JPS6335607B2 - - Google Patents

Description

[Detailed description of the invention]

The inventor has claimed and described in French Patent Application No. 54983/72 a hair styling composition particularly suitable for application to human hair, which hair styling composition has the general formula () -A-Z-A-Z-A-Z- () (wherein A is a group derived from a heterocycle having two secondary amino groups, preferably a group

[Formula], and Z is a group B or B' which may be the same or different, containing up to 7 carbon atoms in the main chain and substituted by one or more hydroxyl groups; represents a linear or branched alkylene group which is substituted or unsubstituted, and this alkylene group is an ether, thioether, sulfoxide, sulfone, sulfonium, amino, alkylamino, alkenylamino, benzylamino, amine oxide, amide, At least one oxygen, nitrogen or sulfur atom present in the form of an imide, alcohol, ester and/or urethane group and one or more aromatic rings and/or multiple rings.
It contains at least one cationic film-forming polymer represented by the formula (3) in an aqueous solution or an aqueous alcoholic solution. The polymers may be in the form of quaternary ammonium salts as well as in the form of oxidation products. Using these polymers it is possible to limit or eliminate defects resulting from the general condition of the hair or from treatments that damage the hair, such as bleaching, permanent waving or dyeing treatments. Become. The present inventor has proposed a composition suitable for washing or treating human hair, which has the following formula: -A-Z- () [wherein A is

[Formula] and Z is a group B or a group B ₁ , provided that at least one Z represents a group B ₁ ; the group B is -(CH ₂ ) _t1 -(CHOH) _u -(CH ₂ ) _t2 - (However, t ₁ + t ₂ = 6, u = 0 or 1),
Group B ₁ is -(CH ₂ ) _n1 -(CHOH) _p1 -(CH ₂ ) _n2 -N-
(CH ₂ ) _n3 —(CHOH) _p2 —(CH ₂ ) _n4 (R), where the nitrogen atom is a group R ₁ having the following formula,
Substituted by one of R ₂ or R ₃ , -(CH ₂ ) _o1 - (O) _q - (CH ₂ ) _o2 - (OH)
( _R1 ) -(CH ₂ ) _o5 -COOH (R ₃ ) However, formula (R), (R ₁ ), (R ₂ ) and (R ₃ )
, (m ₁ +m ₂ +m ₃ +m ₄ ) is 7 or less, each of n ₁ , n ₂ , n ₃ , n ₄ and n ₅ is the same or different and represents an integer from 1 to 3, and P ₁ and P ₂ are the same or different, represent zero or 1, q is zero or 1, and v is zero or 1] At least one molecular weight 15000
The following film-forming polymers, or formula B or expression (wherein G is methyl, ethyl or benzyl, Y represents chloride, bromide, iodide, sulfate, mesylate or tosylate anion, and Z ₁ has the meaning of Z quaternized or not) at least one quaternary ammonium salt having the formula or expression (In the formula, Z ₂ is the same as the definition of Z in the formula.)
at least one amine oxide or di having the formula -A-Z ₃ - () (wherein A is

[expression] and

It is a mixed group of [Formula], Z ₃ is a unit obtained by betaination of B, B ₁ and B ₁ ,
or Z ₃ is a unit obtained by betaination of B ₁ and B ₁ , with the proviso that at least one Z ₃ is a unit obtained by betaination of B ₁ or We have found a composition as described above, characterized in that it contains a carrier or a diluent that can be used as a carrier or a diluent. These polymers have properties as described above that make them particularly suitable as hair treatments and conditioners. In addition to the benefits in conditioners such as improved combability, shine, flexibility and ease of styling of wet hair, the polymers according to the invention are commonly used in hair treatment compositions. improved compatibility with surfactants, especially anionic surfactants. These quaternary ammonium salts are obtained by quaternizing the basic groups of this polymer with chloroacetic acid or chloroacetates, especially sodium chloroacetate. The inventors have discovered that by quaternizing this polymer as described above, its compatibility with anionic surfactants commonly used in such compositions is improved. The cationic polymers according to the invention can be produced by direct or indirect polycondensation. Direct polycondensation methods generally combine piperazine and hydroxylated amines such as diglycolamine or 2-amino-2-methyl-propane-1,3-diol, and/or amino acids such as glycine with epichlorohydrin or epibromohydrin. It consists of reacting in an aqueous medium with an epihalohydrin such as by adding sodium carbonate as an acceptor for the hydrohalic acid isolated during the reaction and then heating this mixture to a temperature of 80-90 ° C. . The indirect polycondensation process generally consists first of all of preparing intermediate derivatives X, which are obtained from the reaction of epihalohydrin with piperazine or with hydroxylic amines and/or amino acids. This intermediate derivative X is then reacted with a second amine. Subsequently, some epihalohydrin is added if necessary, followed by a base such as sodium hydroxide, and the mixture is heated to a temperature of 80-90°C. The proportions of piperazine, epihalohydrin and hydroxyl amine and/or amino acid that can be used depend on the sequence of units A, B ₁ and B' ₁ desired in the final polymer. Preferably, the epihalohydrin and the piperazine, hydroxyl amine and/or amino acid mixture are present in equimolar proportions. Suitably, the mixture of piperazine, hydroxyl amine and/or amino acid contains 90-50 mole % piperazine and 10-50 mole % hydroxyl amine and/or amino acid. The polymers thus obtained can be oxidized with hydrogen peroxide or other peracids in a known manner as described in the specification of said application and can be oxidized with lower alkyl-, preferably methyl- or ethyl-bromide, chloride, iodide. , sulfate, mesylate or tosylate; benzyl chloride or benzyl bromide. In this oxidation reaction, some or all of the nitrogen-containing groups are converted to oxidized amine groups.
it is conceivable that. As mentioned above, the polymer of general formula () can be converted into "betaine" by quaternizing the basic group that can be quaternized with, for example, 0 to 66% sodium chloroacetate or chloroacetic acid. ” has proven particularly advantageous. The yield of this reaction is generally 60-100%. The degree of "betaineation" can be defined as the ratio of the number of equivalents of quaternized nitrogen to the number of equivalents of total nitrogen that can be quaternized multiplied by 100. The yield of quaternization in this reaction can be defined as the ratio of the number of equivalents of nitrogen actually quaternized to the number of equivalents of the quaternizing agent used multiplied by 100. The inventor has found that only one of the two tertiary nitrogen atoms of unit A can be easily quaternized. The betaination reaction is carried out by the general formula -A'-Z'- () (where A' is a group

[Formula] and

and Z' is B ₁ or, if the groups B, B' or B' ₁ contain one or more nitrogen atoms, these groups B,
Units obtained by betaination of B' or B' ₁ - this is

It can be assumed that it is in the form of [Formula]. ) gives the equivalent unit. Accordingly, the present invention also provides polymers of the general formula -A'-Z'- (). However, in the above general formula (), A' and Z' are the same as defined above, and (1) Z' is B or B', or if B or B' has one or more basic nitrogen atoms. If so, is it a unit obtained by betaination of B or B' (however, B and
B′ is the same as defined above), or (2) Z′ is B ₁ or B′ ₁ and at least one
It is a unit obtained by betaination of B' 1 with the condition that Z' is B' ₁ or a unit derived from B _{' 1} [However, B ₁ and B' ₁ are the same as the above and the general formula - A'-Z- () (However, A' is the same as defined above, and Z' is B ₁ or B' ₁ and/or B or B', or B ₁ and/or B and B ′ is 1
Since it contains at least 1 nitrogen atom, it is a unit obtained by betaineization of B ₁ and/or B and B'. ) is the same as the definition in the hair styling composition containing the polymer]. The inventors have found that the entities of the invention are simulative and have relatively low molecular weights, ie molecular weights not exceeding 15,000 (measured by vapor pressure drop). These polymers are soluble in water or an aqueous alcoholic medium. These polymers are particularly effective when used on hair that has been sensitized as a result of treatments such as bleaching, permanent waving or dyeing, but can also be used advantageously on normal hair. . These polymers are suitably included as the main ingredient in various hair styling compositions such as lotions, creams or hair styling gels in an amount of 0.1 to 5% by weight, preferably 0.2 to 3% by weight based on the total weight of the composition. as an anionic, cationic, nonionic, amphoteric or zwitterionic surfactant in shampoos, wave setting compositions, permanent wave fixatives and dye compositions. , cinergist,
Incorporation as an auxiliary ingredient in the presence of other compounds such as foam stabilizers, sequestrants, fatliquors, thickeners, softeners, cosmetic resins, preservatives, dyes, fragrances and fungicides. Can be done. These can then be used as mixtures with other anionic, cationic, amphoteric or nonionic polymers. These polymers are present in various compositions, depending on their PH (generally PH 3-11), either in salt form or in free base form. The composition of the invention may be in the form of an aqueous, hydroalcoholic or alcoholic solution, or as a cream,
Suitably it is in the form of a paste, gel or powder. They may also contain an aerosol of the radiopharmaceutical or may be packaged in an aerosol container. Hair shampoo compositions according to the invention may be anionic, cationic, nonionic, amphoteric and/or
In addition to a zwitterionic surfactant and one or more polymers of the general formula ~, a synergist,
Bubble stabilizers, sequestrants, fatliquors, thickeners, hair styling resins, softeners, dyes, fragrances, bactericides,
It optionally contains preservatives and other adjuvants commonly used in such compositions. The compositions of the invention may also be in the form of, for example, wave setting lotions, treatment creams, hair conditioners and anti-dandruff lotions. The following examples further illustrate the invention. In these examples, parts are by weight. Example 1 First step: formula referred to below as intermediate X The intermediate derivative N,N-bis-[β-
Production of hydroxy-γ-chloropropyl]-diglycolamine. 740 g (8 moles) of epichlorohydrin and 2700 g of water
The mixture was added dropwise to a solution of 420 g (4 mol) of diglycolamine in 10 g over 1 hour while stirring at 10 to 15°C. The reaction mixture was stirred at 20° C. for 4 hours, and the epoxide groups virtually disappeared. A clear solution with a solids content of 30% with a very slight green tinge is thus obtained. Second stage: A

[Formula], Z is B ₁ or B' ₁ , B ₁ is -CH ₂ -CHOH-CH ₂ -, and B' ₁ is A polymer of the formula -A-Z-, in which the ratio of units A/B' ₁ /B ₁ is 4/1/3 (the molar ratio of piperazine/diglycolamine/epichlorohydrin is 4/1/ 5) Production of a polymer. 965 g (1 mol) of solution of intermediate X produced above
to 775 g (4 moles) of pepyrazine hexahydrate at a temperature of
Add while maintaining the temperature at 20℃. 277 g (3 mol) of epichlorohydrin are then added while still maintaining the temperature at 20°C. Subsequently, 500 g (5 mol) of 40% strength sodium carbonate solution are added over the course of 1 hour. The mixture is then heated to 80-90°C and kept at this temperature for 1 hour. A solution containing 20% of the active substance is thus obtained by dilution with 1130 g of water. Example 2 Direct preparation of a polymer of the formula -A-Z- in which the units A and Z have the same meaning as in Example 1, but the piperazine and diglycolamine are statistically distributed. The ratio of units A/B' ₁ /B ₁ is the same as above, 4/
It is 1/3. The same relative molar ratios of piperazine, diglycolamine and epichlorohydrin as in Example 1 are used. That is, 4/1/5. 92.5g (1 mol) of epichlorohydrin to 140g of water
161 g (0.83 mol) of piperazine hexahydrate and 21 g (0.2 mol) of diglycolamine dispersed in 20 ml
Add over 1 hour at °C. One hour after the addition, 100 g (1 mol) of 40% strength sodium hydroxide are added dropwise while still maintaining the temperature at 20.degree. The mixture is then heated to a temperature of 80-90°C and held for 1 hour. The reaction mixture is then diluted with 227 ml of water to obtain a solution containing 20% active substance. The solution thus obtained is colorless and 25
The viscosity measured at °C is 0.7 poise. Example 3 A is

[Formula], Z is B′ ₁ , and B′ ₁ is Preparation of a polymer of the formula -A-Z-. The ratio of units A/B' ₁ is 1/1. The molar ratio of piperazine/diglycolamine/epichlorohydrin is 1/1/2. 1 mol of intermediate X produced in Example 1 at a concentration of 30%
(970 g) dropwise to a solution of 1 mol (194 g) of piperazine hexahydrate in 742 g of water at 20 DEG C. under a nitrogen atmosphere with stirring over the course of 1 hour. After the addition was completed, the reaction mixture was stirred at 20°C for 1 hour. Next, 167.5g of sodium carbonate with a concentration of 48%
(2 mol) are added over 1 hour at the same temperature. Stirring is continued at this temperature for an additional hour, and then the mixture is heated to 80-90°C for 2 hours. Addition of 1026.5 g of water gives a clear, practically colorless solution of the polyamine containing 10% of the active substance. Example 4 First stage: Mostly formula Production of prepolymer P which is said to be. Piperazine hexahydrate in 500 g of water in the form of a 30% strength solution (1935 g) of intermediate X of Example 1
Add 776 g (4 moles) of the solution according to the procedure of Example 3. After the addition is complete, the reaction mixture is stirred for 1 hour at 20°C. 4 mol of sodium hydroxide in the form of a 48% strength solution (335 g) are then added at the same temperature over the course of 1 hour. Stirring is continued for an additional hour at the same temperature and then the mixture is heated to 80-90°C for 2 hours. A clear solution of prepolymer P of the above formula is thus obtained. Second stage: A

[Formula], Z is B ₁ or B' ₁ , B ₁ is -CH ₂ -CHOH-CH ₂ -, and B' ₁ is Preparation of a polymer of the formula -A-Z-. The ratio of units A/B' ₁ /B ₁ is 2/1/1. The molar ratio of piperazine/diglycolamine/epichlorohydrin is 2/1/3. 92.5 g (1 mol) of epichlorohydrin was added to half the solution of prepolymer P (1.835
g) (corresponding to 2 equivalents of secondary amine) with stirring. After the addition was completed, the reaction mixture was stirred at 20°C for 1 hour. Next, 83 g of sodium hydroxide solution with a concentration of 48%
(1 mol) is added over 1 hour at the same temperature. Stirring is continued for an additional hour at the same temperature, and then the mixture is heated to 80-90°C for 1 hour. Addition of 2625 g of water gives a clear, practically colorless solution of the polyamine containing 10% of the active substance. Example 5 A is

[Formula], Z is B ₁ or B′ ₁ , and B′ ₁ is and the formula -A-Z- where B ₁ is -CH ₂ -CHOH-CH ₂ -
Production of polymers of the type. The ratio of units A/B' ₁ /B ₁ is 4/1/3. The relative molar ratio of piperazine/diglycolamine/epichlorohydrin is 4/1/5. Formula containing 0.43 equivalents of secondary amine 5.1 g of 1,3-bis-piperazino-propan-2-ol - corresponding to 0.215 mol - are added with stirring to 394.5 g of the above solution of prepolymer P containing 0.43 equivalents of secondary amine. This 1,3-bis-piperazino-propan-2-ol can be prepared according to the method described in Example 15 of the aforementioned patent application. 39.7 g (0.43 mol) of epichlorohydrin are added to this solution over a period of 1 hour at 20°C. This mixture is stirred at the same temperature for 1 hour. Then the concentration
35.8 g (0.43 mol) of 48% sodium hydroxide solution
over 1 hour at 20°C. After stirring at the same temperature for 1 hour, the reaction mixture was
Heat to 90°C for 1 hour. Addition of 1099 g of water gives a polyamine solution containing 10% active substance. Example 6 A is

[Formula], Z is B ₁ or B′ ₁ , and B′ ₁ is and the formula -A-Z where B ₁ is -CH ₂ -CHOH-CH ₂ -
- production of polymers of the type. The ratio of units A/B' ₁ /B ₁ is 1/0.42/0.56,
And the units B ₁ and B′ ₁ are statistically distributed. The polymer contained piperazine (1.07 mol), 2-amino-2-methyl-propane-1,3-diol (0.45 mol) and epichlorohydrin (1.5 mol).
according to the direct method of Example 2. Piperazine hexahydrate 209g (1.07mol) and water 250g
2-amino-2-methyl-propane-1 in ml,
Mix with 47.2g of 3-diol. 139 g (1.5 mol) of epichlorohydrin are added over 1 hour at 20°C. 150g of sodium hydroxide with a concentration of 40%
(1.5 mol) was also added, and this mixture was
Heat to °C and hold at this temperature for 1 hour. At the end of the reaction, the mixture is diluted with 760 ml of water, giving a clear solution containing 20% solids. Example 7 A is

[Formula], Z is B ₁ or B′ ₁ , and B′ ₁ is and the formula where B ₁ is -CH ₂ -CHOH-CH ₂ -
Production of A--Z- type polymers. The ratio of units A/B′ ₁ /B ₁ is 1.2/0.8/0.4,
The units B ₁ and B′ ₁ are statistically distributed. The relative molar ratio of piperazine/glycine/epichlorohydrin is between 1.2 and 0.8/2. 60 g (0.8 mol) of glycine of the formula H ₂ N—CH ₂ —COOH dispersed in 218 g of water
is neutralized with 80 g (0.8 mol) of 40% strength sodium hydroxide solution. 233 g (1.2 mol) of piperazine hexahydrate are added to the above solution. Next, 185g of epichlorohydrin
(2 mol) is added over 1 hour at 15-20°C with stirring. After stirring at this temperature for 1 hour, concentrate at the same temperature.
Add 200 g (2 mol) of 40% sodium hydroxide solution. Stir for another hour at 20°C, then at 80°C for 1 hour.
Continue time. Cool this solution and add water to 124
Bring the content of active substance to 25% by adding g. A clear, very slightly yellow colored solution is thus obtained. Evaporation of the dilute solution yields a hard, only slightly sticky film. Example 8 (reference) A' is a group -N N-

Preparation of betainated polymers of the formula -A'-Z'-, which are mixtures of the formula, Z' is B, and B is -CH ₂ -CHOH-CH ₂ -. Sodium monochloroacetate 58.25g (0.51mol)
, Z is B and A is

Add to 500 g of an aqueous solution of a polymer of the formula -A-Z, where B is -CH ₂ -CHOH-CH ₂ -. This aqueous solution was obtained by condensing 100 g (0.51 mol) of piperazine hexahydrate, 47.7 g (0.51 mol) of epichlorohydrin, and 20.2 g (0.51 mol) of sodium hydroxide in an aqueous solution, which contains active substances. 14.2%
contains 1 equivalent of nitrogen that can be quaternized, and
It has a viscosity of 320 cps at 20°C. next,
Heat this mixture to 90°C for 5 hours. After cooling,
Analysis of this solution shows a quaternization yield of 83.4%. The degree of betaine conversion is 41.7%. The viscosity of this solution after quaternization is 130 cps. The degree of betaination is 41.7%, which means that the unit
83.4% of A′

It shows that [Formula]. Example 9 Sodium monochloroacetate 46.7g (0.4mol)
was added to 812 g of an aqueous solution of a cationic polymer containing 14.2% of the above active substance and 1.6 equivalents of quaternizable nitrogen, and the mixture was then heated at 90°C.
Cook for 5 hours. The yield of quaternization is 85%. The degree of betaineization is 21%. In this betaine polymer, the unit A
42% of It is. Example 10 A′ is a group

[Formula] and

It _is a mixture _{of the formula} as well as Preparation of betainated polymers of the formula -A'-Z'- which are mixtures of. Piperazine hexahydrate 483g (2.49mol), diglycolamine 63g (0.6mol), epichlorohydrin 277.5g (3mol) and sodium hydroxide 120g
The polymer obtained by solution condensation of (3 mol) is converted into betaine. The viscosity of this solution at 25℃ is
It is 75cps. This starting polymer has A

[Formula], Z is B ₁ or B′ ₁ , and B′ ₁ is and is of the type of formula -A-Z-, where B ₁ is -CH ₂ -CHOH-CH ₂ -. The ratio of units A/B' ₁ /B ₁ is 2.4/0.6/1.8. Sodium monochloroacetate 157.4g (1.34mol)
is added to 1005 g of the polymer containing 20% active substance and 2.5 equivalents of total nitrogen, and the mixture is then heated to 95° C. for 5 hours. The yield of quaternization is 70-71% and the viscosity of the obtained compound is 67 cps at 25°C. The degree of betaination is 37.5%, that is, the basic nitrogen atom
37.5%

It is in the form of [expression]. Example 11 Sodium monochloroacetate 78.8g (0.67mol)
is added to 1005 g of the cationic polymer used in Example 10 containing 20% active substance and 2.5 equivalents of total nitrogen, and the mixture is then heated to 85-100° C. for 5-6 hours. The yield of quaternization is 71%, and the viscosity after the reaction is 60 cps at 25°C. The degree of betaineization is
It is 19%. The betainated polymer was of the same type as that produced in Example 10, with basic nitrogen atoms
19%

It is simple in that it is in the form of [formula]. are different. Example 12 A is

[Formula], Z is B ₁ or B' ₁ , B ₁ is -CH ₂ -CHOH-CH ₂ -,
and B′ ₁ is Quaternization of the compound of Example 2 with dimethyl sulfate. This quaternized polymer essentially consists of two types of units: The ratio is 80/20. While stirring 254.5 g (2.02 mol) of dimethyl sulfate at a temperature below 30°C, about 80% of the sodium chloride was removed by dialysis, and 3.37 g of nitrogen was removed.
of the polymer prepared according to Example 2 containing atoms
Add to 1082g of 27% aqueous solution. After stirring for 3 hours at the same temperature, the solution is brought to 30% active substance content by adding 485 g of water. The film obtained by evaporation of the aqueous solution is hard and slightly sticky. Example 13 Quaternized with dimethyl sulfate to produce the following two types of units: and in a ratio of approximately 80/20. 185 g (2 moles) of epichlorohydrin was added to a mixture of 141 g (1.64 moles) of piperazine and 42 g (0.4 moles) of diglycolamine dissolved in 300 c.c. of methanol with stirring at 20°C over a period of 1 hour, and the mixture was then 30 to reflux temperature of solvent
Heat for a minute. 30% methanol solution of sodium methylate
360 g (2 mol) are then added over a period of 2 hours with continued heating to the reflux temperature of the methanol. Sodium chloride is removed by filtration. 261 g of a redundant solution containing 0.942 atoms of nitrogen is heated under reduced pressure to remove methanol. Add 200 c.c. of dimethylformamide. 119 g (0.942 mol) of dimethyl sulfate are added to the new solution and the reaction mixture is then heated to 90° C. for 4 hours with stirring. The polymer is isolated in the form of a highly hygroscopic powder by dropping the above solution into a large excess of acetone. The film obtained by evaporation of the aqueous solution is transparent, hard and non-stick. Application Example Example A1 Anionic shampoo: Compound according to Example 3...1g Triethanolamine lauryl sulfate...15g Copradiethanolamide...3g Add lactic acid and PH7.4 Add water to bring the total amount to
...Suppose it is 100g. Example A2 Anionic shampoo: Compound according to Example 4...1.2 g Disodium salt of sulfosuccinate half ester of monoethanolamide [sic]
...10g Sodium lauryl-ether-sulfate condensed with 2.2 moles of ethylene oxide*
...15g Copradiethanolamide ...4g Add water to bring the total amount to ...100g. PH is 7. *Lauryl alcohol and ethylene oxide 2.2
Sodium salt of the reaction product sulfate with mole. Example A3 Shampoo: Compound according to Example 5 ...0.75 g Lauryl alcohol polyethoxylated with 12 moles of ethylene oxide ...12 g Copradiethanolamide ...4 g Trimethylacetylammonium bromide
...Add 0.5g citric acid to pH 4, add water and bring the total amount to
...Suppose it is 100g. Example A4 Shampoo: Compound according to Example 3...1 g Sodium lauryl-ether-sulfate condensed with 2.2 mol of ethylene oxide
...10g Formula commercially available under the product name "MiranlC2M" Alkylimidazoline...2g Copra monoethanolamide...1.5g Add lactic acid to pH 7.5, add water to bring the total amount to
...Suppose it is 100g. Example A5 Shampoo: Compound according to Example 4...1.5g Lauryl alcohol polyethoxylated with 12 moles of ethylene oxide...8g N-(N',N'-diethylaminopropyl)
-N ² - Sodium salt of dodecyl-asparagine...4g Copradiethanolamide...2g Add lactic acid to pH 5, add water to bring the total volume to
...Suppose it is 100g. Example A6 Anionic shampoo: Compound according to Example 2 ... 1 g Triethanolamine lauryl-sulfate ... 10 g Sodium lauryl-ether-sulfate oxyethyleneated with 2.2 mol of ethylene oxide ... 10 g Pupradiethanolamide ... 3 g Add water to make the total amount PH8...100g. PH8 Example A7 Anionic shampoo: Compound of Example 10...1g Triethanolamine lauryl-sulfate...10g Sodium lauryl-ether-sulfate oxyethyleneated with 2.2 moles of ethylene oxide...10g Copradiethanolamide... Add 3g of water to make the total amount...100g. PH7.5 Example A8 Anionic shampoo: Compound of Example 10 ...0.75 g Sodium lauryl ether sulfate oxyethyleneated with 2.2 moles of ethylene oxide ...10 g Lauryl dimethylamine oxide [commercially available under the name (AmmonyxLO) ] ...2g Copradieethanolamide ...2.5g Add water to make ...100g. PH7.5 Example A9 Cationic shampoo: Compound of Example 2...1.2g Lauryl alcohol polyethchelated with 12 moles of ethylene oxide...12g Trimethylacetylammonium bromide [sold under the trade name (Cetavlon)]... 1g Copradiethanolamide...2g Add lactic acid to pH 5, add water to bring the total amount to
...Example A10 with 100 g Compound according to Example 7 ...1.5 g Compound of formula C ₁₂ H ₂₅ O [C ₂ H ₃ O (CH ₂ OH] - ₄ H ... 6 g Formula R-CHOH-CH _2O [ _CH2 -CHOH- _CH2O
]- _3.5 H compound (where R is a _{C9 - C12} alkyl group)...5g Lauryldimethylamine oxide (commercially available under the name "AmmonyxLO")...2g Add lactic acid, pH 4, and water. Take the entire amount
...Suppose it is 100g. Example A11 Shampoo: Compound according to Example 7...1g Triethanol lauryl sulfate
...15g Lauroyl diethanolamide ...3g Add water to bring the total amount to ...100g. PH7.5 Example A12 (Reference) Shampoo: Compound of Example 8...2g Sodium lauryl-ether-sulfate converted into polyoxyethyleneate with 2.2 moles of ethylene oxide...12g Copraethanolamide...2.5g Carboxymethylcellulose... Add 0.5g of water to make the total amount...100g. PH7.3 Example A13 (Reference) Xiangpu: Compound according to Example 8...1.5g Formula R.CHOH-CH2O[ _{CH2- CHOH} - _CH2O ] _-3 .
₅ H (where R is a C ₉ - C ₁₂ alkyl group) compound...6g Lauryl alcohol polyethoxylated with 12 moles of ethylene oxide...5g Add lactic acid to pH 5, add water to bring the total amount to
...Suppose it is 100g. Example A14 Anionic shampoo: Compound of Example 12...1.5g Monoethanolamine lauryl myristyl ether sulfate oxyethyleneated with 2.2 moles of ethylene oxide...12g Copraethanolamide...2.5g Add water to total amount Let ……100g. PH8 Example A15 Anionic shampoo: Compound of Example 12...1g Aminolauryl oxide...1.5g Copraethanolamide...2g Sodium lauryl myristyl ether sulfate oxyethyleneated with 2.2 moles of ethylene oxide...8.5g Add water to make the total amount PH7.5...100g. Example A16 Anion Shampoo: Compound of Example 12...2g Lauryl alcohol oxyethyleneated with 12 moles of ethylene oxide...10g Copradiethanolamide...3g Dimethylamine lauryl oxide...2.5g Add water to make up the total amount. PH5...100g. Example A17 1 Dry hair treatment cream piperazine/diglycolamine/epichlorohydrin 4/
Polymer obtained by polycondensation at a molar ratio of 1/5
...2.5g Cetyl alcohol ...2g Stearyl alcohol ...2g Cetyl-styaryl alcohol oxyethylated with 15 mole ethylene oxide ...4g Hydroxyethylcellulose ...2g Water ...Adjust to 100g Apply this cream to clean, damp hair. After contacting for several minutes, rinse and dry. 2 Conditioner for dry hair Polymer obtained by polycondensation of piperazine/diglycolamine/epichlorohydrin in a 4/1/5 molar ratio betainated with sodium chloroacetate...0.6g polyvinylpyrodone/vinyl acetate 70/ 30 copolymer (molecular weight)...0.4g Water...adjusted to 100g Apply this lotion to clean, damp hair,
I left it on without rinsing. Comparative Example The polymer described in Example 9 of the present invention (referred to as Compound A) was compared with the compound described in Example 9 of JP-A-48-75732 (referred to as Compound B). Compatibility with anionic surfactants Example A6 of the present invention was prepared with the following composition: 1 Composition A Compound of Example 10...1g Triethanolamine lauryl sulfate
...10g Sodium lauryl ether sulfate oxyethylated with 2.2 moles of ethylene oxide ...10g Copradiethanolamide ...3g Water ...100g Adjusted to PH7.5 2 Composition B The compound of Example 9 of the above publication was used according to the present invention Example of
Same as composition A except that 10 compounds were replaced. Composition A is clean and transparent, while composition B shows a precipitate. This comparative experiment shows that the polymers of the present invention are more compatible with anionic surfactants than those of the prior art. Retention Test Compositions A and B were tested to determine conditioning properties. I used a bundle of bleached straight hair that was 24cm long and weighed 2.5g. Preparation of hair tresses The hair tresses to be tested are dampened with tap water, excess water is removed, 1 ml of composition A or B is applied per 2.5 g of hair tresses, the hair is rinsed and 2 ml of the composition is applied. A control bundle was treated in the same manner, except that compositions A and B were replaced with a control shampoo of a 2% solution of sodium lauryl sulfate. The treated hair strands were placed on a hair curler with a diameter of 20 mm. It was dried for 45 minutes at 60°C. The locks were then untied and the hair was styled by brushing and combing to obtain the natural movement of the hair. This bundle is fixed on the artificial head, six hair bundles treated with compositions A and B are fixed on the right side of the artificial head,
Six control hair tresses (treated with control solution) were fixed on the left side. To mimic daily activities, this artificial head rotates alternately at 75 times per minute and at relative humidity of 52% and 26%.
It was placed in a chamber at ℃. After 180 minutes, brush and comb the hair.
The degree of sagging was measured. The improvement in retention was superior to the bundles treated with the control solution (sodium lauryl sulfate). The improvement was expressed by the following formula. D-D'/D x 100 where D is the slackness of the control bundle and D' is the slackness of the compositions A and B.
This is the loosening of the hair strands treated with. All tests were performed twice and the results are the average values. Result

[Table] From the above results, the hair treated with the shampoo according to the present invention showed a 63% (45+18) improvement in retention compared to the hair treated with the conventional product. Therefore, the polymer of the present invention had excellent compatibility with anionic surfactants and also had excellent conditioning effects.

Claims (1)

[Scope of Claims] 1. A composition suitable for cleaning or treating human hair, which has the following formula: -A-Z- () [wherein A is [Formula], and Z is a group B or a group B ₁ , where at least one Z represents a group B ₁ ; the group B is −(CH ₂ ) _t1 −(CHOH) _u −(CH ₂ ) _t2 − (where t ₁ +t ₂ =6, u=0 or 1),
Base B ₁ is However, the nitrogen atom is a group R ₁ having the following formula,
Substituted by one of R ₂ or R ₃ , -(CH ₂ ) _o1 - (O) _q - (CH ₂ ) _o2 - (OH)
( _R1 ) -(CH ₂ ) _o5 -COOH (R ₃ ) However, formula (R), (R ₁ ), (R ₂ ) and (R ₃ )
, (m ₁ +m ₂ +m ₃ +m ₄ ) is 7 or less, each of n ₁ , n ₂ , n ₃ , n ₄ and n ₅ is the same or different and represents an integer from 1 to 3, and P ₁ and P at least one repeating unit having _a molecular weight of 15,000
The following film-forming polymers, or formula B or expression (wherein G is methyl, ethyl or benzyl, Y represents chloride, bromide, iodide, sulfate, mesylate or tosylate anion, and Z ₁ has the meaning of Z quaternized or not) at least one quaternary ammonium salt having the formula or expression (In the formula, Z ₂ is the same as the definition of Z in the formula.)
at least one amine oxide or di having the formula -A-Z ₃ - () where A is a mixed group of [Formula] and [Formula], and Z ₃ is a betaylation group of B, B ₁ and B ₁ is the unit obtained by
or Z ₃ is a unit obtained by betaination of B ₁ and B ₁ , with the proviso that at least one Z ₃ is a unit obtained by betaination of B ₁ or and a carrier or diluent that can be used.