addition was complete, stirring was continued for another 10 minutes. A vacuum of 280mbar is then applied, the reaction mixture is heated to a temperature of 75 ℃ and the ethanol and methanol liberated during the reaction are distilled off. The distilled alcohol was collected in a cooled receiver. Under the selected reaction conditions, the distillation was continued until no more alcohol was condensed in the receiver. The reaction mixture was then allowed to cool to room temperature. Then, 3.33kg of hexamethyldisiloxane was added dropwise to the thus-obtained mixture while stirring. Stirring was continued for 10 minutes, the silane blend 3 was poured into a bucket, and the bucket was tightly closed.

1.4. Preparation of silane blend 4 (comparative example)

A reactor having a heatable/coolable housing and a capacity of 10 liters was filled with 4.67kg of methyltrimethoxysilane. Then, 1.33kg of (3-aminopropyl) triethoxysilane was added with stirring. The mixture was stirred at 30 ℃. Subsequently 670ml of water (distilled) are added rapidly with vigorous stirring. The addition was carried out without external temperature control and the reaction mixture was heated to 75 ℃. After the water addition was complete, stirring was continued for another 10 minutes. A vacuum of 280mbar is then applied, the reaction mixture is heated to a temperature of 75 ℃ and the ethanol and methanol liberated during the reaction are distilled off. The distilled alcohol was collected in a cooled receiver. Under the selected reaction conditions, the distillation was continued until no more alcohol was condensed in the receiver. The reaction mixture was then allowed to cool to room temperature. Then, 3.33kg of hexamethyldisiloxane was added dropwise to the thus-obtained mixture while stirring. Stirring was continued for 10 minutes, the silane blend 4 was poured into a bucket, and the bucket was tightly closed.

2. Dyeing test

In each case 100g of the silane blend prepared at point 1 were weighed out.

Preparation (A)

The following colorant (formulation (B)) is provided.

Preparation (B)

Ready-to-use colorants were prepared by shaking 10g of formulation (a) and 100g of formulation (B), respectively (3 minutes shaking). Then, the mixture was allowed to stand for 5 minutes.

For application, a bundle of hair (Kerling dark brown) is dipped into the ready-to-use dye and left there for 1 minute. Excess agent is then removed from each bundle of hair. Each tress of hair was then washed with water and dried. Subsequently, the tresses were visually evaluated under fluorescent light. The following results were obtained: