JPH0252680B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION This invention relates to cleaning and cleaning compositions. Cleaning and cleaning compositions intended for use as cosmetic detergent products not only exhibit good cleaning and foaming properties, but also are non-irritating or
It should have a low irritant effect on the skin and eyes. Synthetic detergents useful in such cleaning and cleaning compositions are well known in the art and include anionic, cationic,
Included are amphoteric and nonionic detergents or surfactants, and the like. Generally, surfactants that exhibit better properties in terms of foaming, cleanliness and end result attributes are anionic detergents. Therefore, most detergent and detergent formulations used for cosmetics contain anionic surfactants as one of the active ingredients. However, these surfactants tend to be extremely irritating to the skin and eyes at conventional usage levels, ie, levels above 10% based on the weight of the total composition. For this reason, cleaning compositions used for cosmetics containing anionic surfactants have been modified by using instead significant amounts of nonionic surfactants.
These nonionic surfactants are generally mild, but have poor foaming and cleaning abilities. Certain amphoteric surfactants are also reported to have low ocular irritation. Although a large number of cleaning agents and cleaning compositions are commercially available, there remains a strong desire to develop compositions that are less irritating without sacrificing desirable properties such as cleaning and foaming properties. Compositions comprising both amphoteric and nonionic surfactants incorporated into cleaning compositions containing anionic surfactants have been disclosed in several US patent specifications. For example, US Pat. Nos. 2,999,069 and 3,055,836 disclose shampoo compositions comprising specific mixtures of ethoxylated anionic, amphoteric and polyethoxylated nonionic surfactants. Additionally, U.S. Patent No. 3928251
No. 4,923,603 discloses shampoo compositions comprising a specific mixture of anionic, nonionic and zwitterionic surfactants. Similarly, US Pat. No. 3,950,417 discloses shampoo compositions characterized by low eye irritation. In these compositions, the anionic surfactant is modified by the addition of nonionic and amphoteric surfactants. All of these compositions contain an anionic surfactant and a nonionic surfactant as essential ingredients. As mentioned above, these surfactants have various drawbacks. It is therefore an object of the present invention to provide improved cleaning and cleaning compositions. Another object of the invention is to provide improved cleaners and cleaner compositions that are less irritating to the eyes and skin. Another object of the invention is to provide improved cleaning and cleaning compositions that exhibit good foaming properties and excellent foam stability. Other objects of the invention are described below. Also,
It will become clear from the detailed description of the invention below. The foregoing and other objects and advantages of the present invention are achieved by a cleaning and cleaning composition comprising a synergistic mixture of surfactants with low eye and skin irritation and good foaming properties. be done. More particularly, the present invention relates to cleaning and cleaning compositions comprising synergistic mixtures of certain amphoteric compound-fatty acid complexes and certain anionic surfactants containing at least one carboxylic acid moiety. In short, the present invention provides a combination of a specific amphoteric compound-fatty acid complex and a specific anionic surfactant of about 1
and a synergistic mixture in a ratio of 4 to 4 to 1. As used herein, the term "synergistic mixture" refers to a mixture of two separate compounds that exhibits a degree and quality of initial cell height that is greater than the sum of the initial cell heights of the individual compounds. The particular amphoteric compound-fatty acid complexes found to be useful in the present invention are generally non-zwitterionic and are represented by the formula: [wherein R ₁ is alkyl containing about 6 to 18 carbon atoms or substituted alkyl and mixtures thereof; R ₂ is alkyl containing about 8 to 18 carbon atoms and mixtures thereof or formula (wherein R ₃ is alkylene containing 8 to 18 carbon atoms; Z is hydrogen or alkyl containing 1 to 4 carbon atoms; Y is alkylene containing 1 to 4 carbon atoms; It is a lower alkyl containing.)
A ₁ and A ₂ are the same or different, [-CH ₂ CH ₂ -COOX] _o [-CH ₂ -COOX] _o [-CH ₂ CHOH-CH ₂ -SO ₃ ^] _o ^[ —CH ₂ ^{CHOH —} _{CH 2} —OPO ₃ is an integer of ). However, if only one of A ₁ and A ₂ is selected from the anionic salt moieties described above, the other can also be lower alkyl or lower hydroxyalkyl containing 1 to 4 carbon atoms. ] The amphoteric compound-fatty acid complexes useful in the present invention are novel compounds and are disclosed and claimed in Japanese Patent Application No. 57-035970. The complexes can be prepared according to the methods disclosed therein. Representative examples of amphoteric compound-fatty acid complexes useful in the present invention are as follows. (In the formula, R ₁ is a C ₁₁ H ₃₃ —C ₁₈ H ₃₇ mixture.) (In the formula, R ₁ is 80% of tallow fatty acid and coconut fatty acid/
20% mixture. ) (In the formula, R ₁ is tallow fatty acid, R ₂ is C ₁₁ H ₂₃ -
It is _{a C17H35} mixture. ) (In the formula, R ₁ is 70% of lauric acid and myristic acid.
%/30% mixture. ) (In the formula, R ₁ is tallow fatty acid.) (wherein R ₁ is a C ₆ H ₁₃ -C ₁₈ H ₃₇ mixture.) The amphoteric compound-fatty acid complexes useful in the compositions of the present invention have a range of from about
50%, preferably about 5-15% based on the total weight of the composition. Particular anionic surfactants found useful in the present invention are those containing at least one carboxylic acid moiety, including sulfosuccinates, alkyl carboxylates, alpha-sulfo fatty acids and selected from the group consisting of α-sulfo fatty acid esters, alkyl succinates, alkyl sarcosinates and fatty acid-protein condensates. All of these compounds are well known in the art and can be prepared by conventional methods. Sulfosuccinates are represented by the following general formula. This compound can be prepared by reacting maleic acid with a suitable fatty alcohol followed by addition of NaHSO ₃ to the double bond. The α-sulfo fatty acids and α-sulfo fatty acid esters are each represented by the following general formula. and These can be produced by sulfonating appropriate fatty acids and fatty acid esters. Alkyl carboxylates are represented by the following general formula. R—O[(CH ₂ ) ₂ O] _a —CH ₂ COOX (where a is 1 to 4) These compounds are synthesized using Williamson's ether synthesis method, which consists of reacting an alkoxide with chloroacetic acid. It can be manufactured by Alkyl succinates are represented by the following general formula. Alkyl succinates are reaction products of suitable fatty alcohols with succinic acid or succinic anhydride. Alkyl sarcosinates are represented by the following general formula. Alkyl sarcosinates are the reaction products of suitable fatty acids with lower substituted amines such as glycine or N-methylglycine. The fatty acid-protein condensate is represented by the following general formula. It is a reaction product of a suitable fatty acid and an amino hydrolyzate. Specific examples of suitable anionic surfactants are as follows. (In the formula, R is a 50/50 mixture of C ₁₂ H ₂₅ - C ₁₄ H _29. ) Anionic surfactants useful in the compositions of the present invention include about 2 to 50% by weight of the total composition;
Preferably from about 5 to 5, based on the weight of the entire composition.
It is blended in an amount of 40%. Further, to obtain the desired results of the present invention, the ratio of the amphoteric compound-fatty acid complex to the particular anionic surfactant is between about 4:1 and 1:4, preferably between about 2:1 and 1:4.
There should be a 1:2 ratio. When manufacturing various formulations and compositions, if necessary,
If compatible, dyes, preservatives, fragrances, which are commonly added to cosmetic detergent and cleaning compositions,
Other ingredients such as thickeners, opacifiers, conditioners, emollients, buffers, etc. may also be added in small amounts. Ingredients like dyes, preservatives and fragrances are usually
Together, they are incorporated in an amount of less than 2% based on the weight of the entire composition. Thickeners can be added to the composition in an amount of about 1% to about 3%, based on the total weight of the composition. The cleaning agent and cleaning agent compositions of the present invention may be in the form of either a liquid cleaning agent composition or a solid cleaning agent composition, as desired. Liquid detergent formulations using the compositions of the present invention are prepared by mixing the amphoteric compound-fatty acid complex and anionic surfactant at room temperature or at a temperature slightly above room temperature (approximately 50°C); It can be made by adding enough deionized water to bring the composition to about 3/4 of its intended weight. Other surfactants, various cleaning aids, fillers, carriers,
Other ingredients such as fragrances, preservatives, gelling agents, etc. are added as required, followed by the addition of the remaining water in an appropriate amount to reach the desired total volume. Then optionally a strong acid, e.g. HCl or a strong base, e.g. NaOH
Adjust the pH value within the desired range by adding . Solid detergent formulations using the compositions of the present invention are prepared by mixing the amphoteric compound-fatty acid complex and anionic surfactant in a rotary mixer with a steam jacket at a temperature within the range of 60-80°C. It can be manufactured by Other surfactants, fillers, whitening agents, and process oils can be added to the hot slurry as desired. After thorough mixing to obtain homogeneity and water balance, the product is cold rolled or drum dried into flakes. The dye and flavor are added to the flakes in a standard mixer with additional water to obtain a suitable solid product. After mixing thoroughly, the flakes are rolled and formed into a log,
Blanks are then cut out from this, and finally a solid product is produced. The eye irritation of the cleaning composition of the present invention is evaluated as follows.
Draize test method (JHDraize et al., “Toilet Goods
Assn.No.17”, May 1952, No.1, Proc.Sci.Sect)
It can be tested by a modified method. A 0.1 ml sample of the test neutral composition is instilled into one eye of a white rabbit, and the other eye is used as a control. Six rabbits are used for each composition. Observe the condition of the eyes 1, 24, 48, 72 and 96 hours and 7 days after the first instillation.
After the hourly observation, the second and third eye drops are applied. The results showed that even after 7 days there was no change in the appearance of the rabbit's eyes, or that the rabbit's eyes went from minimally irritating to extremely irritating and/or that the cornea was intact. Wide range of conditions, including turbidity. Ocular lesions are scored for the cornea, iris, and conjunctiva. The higher the evaluation score, the greater the irritation to the eyes. The obtained evaluation scores are integrated to obtain a total score for each observed value of the six rabbits, and then the average value is determined. The average score obtained indicates the degree of irritation of the test composition. In some cases, a qualitative evaluation of irritation, such as "none, weak, average, strong", can be made based on the average score. The well-known Ross-Miles foaming test method “Oil and
The cleaning compositions of the present invention exhibit high foaming values and, moreover, remarkable foam stability, as measured by a modified method of "Soap", 18.9-102 (1941). and 2.5 g of lanolin to 100 g of dioxane. The lanolin is first mixed with 25 c.c. of dioxane. The mixture is heated on a steam bath for 45 minutes to dissolve the lanolin in the dioxane. The mixture is then heated on a steam bath for 45 minutes. Add remaining dioxane and mix. This lanolin-dioxane solution must be stored in an amber bottle and freshly prepared on the day of testing. 4 g of composition to 376 c.c. of distilled water. and then dilute the test composition by adding with mixing 20 c.c. of the lanolin-dioxane solution described above.
When adding the lanolin-dioxane solution to the aqueous solution of the test composition, heat is generated, so the temperature of the solution is
Care must be taken to maintain the temperature within 25°C. Therefore, both the test composition aqueous solution and the lanolin-dioxane solution must be at 23° C. before mixing. To avoid precipitation of lanolin, the lanolin-dioxane solution must be cooled slowly. Thus, 24-25℃
A final solution at a temperature of is obtained. The final solution consisting of the test composition, water, dioxane and lanolin was then mixed with the modified
Test as usual in a Ross-Miles foam column. All tests are performed twice and the two results are averaged. Cell stability is determined by measuring the rate of decrease in cell height after 2 minutes. The reduction rate is expressed as a percentage of the original height. Specific embodiments of the invention are illustrated by the following representative examples. However, the invention is not limited by the specific limitations set forth in each example, but only by what is set forth in the claims. Examples 1-9 By mixing the surfactant components, adjusting the pH to 7.2 ± 0.2 with dilute acid or base as necessary, and adding an appropriate amount of deionized water to bring the total volume to 100%. The following compositions were produced.

Table: Example 10 The compositions of Examples 1-9 were tested for hard water foaming using a modification of the Ross-Miles method described above. The results are shown below. Example Initial bubble height in 200 ppm hard water (mm) 1 358 2 330 3 348 4 330 5 330 6 365 7 375 8 368 9 378 As can be easily understood from the above results, the specific amphoteric compound of the present invention - Compositions containing mixtures of fatty acid complexes and anionic surfactants (Examples 6-9) synergistically increase initial cell height. Furthermore, the bubbles produced by the composition of the present invention are qualitatively superior to the bubbles of other compositions in that they are denser and creamier than the bubbles of other compositions. The resulting bubbles with such properties are not only perceived by consumers to be better, but also capture dirt better than the more continuous and lacy bubbles of the compositions of Examples 1-4; And, because of its slightly better floating properties, dirt can be removed more easily. Example 11 In a rotary mixer with a steam jacket, 23.7 parts by weight of stearic acid, 13.3 parts by weight of dextrin, 35.1 parts by weight of disodium sulfococcoate, and the compound
A solid detergent composition was prepared by adding 14.2 parts by weight of A, 0.2 parts of titanium dioxide and 10.0 parts of water. The mixture was heated to 50-60 °C, mixed until homogeneous, and the PH was adjusted to 7.2 ± 0.2 with 50% NaOH solution. The resulting product was cooled, rolled into flakes, ground, shaped into logs, and finished into a solid detergent having the following composition. Ingredient content (% wt/wt) Stearic acid 23.7 Dextrin 13.3 Disodium sulfococcoate 35.1 Compound A 14.2 TiO ₂ 0.2 50% NaOH 5.2 Deionized water 8.3 100.0 The obtained solid detergent foamed vigorously in hard and soft water. . No limescale deposits were formed.
Additionally, when this detergent was tested, it was found to be mildly irritating to the eyes. Example 12 A low PH solid detergent composition was prepared according to the method of Example 11. This composition had the following composition. Ingredient content (% wt/wt) Compound B 20.00 Stearic acid 15.00 Polyethylene glycol 4000 5.00 Dextrin 10.00 Talc 10.00 Disodium lauryl sulfosuccinate 35.00 Deionized water 5.00 100.00 Example 13 Liquid cream settsuken was prepared as follows. Manufactured. Compound C87.5 parts by weight and lauryl succinate
20.0 parts by weight was charged into a container equipped with a stirrer and a steam jacket, and heated to 45°C. The pH value was adjusted to 7.0±0.2 with dilute NaOH, followed by the addition of 1 part propylene glycol and 95 g deionized water. The mixture was cooled to 30°C, 2 parts of perfume were added and then filled into tubes. The product obtained had the following composition. Ingredient content (% wt/wt) Compound C 42.57 Lauryl succinate 9.73 Propylene glycol 0.48 Fragrance 0.97 Deionized water suitable Quantity 100% The product is a smooth, opaque, mild creamy gel that can be easily removed from the tube. I was able to dispense a small amount. Example 14 An opaque water soap having the following composition was prepared. Ingredient content (% wt/wt) Compound D 30.0 Lauryl sarcosinate 20.0 Polyethylene glycol 6000 distearate
3.0 Deionized water as appropriate Total volume 100 The PH value of the above formulation was adjusted to 6.0 with dilute HCl. Example 15 An opaque water soap having the following composition was prepared. Ingredient blending amount (% wt/wt) Sulfosuccinate 3.00 Compound A 2.50 Ammonium lauryl(3) ether sulfate
3.00 Polyoxyethylene 80 Sorbitan Monolaurate 5.00 Preservatives 0.10 Dyes and Fragrances 0.25 Deionized Water as per Total Volume 100.00 The PH value of the above formulation was adjusted to 6.0 with dilute HCl. Besides the preferred embodiments described above, other embodiments, changes and modifications can be made by those skilled in the art within the spirit of the invention and the scope of the claims.

Claims (1)

[Scope of Claims] 1. A hypoallergenic detergent and cleaning agent composition whose active ingredients consist of the following (a) and (b): (a) 1 to 50% by weight of an amphoteric oxide-fatty acid complex of the following formula: : [wherein R ₁ is alkyl containing 6 to 18 carbon atoms or substituted alkyl and mixtures thereof; R ₂ is alkyl containing 8 to 18 carbon atoms and mixtures thereof or (wherein R ₃ is alkylene containing 8 to 18 carbon atoms, Z is a hydrogen atom or lower alkyl containing 1 to 4 carbon atoms, and Y is a hydrogen atom or lower alkyl containing 1 to 4 carbon atoms. lower alkyl); A ₁ and A ₂ are the same or different; (-CH ₂ CH ₂ -COOX) _o (-CH ₂ -COOX) _o (-CH ₂ CHOH- _{CH 2} —SO ₃ X) _o (—CH ₂ CHOH—CH ₂ OPO ₃ selected from the group. However, if only one of A ₁ and A ₂ is selected from the above anionic salt moieties, the other one has one carbon atom
and (b) sulfosuccinates, alkyl carboxylates, α-sulfo fatty acids and α-sulfo fatty acid esters, alkyl succinates. ,
2 to 50% by weight of an anionic surfactant selected from the group consisting of alkyl sarcosinates and fatty acid-protein condensates. 2. The composition according to claim 1, wherein the amphoteric compound-fatty acid complex and anionic surfactant are blended in a ratio of 1:4 to 4:1. 3. The composition according to claim 1, wherein the amphoteric compound-fatty acid complex has the following formula: (wherein R ₁ is a C ₁₁ H ₂₃ -C ₁₈ H ₃₇ mixture). 4. The composition according to claim 1, wherein the amphoteric compound-fatty acid complex has the following formula: (wherein R ₁ is a C ₆ H ₁₃ —C ₁₈ H ₃₇ mixture). 5. The composition according to claim 1, wherein the amphoteric compound-fatty acid complex has the following formula: A composition as shown in 6. The composition according to claim 1, wherein the amphoteric compound-fatty acid complex is blended in an amount of 5 to 15% based on the weight of the entire composition. 7. The composition according to claim 1, wherein the anionic surfactant is an alkyl sarcosinate. 8. The composition according to claim 1, wherein the anionic surfactant is sulfosuccinate. 9. The composition according to claim 1, wherein the anionic surfactant is an alkyl succinate. 10. The composition according to claim 1, wherein the anionic surfactant is blended in an amount of 5 to 40% based on the weight of the entire composition.