WO2008138363A1

WO2008138363A1 - Nitrogen-containing polyether-polysiloxane block copolymers, process for preparing them and their use for enhancing the surface properties of fabrics and fibres

Info

Publication number: WO2008138363A1
Application number: PCT/EP2007/004123
Authority: WO
Inventors: Arndt Brückner; Frank König; Holger Leidreiter; Tobias Maurer; Peter Schwab
Original assignee: Evonik Goldschmidt Gmbh
Priority date: 2007-05-10
Filing date: 2007-05-10
Publication date: 2008-11-20

Abstract

The invention relates to nitrogen-containing polyether-polysiloxane block copolymers and also to a process for preparing them. It further relates to the use of these polymers as an additive to formulations for the care and cleansing of keratinic fibres, such as, for example, as conditioners for hair, and also for woven and nonwoven fabrics and/or fibres made from natural and/or synthetic raw materials and textiles, for example as softeners/emollients.

Description

G o l d s c h m i d t GmbH, Essen

Nitrogen-containing polyether-polysiloxane block copolymers, processes for their preparation and their use for improving the surface properties of fabrics and fibers

The invention relates to nitrogen-containing polyether-polysiloxane block copolymers and to a process for their preparation. It further relates to the use of these polymers as an additive in formulations for the care and cleaning of keratinic fibers, such as hair conditioners, as well as for fabrics, non-wovens and / or fibers of natural and / or synthetic raw materials and textiles such as as a plasticizer.

Nitrogen-containing polyether-polysiloxane block copolymers and their use as additives for fabric softening agents are known from the patent literature. Thus, for example, WO-A-02/10256 and WO-A-04/042136 describe linear polyamino-polysiloxane copolymers based on silicones and functionalized hydrocarbon radicals in which α, ω-epoxy-siloxanes react with α, ω-epoxy-functionalized hydrocarbons Amine units are linked together. In particular, the cited documents describe polymers based on tertiary amines (eg N, N, N ', N'-tetramethylhexanediamine) and short-chain epoxy-functionalized hydrocarbons (eg ethylene glycol diglycidyl ether) which contain tetraalkylammonium units in high density. All softener formulations based on polysiloxane polymers of the prior art have in common that even after a single washing of a textile finished with them, the softening property is largely lost. If a textile is treated with such compounds, it will indeed receive a good softness, but the siloxane is easily removable again from the corresponding textile due to its low substantivity, such as by washing operations. However, it is desirable that the siloxane remains on the fabric even after washing and thus the soft touch is not lost.

The invention is therefore based on the object to find polyether-polysiloxane polymers which have the desired property profile, in particular a very good hydrophilic soft touch and increased permanence on textiles. In addition, a high elasticity of elasticity, reduced tendency to wrinkling and an improved desensitizing tendency, for example during ironing, of a finished product are to be regarded as a further positive characteristic.

The use of polyether-polysiloxane block copolymers with tetraalkylammonium units as haircare additives is also known from WO-A-02/10256 and WO-A-04/042136.

Human hair is exposed daily to a variety of influences. In addition to mechanical stress caused by brushing, combing, putting up or tying back, the hair is also attacked by environmental influences such as strong UV radiation, cold, wind and water. Also the physiological status (eg age, health) of the respective person influences the condition of the keratin fibers.

In particular, the treatment with chemical agents changes the structure and surface properties of the hair. Methods such as perming, bleaching, dyeing, tinting, smoothing, etc., but also frequent washing with aggressive surfactants contribute to causing more or less severe damage to the hair structure. For example, in a perm, both the cortex and the cuticle of the hair are attacked. The disulfide bridges of cystine are broken up by the reduction step and partially oxidized to cysteic acid in the subsequent oxidation step.

Bleaching not only destroys melanin but also oxidizes about 15-25% of the disulfide bonds of cystine with mild bleaching. With an excessive bleaching, it may even be up to 45% (K.F. de Polo, A Short Textbook of Cosmetology, 2000, Verlag für chemische Industrie, H. Ziolkowsky GmbH).

Thus, the chemical treatments, the frequent washing or the UV irradiation result in adverse mechanical properties for the hair caused by the removal of naturally-eliminated hair follicles or humectants (sebum). It is thus brittle, dry, lackluster, porous and poorly combed.

In addition, thoroughly cleansed hair is usually very difficult to comb, both in wet and in dry state, as the individual hairs tend to become frizzy and knotted. So it loses its resistance only when washing and then combing. This is reflected in a significant decrease in tensile elongation at wet hair. In addition, it is less resistant to further damage from chemicals, surfactants and environmental influences than healthy hair.

For the care of such damaged hair, there are special preparations, such as hair conditioners, hair conditioners, shampoos, leave-in conditioners, etc., but above all can improve the combing and the handle damaged hair. Such commercial hair care products contain mainly alkylammonium-based cationic surfactants, as well as the compounds exemplified in WO-A-02/10256 and WO-A-04/042136, polymers, waxes or oils or silicone oils. The effectiveness of these compounds can be u.a. attributed to a hydrophobization of the hair surface.

While all these funds, a good conditioning effect (conditioning) of the hair is achieved, but the appearance, especially the luster of the hair is not improved by the care products, but sometimes even worse.

There is therefore still a need for versatile active ingredients for body cleansing and care products such as shampoos, hair treatment agents and hair treatment agents, which improve the care of the hair in addition to the cleansing effect and at the same time give good shine, the hair from damage Protect the hair structure and minimize the already caused structural damage to the hair caused by environmental influences and form and coloring treatments.

It is a further object of the invention to provide such an active ingredient which is capable of improving properties such as combability, softness, volume, moldability, handleability, unraveling of undamaged and damaged hair, as well as hair to give beautiful shine. The compounds should therefore show an improved or at least equally good individual effect, but overall an improved combined effect of mechanical and other properties.

It has surprisingly been found that the linear amino-functional polyether-polysiloxane block copolymers described in greater detail below correspond to the previously defined requirement profiles. The compounds according to the invention also have the advantage that they are free of tetraalkylammonium units, which must be avoided for reasons of toxicity (see, for example, Dr. Peter Hardt, "Environmentally friendly textile softeners"), lecture on the 37th German Dyeing Day in Melliand Textilberichte 9/1990, p 699-706).

An object of the invention are therefore linear polyether-polysiloxane block copolymers of the general formula (I)

[(- Q - R - S - R -) _p (- Q - R - P - R -) _q ] _r (I) in which the units (- Q - R - S - R -) and (- Q - R - P - R -) are linked together in any order and in which p is 1 to 10, q is 1 to 10, r is 1 to 50 and r * p> 3 and r * q> 3

where S is a divalent siloxane unit of the general formula (II)

(ID

and a is 5 to 500, preferably 10 to 60, b is 0 to 50, preferably 0, c is 0 to 60, preferably 10 to 60, and

R ^{1 are} identical or different aliphatic or aromatic hydrocarbon radicals having 1 to 8 C atoms,

P is a divalent polyether unit of the general formula (III)

- [O ⁽ C ₂ H ₄ -dR dθ ⁾ _β ] - (III) represents and

Each R ³ is independently hydrogen or

Methyl, each independently of one another 0 or 1, e 8 to 40, preferably 10 to 30, particularly preferably 12 to 25,

Q is the piperazine radical

and

wherein the chain ends can be modified as desired.

The values a, b and c of the general formula II are to be understood as average values in the molecule, since the polysiloxanes to be used according to the invention are generally present in the form of equilibrated mixtures. It is well known to those skilled in the art that the compounds are due to their polymeric nature in the form of a mixture with a substantially regulated by statistical laws distribution. The values for all indices therefore represent mean values.

It is familiar to the person skilled in the art that the compounds according to the invention are present in the form of a mixture having a distribution governed essentially by statistical laws. Another object of this invention is a process for the preparation of the products according to the invention, This is characterized in that

a) a diglycidylsiloxane of the general formula (IV)

(IV)

where a is 5 to 500, preferably 10 to 60, b is 0 to 50, preferably 0, c is 0 to 60, preferably 10 to 60, and

R ^{2 is} CH ₂ OCH ₂ CH ₂ CH ₂ ,

b) a diglycidyl ether of the general formula (V)

in which

R 1 is CH ₂ OCH ₂ CH ₂ CH ₂ , Each R ³ is independently hydrogen or

Methyl, each independently of one another is 0 or 1, e is from 8 to 40, preferably from 10 to 30, particularly preferably from 12 to 25,

c) piperazine

be reacted with or without solvent, simultaneously or successively in any order, continuously or discontinuously, optionally with the aid of a catalyst with each other.

Preferred catalysts according to the invention are ZrCl ₄ , ZnCl ₂ , montmorillonite, LiBr, Cu (BF ₄ J ₂ .H ₂ O, LiClO ₄ , Yb (OTf) ₃ , BF ₃ , carboxylic and mineral acids such as acetic acid, HCl and H ₂ SO ₄ Particularly preferred according to the invention is LiBr.

It is known to the person skilled in the art that side reactions can be expected in the context of such a reaction sequence. Thus, the OH groups of the units R themselves can also open epoxide rings and thus lead to branched structures. The extent of side reactions depends, among other things, on the nature of the starting materials and on the reaction conditions.

A further subject of this invention is the use of the compounds of the general formula (I) and the compounds of the general formula (I) or the technical mixtures prepared according to the process according to the invention as softening agents in optionally surfactant-containing aqueous care and cleaning formulations for fabrics, non-wovens and / or fibers of natural and / or synthetic raw materials.

Another object of this invention is the use of the compounds of general formula (I) and the compounds of general formula (I) prepared according to the inventive method or the technical mixtures prepared according to this method for the preparation of fabric softeners, detergents and cleaners for fabrics , Non-wovens and / or fibers of natural and / or synthetic raw materials.

A further subject of this invention is the use of the compounds of the general formula (I) and of the compounds prepared by the process according to the invention

Compounds of the general formula (I) or of the technical mixtures produced according to this process for

Preparation of care or conditioning agents for keratinic fibers.

A further subject of this invention is the use of the compounds of the general formula (I) and of the compounds of the general formula (I) prepared according to the process according to the invention or of the technical mixtures prepared according to this process for the production of gloss-improving care formulations for keratinic fibers.

A further subject of this invention is the use of the compounds of the general formula (I) and the compounds of the general formula (I) prepared according to the process according to the invention or technical mixtures prepared for the treatment of surfaces, as a coating agent, for Oberflächenhydrophobierung, as a wetting agent for surfaces, as an additive in wetting agents, as a lubricant, as an additive in lubricants, as an additive in drilling fluids, as an impregnating agent, as an additive in impregnating agents, as a corrosion inhibitor, as an additive in anticorrosion agents, as an antifogging agent, as an additive for paints and varnishes, in the manufacture of composites, in the manufacture of compounds, for the coating of particles, fillers and pigments, and for the improvement of the rheological properties of pigments.

EXAMPLES

The following examples are intended to illustrate the invention, but they are not limiting.

Production examples:

The amine number indicates the percentage by weight of nitrogen in the sample in percent.

Use of aromatic hydrocarbons as solvent Synthesis Example 1 according to the invention:

Silicone chain length of 80 Si, diglycidyl EO polyether, formulation in Dowanol® TPM:

In a 2-L three-necked flask equipped with a stirrer, an intensive condenser, a mushroom heating hood, a thermometer and a dropping funnel, 0.44 mol

Piperazine submitted in 500 g of xylene. At 130 ⁰ C were

0.23 mol of an α, ω-bis (glycidyloxypropyl) polydimethyl siloxane added dropwise with an average chain length of 80 Si and stirring for 11 h at 130 ⁰ C.

511 g of the resulting mixture were then in the

Reaction apparatus diluted with 200 g of xylene. At 120 ⁰ C 35 g of a Polyethylenglykoldiglycidylethers were added dropwise with an average of 10 EO units and stirred at 125 ⁰ C for a further 19 h. Subsequently, with 400 g

Dowanol® TPM (tripropylene glycol monomethyl ether, Dow Chemical) and the solvent distilled off xylene under reduced pressure. A pale yellow colored, viscous product was obtained. It is the above to understand the formula mentioned so that it is a random copolymer. Weight average molecular weight 69,272 g / mol.

Tertiary nitrogen : 0.42%; theor .: 0.44%.

Synthetic Example 2 - according to the invention:

Silicone chain length of 30 Si, diglycidyl PO polyether,

Formulation in Dowanol® TPM:

In a 2-L three-necked flask equipped with a stirrer, an intensive condenser, a mushroom heating hood, a thermometer and a dropping funnel, 1.0 mol of piperazine in 300 g of xylene were introduced. At 130 ⁰ C for 0.5 ω-bis- (glycidyloxypropyl) -polydimethylsi- loxans were mol of an α, added dropwise with an average chain length of 30 Si and subsequently stirred for 14 h at 130 ⁰ C. 780 g of the resulting mixture were then diluted in the reaction apparatus with 400 g of xylene. At 130 ⁰ C, 253.5 g of a Polypropylenglykoldiglycidylethers were added dropwise with an average of 11 PO units and stirred at 130 ⁰ C for a further 17 h. 716 g of these xyloligen

Reaction mixture were mixed with 441 g Dowanol® TPM (tripropylene glycol monomethyl ether, Dow Chemical) and the solvent xylene distilled off under reduced pressure. A pale yellow colored, viscous product was obtained. Tertiary nitrogen: 0.81%; theor .: 0.83%.

Synthesis Example 3 according to the invention:

Silicone chain length of 30 Si, diglycidyl PO polyether, formulation in Varonic® APM: 563 g of the xylene-containing reaction mixture from Example 2 were admixed with 347 g of Varonic® APM (Degussa) and the solvent xylene was distilled off under reduced pressure. A pale yellow colored, viscous product was obtained.

Tertiary nitrogen : 0.80%; theor. : 0.83%.

Synthesis Example 4 according to the invention:

Silicone chain length of 80 Si, diglycidyl PO polyether,

In a 2-L three-necked flask equipped with a stirrer, an intensive condenser, a mushroom heating hood, a thermometer and a dropping funnel, 0.44 mol of piperazine in 500 g of xylene were introduced. At 130 ⁰ C 0.23 mol of an α, ω-bis (glycidyloxypropyl) polydimethyl siloxane were added dropwise with an average chain length of 80 Si and stirred for 11 h at 130 ⁰ C. 643.2 g of the resulting mixture were then diluted in the reaction apparatus with 320 g of xylene. At 120 ^° C., 77.6 g of a polypropylene glycol diglycidyl ether were added dropwise at an average of 11 PO units and the mixture was stirred at 135 ^° C. for a further 8 hours. Subsequently, 507 g of Dowanol® TPM (tripropylene glycol monomethyl ether, Dow Chemical) were added and the solvent xylene was distilled off under reduced pressure. A pale yellow colored, viscous product was obtained. Tertiary nitrogen: 0.40%; theor: 0.43%. Synthesis Example 5 according to the invention:

Silicone chain length of 80 Si, diglycidyl PO polyether,

Formulation in Varonic® APM:

In a 2-L three-necked flask equipped with a stirrer, an intensive condenser, a mushroom heating hood, a thermometer and a dropping funnel, 0.23 mol of piperazine in 250 g of xylene were introduced. At 135 ⁰ C 0.11 ω-bis- (glycidyloxypropyl) -polydimethyl- siloxane were mol of an α, added dropwise with an average of 80 Si Kettenlängp and further stirred for 5 h at 135 ⁰ C. It was then diluted with 500 g of xylene at 125 ⁰ C 111 g of a Polypropylenglykoldiglycidylethers with an average added dropwise 11 PO units, and a further 10 h at 125 ⁰ C. 529 g of this approach were used at 264 g

Varonic® APM is added and the solvent is distilled off xylene at reduced pressure. A pale yellow colored, viscous product was obtained. Tertiary nitrogen : 0.41%; theor: 0.43%.

Synthetic Example 6 - not according to the invention:

Silicone chain length of 80 Si, butanediol diglycidyl ether, formulation in Dowanol® TPM:

In a 2 L three-necked flask equipped with a stirrer, an intensive condenser, a mushroom heating hood, a thermometer and a dropping funnel, 0.42 mol of piperazine in 250 g of xylene were introduced. At 125 ⁰ C 0.21 ω-bis- (glycidyloxypropyl) -polydimethyl- siloxane were mol of an α, added dropwise with an average chain length of 80 Si and subsequently stirred for 7 h at 125 ⁰ C. At 125 ⁰ C, 0.21 mol of butanediol diglycidyl ether were added dropwise and stirred at 125 ⁰ C for 12 h. The reaction product was then treated with 1,230 g of Dowanol.RTM. TPM (tripropylene glycol monomethyl ether, Dow Chemical) and the solvent xylene was distilled off under reduced pressure. A pale yellow colored, viscous product was obtained. Tertiary nitrogen : 0.45%; theor. : 0.47%.

Use of polyethers as solvent for the synthesis

Synthesis Example 7 according to the invention:

Silicone chain length of 30 Si, diglycidyl EO polyether,

Reaction control in Dowanol® TPM:

In a 2-L three-necked flask equipped with a stirrer, an intensive condenser, a mushroom heating hood, a thermometer and a dropping funnel, 0.104 mol

Piperazine in 126 g of Dowanol® TPM (tripropylene glycol monomethyl ether, Dow Chemical) submitted. At 115 ⁰ C, 0.05 mol of an α, ω-bis (glycidyloxypropyl) -poly-dimethylsiloxane were added dropwise with an average chain length of 30 Si and stirred at 115 ⁰ C for 5 h. Subsequently, 28.7 g of a polyethylene glycol diglycidyl ether were added dropwise at an average of 10 EO units and stirred at 115 ⁰ C for a further 8 h. A pale yellow, colored, viscous product was obtained. Tertiary nitrogen: 1.03%; theor .: 1.02%. Use of catalysts for epoxy ring opening

Synthetic Example 8 - according to the invention:

Silicone chain length of 80 Si, diglycidyl EO polyether,

Formulation in Dowanol® TPM:

In a 2-L three-necked flask equipped with a stirrer, an intensive condenser, a mushroom heating hood, a thermometer and a dropping funnel, 0.11 mol of piperazine and 320 mg of lithium bromide in 200 g of xylene were introduced. At 125 ⁰ C, 05 ir.ol a cc.co-bis- (glycidyloxypropyl) -polydimethylsiloxans were added dropwise with an average chain length of 80 Si 0 and further stirred for 4 h at 125 ⁰ C. 491 g of the resulting mixture were then added dropwise in the reaction apparatus with 30 g of a polyethylene glycol diglycidyl ether with an average of 10 EO units of 5.6% and stirred at 125 ⁰ C for a further 4 h. Subsequently, with

258 g of Dowanol.RTM. TPM (tripropylene glycol monomethyl ether, Dow Chemical) are added and the solvent xylene distilled off under reduced pressure. A pale yellow colored, viscous product was obtained.

Synthesis Example 9 - not according to the invention:

Silicone chain length of 80 Si, 1,8-bis (methylamino) -3,6-dioxaoctane, formulation in Dowanol® TPM:

In a 2 L three-necked flask equipped with a stirrer, an intensive condenser, a mushroom heating hood, a thermometer and a dropping funnel, 0.04 mol of 1, 8-bis (methylamino) -3,6-dioxaoctane in 200 g of xylene submitted. At 120 ⁰ C 0.04 mol of an α, ω-bis (glycidyloxypropyl) polydimethylsiloxane were added dropwise with an average chain length of 80 Si and stirred for a further 27 h at 125 ⁰ C. Subsequently, with

222 g of Dowanol.RTM. TPM (tripropylene glycol monomethyl ether, Dow Chemical) are added and the solvent xylene distilled off under reduced pressure. A pale yellow colored, viscous product was obtained.

Examples of the application for improving the surface properties of fabrics and fibers Formulation examples:

General formulation:

5 to 50% by weight of the siloxanes according to the invention or their solutions are stirred in a beaker with propeller stirrer to give a mixture of 1.25 to 12.5% by weight of an isotridecyl alcohol ethoxylate with an ethoxylation degree of 6, 0.05 to 0.5% by weight of concentrated acetic acid and 37.0 to 93.7% by weight of water.

Formulation Example 1 according to the invention:

20% by weight of the product of Synthesis Example 1 are added in a stirred glass beaker to a mixture of 5.0% by weight of an isotridecyl alcohol ethoxylate having a degree of ethoxylation of 6, 0.2% by weight of concentrated acetic acid and 74.8% % By weight of water. A clear to opaque low-viscosity formulation is obtained.

Analogously to the preparation of the general formulation, the formulations listed in Table 1 were prepared. The comparative product Wetsoft® CTA is a self-dispersing amino-functional silicone fluid with polyether groups from Wacker, which can be used as a hydrophilic softener for fibers and textiles. The comparative product Wetsoft® NE 810 is a self-dispersing polyether-amino-functional silicone fluid from Wacker, which can be used as a hydrophilic softener for fibers and textiles. Table 1 :

Prepared formulations

Application examples:

To check the feel and the hydrophilicity of the products according to the invention, products consisting of native fibers were equipped with the following procedure:

Padding method:

To test the softness of the respective emulsions, cotton knitted fabric (160 g / m ² ) and cotton terry toweling (400 g / m ² ) were padded with a liquor containing 20 g / l of the corresponding emulsion, to about 100 % Liquor pick-up and dried at 130 ⁰ C for three minutes.

To examine the hydrophilicity cotton woven (200 g / m ^{2), and} padded with a liquor containing each 50 g / l of the corresponding emulsion and squeezed to about 100% wet pickup, and dried at 130 C for three minutes ^0th Exhaust process:

To test the softening, cotton mesh (160 g / m ² ) and cotton terry (400 g / m ² ) were dipped in a 0.025% (based on silicone active) liquor at a liquor ratio of 1 to 12 for 20 minutes with light mixing, gently wrung and dried at 100 ⁰ C in the oven. To test the hydrophilicity, cotton weave (200 g / m ² ) was immersed in a 0.025% (based on silicone active) liquor with a liquor ratio of 1 to 120 for 20 minutes with slight mixing and dried at 100 ^° C. in an oven.

Test methods:

Hand Assessment:

To assess the product handle, an experienced team was put together to evaluate the anonymized handle patterns, the knitted and terry towels finished with the emulsions, using a hand panel test. In the knitted fabric knitwear samples, an untreated unmarked sample was additionally added.

Washing process:

The washes were washed in a Miele Novotronic washing machine commercially available W 918 with colored fabrics without pre-washing at 40 ⁰ C with wfk IECA standard detergent base and 3 kg of cotton ballast fabric. Last was The fabric thus treated was dried for 12 hours at room temperature.

Testing the hydrophilicity:

To check the hydrophilicity, the internal test method based on DIN 53924 was used to measure the rise height of water. The finished cotton test fabric is cut into five 25 cm long and 1.5 cm wide strips, marked with a water-soluble pencil and fastened to a support in a tight vertical position but without tension. The holder is then placed in a water basin for five minutes so that 2 cm of the strip dip into the water. After the holder has stood outside the water tank for 10 minutes, the height of rise is read in cm and determined against the blank value (height of untreated cotton strips x cm = 100%) and expressed in% of the blank value.

Soft-touch test results are shown in Tables 2, 3, and 4 and in Table 5 for hydrophilicity.

Table 2:

Soft grip rating on cotton terry fabric after application by padder

+++ excellent, ++ very good, + good, o satisfactory, - bad

Table 3: Soft handle assessment on cotton knit fabric or cotton terry fabric after application by padder in comparison with commercially available hydrophilic Aminosiloxan

+++ excellent, ++ very good, + good, o satisfactory, - bad Table 4:

Soft grip assessment after application by padder and

exhaust

+++ excellent, ++ very good, + good, o satisfactory, bad

Table 5:

Reverse wetting behavior on cotton fabric in% of the rise height of the untreated cotton strip after application with

Foulard

Summary of the assessment:

The result is a soft, very fluffy and silky feel of the fabrics equipped with the products according to the invention (for example Formulation 1, Tables 3 and 4). In addition, the product thus treated exhibited high elasticity and improved anti-wrinkling properties.

In particular, it can be seen that the softening effect of Formulation Example 1 after application by a coating process is superior to Formulation Example 6 (Table 4). Add to that a better water taking up the tissue represented by the higher reverse net value (Table 5).

In contrast, the softness in the non-permanent product of Formulation Example 4 already deteriorates significantly after a single wash (Table 2).

Examples of application in the cosmetic field

Formulation Examples:

Table 6:

Prepared formulations and application examples for a hair cosmetic cream conditioner

+++ excellent, ++ very good, + good, o satisfactory, - bad The formulations were tested in a comparative test on human hair. Hair strands are treated with the formulations described above as follows: The strands of hair are wetted under running, warm water. The excess water is gently squeezed out by hand, then shampooed with a surfactant solution (1 ml / strand of hair (2 g)). After a residence time of 1 min, the hair is rinsed for 1 min. Afterwards the respective formulation is applied as a rinse and gently incorporated into the hair

(1 ml / strand of hair (2 g)). After a residence time of 1 min, the hair is rinsed for 1 min. In towel moistening

Hair is evaluated directly after rinsing the wet combability sensory. Before the sensory evaluation of dry combability and hair shine, the hair is dried in air at 50% humidity and 25 ⁰ C for at least 12 h. The composition of the test formulations is intentionally simple to avoid influencing the test results by (normally present) formulation ingredients. Formulations according to the invention may contain, in addition to the ingredients mentioned and / or instead of the ingredients mentioned, further ingredients. In particular, the combination with other ingredients can lead to a synergistic improvement in the described effects. Such ingredients may be (but are not limited to): surfactants, wetting agents or emulsifiers from the groups of anionic, cationic, zwitterionic, amphoteric or nonionic surfactants such as fatty alcohol sulfates, fatty alcohol ether sulfates, alkyl sulfonates, alkyl benzene sulfonates, alkyl sulfosuccinates, quaternary ammonium salts, alkyl betaines, fatty acid amidoalkyl betaines, derivatives of monomeric or condensed saccharides such as sugar esters, methyl or ethyl glucoside fatty acid esters, alkyl glucosides, ethoxylated fatty alcohols, fatty acid alkanolamides or ethoxylated fatty acid esters, thickeners such as kaolin, bentonite fatty acids, fatty alcohols, starch, polyacrylic acid and its derivatives, cellulose derivatives , Guarderivate, alginates, chitosan, petrolatum or paraffin, further opacifiers such as glycol ester derivatives or alcohols such as ethanol, propanol, isopropanol, propylene glycol or glycerol, solubilizers, stabilizers, buffer systems, perfume oils, dyes and in particular also other conditioning agents and conditioning additives, such as other cationic or amphoteric polymers, lanolin and its derivatives, cholesterol, ceramides, pantothenic acid, betaines, creatine, other silicones or silicone derivatives.

Assessment criteria:

The sensory evaluations are based on grades awarded on a scale from - to +++, with - the worst and +++ the best rating. The individual test criteria each receive their own rating.

The test criteria are: wet combability, dry combability, appearance / gloss.

Summary of the assessment:

It is known to those skilled in the art that an improved conditioning performance in the combination of cationic Conditioners such as cetyltrimethylammonium chloride with silicone derivatives results. This becomes clear from the comparison between Formulation 7 and Formulations 8, 9 and 10. Compared with the prior art (formulation 10), the products according to the invention have significantly improved wet and dry combability. The gloss rating is also improved by the products according to the invention. In comparison of the products according to the invention, formulation 9 is distinguished by a significantly better gloss evaluation.

Claims

Claims:

1. Linear Polyether-Polysiloxane Block Copolymers of the General Formula (I)

[(- Q - R - S - R -) _p (- Q - R - P - R -) _q q] Jr: D

in which the units (- Q - R - S - R -) and (- Q - R - P - R -) are linked together in any order and in which p is 1 to 10, q is 1 to 10, r is 1 to 50 and r * p> 3 and r * q> 3

where S is a divalent siloxane unit of the general formula (II)

and a is 5 to 500, b is 0 to 50, c is 0 to 60, and so is R ^{1 are} identical or different aliphatic or aromatic hydrocarbon radicals having 1 to 8 C atoms,

P is a divalent polyether unit of the general formula (III)

- [O ⁽ C ₂ H ₄ -dR ³ dO ⁾ e] - ⁽ HD

and R ^{3 are} each independently hydrogen or

Methyl, d are each independently 0 or 1, e 8 to 40, Q is the piperazine radical

and

OH R is the radical - (CH ₂ ) 3 OCH ₂ JCLHCH ₂ -

is.

2. Linear polyether-polysiloxane block copolymers according to claim 1, characterized in that S is selected from the group of siloxane units with b = 0 and a = c = 10 to 60.

3. Linear polyether-polysiloxane block copolymers according to at least one of claims 1 and 2, characterized in that P is selected from the group of polyether units with e = 10 to 30.

4. Linear polyether-polysiloxane block copolymers according to at least one of claims 1 and 2, characterized in that P is selected from the group of polyether units with e = 12 to 25.

5. A process for the preparation of block copolymers according to the general formula (I), characterized in that

a) a diglycidylsiloxane of the general formula (IV)

(IV)

where a is 5 to 500, b is 0 to 50, c 0 to 60, is as well

R ^{1 are} identical or different aliphatic or aromatic hydrocarbon radicals having 1 to 8 C atoms, R ^{2 is} CH ₂ OCH ₂ CH ₂ CH ₂ ,

b) a diglycidyl ether of the general formula (V)

in which

R ^{2 is} CH ₂ OCH ₂ CH ₂ CH ₂ ,

Each R ³ is independently hydrogen or

Methyl, each independently of one another is 0 or 1, e is from 8 to 40, and

c) piperazine

be reacted with or without solvent, simultaneously or sequentially in any order, continuously or discontinuously, optionally with the aid of a catalyst with each other.

6. The method according to claim 5, characterized in that component a) is selected from the group of diglycidylsiloxanes with b = 0 and a = c = 10 to 60.

7. The method according to at least one of claims 5 to 6, characterized in that component b) selected is from the group of diglycidyl ethers with e = 10 bis

30th

8. The method according to at least one of claims 5 to 6, characterized in that component b) is selected from the group of diglycidyl ethers with e = 12 to 25.

9. Use of the block copolymers according to any one of claims 1 to 8 as a softening agent in optionally surfactant aqueous care and cleaning formulations for tissue, non-wovens and / or fibers of natural and / or synthetic raw materials.

10. Use of the block copolymers according to at least one of claims 1 to 8 for the preparation of fabric softeners, detergents and cleaners for fabrics, nonwovens and / or fibers from natural and / or synthetic raw materials.

11. Use of the block copolymers according to any one of claims 1 to 8 for the preparation of care or conditioning agent for keratinic fibers.

12. Use of the block copolymers according to any one of claims 1 to 8 for the preparation of gloss-improving care formulations for keratinic fibers.

13. Use of the block copolymers according to at least one of claims 1 to 8 for the treatment of surfaces, as coating compositions, for surface hydrophobization, as wetting agents for surfaces, as additives. Set in wetting agents, as a lubricant, as an additive in lubricants, as an additive in drilling fluids, as an impregnating agent, as an additive in impregnating agents, as a corrosion inhibitor, as an additive in corrosion inhibitors, as an anti-fogging agent, as an additive for paints and coatings, in the manufacture of composites, at the production of compounds, for the coating of particles, fillers and pigments as well as for the improvement of the rheological properties of pigments.