KR840001999B1 - Surfactant compositions - Google Patents

Abstract

A surfactant compsn. consists of a 0.5-10 wt.% triester of phosphoric acid of formula (I) and a less than 15 wt.% surfactant selected from cationic, non-ionic, or anionic surfactants. In the formulas, R1, R2, and R3 are indepenently selected from (II) or (III); R4, R5, and R6 are independently alkyl, alkenyl, hydroxyalkyl, arylalkyl, or polyoxyalkylated ether contg. 1-22 carbon atoms with the proviso that at least of R4, R5, and R6 contains at least 8 carbon atoms. R5 and R6) can form a heterocyclic structure together with nitrogen; R7 is alkylene or mono-or polyoxyalkylene; R8 is H, alkenyl; or cycloalkyl; X is Cl-, Br-, or anion; and n is 1-10.

Description

Surfactant composition

The present invention relates to a surfactant composition. In particular, the present invention relates to hairdressing and cleansing surfactant compositions which, when used as soft and cosmetic preparations, do not irritate skin and eyes.

It is known that hair and hair after shampoo treatment are difficult when the hair is treated with washing or shampoo. That is, in the case of shampoo treatment, the hair is entangled and static electricity is generated on the hair, thus the hair is generally unattractive or wind blowing.

In order to cope with this problem in the treatment of shampoos, numerous hair styling products have been developed for use on hair after shampoo treatment. These products generally can easily eliminate tangles and reduce electrostatic charge, making the hair more manageable and attractive.

Although these shampoos are effective for hair-setting, they also have some drawbacks. In other words, the shampoo must be used after the shampoo after a separate operation from the shampoo treatment process itself, which is expensive and consumes time. In addition, these hair shampoos of the prior art had the disadvantage of making the hair covered with a thick viscous coating and thus greatly reducing the sensory cleanliness of the hair. As a result of this latter disadvantage, there is a need for shampooing the hair that has been more frequently hair-set than uncoated hair.

Numerous conventional hairdressing shampoos have also been developed that combine the cleaning and hairdressing steps into a single shampoo treatment. As a conventional hairdressing shampoo, it was possible to simplify the process of obtaining hair that was cleanly haired, but the hair that had been hairdressed was still thickly coated with a viscous material and still had low sensory cleanliness. In addition, these hair shampoos often caused eye irritation. Exemplary conventional hairdressing shampoos include those listed on page 112 of "Soap, Cosmetics, Chemical Specialties" published in September 1974.

It should be noted that sensory cleanliness and hairdressing cannot be done simultaneously, regardless of whether the shampoo and hairdressing products are used separately or when a product that can achieve both functions is used. Accordingly, one object of the present invention is to provide a surfactant composition effective for washing and hair washing of hair in a single use.

Another object of the present invention is to provide a surfactant composition that is soft and does not cause skin and eye irritation.

Another object of the present invention is to provide a surfactant composition that can be soft and also used as fabric cleaners and softeners.

These and other objects of the present invention will become apparent to those skilled in the art by the following detailed description.

The surfactant of the present invention contains, as an active ingredient, at least one surfactant selected from the group consisting of a cationic triester of phosphoric acid and an anion, nonionic, cationic, and amphoteric detergent.

The remaining amount of the composition may consist of various conventionally known detergent adducts and detergent adducts, filler carriers, and the like.

The cleaning and hairdressing surfactant compositions of the present invention comprise, as active ingredients, phosphate cationic triesters and one or more other surfactants.

Cationic triesters of phosphoric acid useful in the present invention are novel compounds represented by the following general formula (I).

In Formula (I), R ₁ , R ₂ , and R ₃ are the same or different groups selected from the group represented by the following Formulas (II) and (III), wherein R ₄ , R ₅ , and R ₆ is the same or different alkyl, alkenyl, hydroxyalkyl, arylalkyl or polyoxyalkylated ether from each other containing 1 to about 22 carbon atoms, provided that at least one of them contains 8 or more carbon atoms, And R ₅ and R ₆ together with the nitrogen atom to which they are attached may form heterocyclic structures such as morpholine, thiomorpholine, indole and the like; R ₇ is alkylene or mono or polyoxyalkylene of 2 to 12 carbon atoms which may be substituted with alkyl, alkoxy, hydroxy or hydroxyalkyl groups of up to about 10 carbon atoms; R ₈ is hydrogen, alkyl up to 7 carbon atoms, hydroxyalkyl, alkenyl or cycloalkyl or polyoxyalkylated hydroxy alkyl up to 10 carbon atoms; n is an integer from about 1 to 10; Further X is C1 ^- is an anion, or the like ^-, Br.

Representative of the useful phosphate triesters of the present invention include compounds having the following structure.

* Ra is a 1: 1 ratio mixture of C ₂₀ H ₄₁ and C ₂₂ H ₄₅ .

The amount of phosphate triester used in the cleaning composition of the present invention is used in the range of 0.5 to 10% by weight of the total composition when the composition of the present invention is used as a cleaning and hairdressing composition, and when the composition is used as a fabric softener, To 5% by weight.

It has been found that the aforementioned phosphate cationic esters can be combined with other known surfactants. The fact that cationic phosphate triesters are generally easily blended with other surfactants, and especially with anionic surfactants, to form various detergent compositions, suggesting that cations and the like generally do not blend easily with other surfactants. Considering the facts and the difficulty in the process was surprising results.

This unexpected harmonization between the particular phosphate triesters and anionic surfactants described herein has made it possible to obtain highly desirable hairdressing and cleaning compositions, as the anionic surfactants are excellent clean and foamed compounds.

A preferred embodiment of the present invention relates to a cleaning and hairdressing detergent composition comprising a phosphate ester and at least one surfactant selected from the group consisting of amphoteric, nonionic, anionic and cationic detergents. Examples of amphoteric surfactants that may be used in the present invention include betaine, sultaine, phosphobetaine, phosphitane, n-alkylamino propionate and n-alkylimino dipropionate.

Betaine and sultine surfactants useful in the present invention are described in US Pat. No. 3,950,417, issued April 13, 1976, which is incorporated herein by reference.

Phosphobetaines and phosphitanes useful in the present invention are described in United States Patent Application Nos. 965,461 and 965,462, respectively, filed November 30, 1978, which is incorporated herein by reference. n-alkylamino propionate and n-alkylimino dipropionate are sold under the trade name Deriphat by General Mills. Examples of preferred betaine amphoteric surfactants include cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethyl-α-carboxyethylbetaine, cetyldimethylcarboxymethylbetaine, lauryl-bis- (2 Alkylbetaines such as -hydroxyethyl) carboxymethylbetaine, oleyldimethyl-gamma-carboxypropylbetaine, lauryl-bis- (2-hydroxypropyl) alpha -carboxyethylbetaine and the like; Sulfines, such as cocodimethylpropylsultine, stearyldimethylpropylsultine, lauryl-bis- (2-hydroxyethyl) propylsultine and the like; And sulfines such as cocoamidodimethylpropylsultine, stearylamidodimethylpropylsultine, laurylamido-bis- (2-hydroxyethyl) propylsultine, and the like.

Examples of preferred phosphobetaines include laurylmidamido 3-hydroxypropyl phosphobetaine, cocamido disodium 3-hydroxypropyl phosphobetaine, laumiristamido disodium 3-hydroxypropyl phosphobetaine Lauryl list amido glyceryl phosphobetaine, laumir list amido carboxy disodium 3-hydroxypropyl phosphobetaine and the like.

Examples of preferred phosphites are cocoamidopropyl monosodium phosphitane, laumiristamido propyl monosodium phosphitane and analogs thereof. Examples of preferred n-alkylamino propionates and n-alkylimino dipropionates include compounds having the following general formula and mixtures thereof.

R in the above general formula has about 8 to 22 carbon atoms. Amphoteric detergents may be present in an amount from 2 to 10 weight percent of the total composition.

의 술폰산 알킬모노글리세릴에테르 ; 일반식

의 황산 알킬모노글리세리드 ; 일반식

의 술폰산 알킬모노글리세리드 ; 일반식 RSO₃X의 술폴산 알킬 ; 일반식Anionic surfactants may be used in the composition of the present invention, and examples thereof include alkyl sulfate of general formula R—CH ₂ —OSO ₃ X; Alkyl sulfate of general formula R (OCH ₂ CH ₂ ) —OSO ₃ X; General formula

Sulfonic acid alkyl monoglyceryl ethers; General formula

Sulfuric acid alkyl monoglycerides; General formula

Sulfonic acid alkyl monoglycerides; Alkyl sulfolate of the general formula RSO ₃ X; General formula

Sulfonate alkylaryl; General formula

의 술포숙신산 알킬 ; 일반식

의 사르코신산알킬 일반식

의 이세티온산 아실 ; 일반식

의 라우르산 알킬 메틸 ; 일반식

의 지방산 단백질 축합물 ; 일반식 RO(CH₂CH₂O)q-CH2CO2X의 카르복실산 알코올 에테르 ; (여기서 R는 7개 내지 17개 탄소원자를 가진 고급알킬 ; R' 및 R"는 각각 수소, 저급알킬, 히드록시저급알킬, 티오저급알킬, 카르복실저급알킬, 아미노저급알킬, 벤질 및 P-히드록시벤질로 구성된 군으로 부터 선정한 것이며 ; X는 알칼리 금속이온, 알칼리토금속이온, 암모늄이온 및 1개 내지 3개 저급알킬로 치환된 암모늄이온이고 ; P는 약 3 내지 약 6의 정수이고 ; q는 2 내지 6의 정수이며, 또 r는 2 내지 10의 정수이다) 및 그 유사체와 같은 것들을 들 수 있다. 음이온 계면활성제의 바람직한 형태는 황산알킬에테르이며, 보다 바람직하게는 P가 1 내지 5인 황산 나트륨트리데실알코올에테르이다. 음이온 세정제는 전체 조성물의 약 2 내지 10중량%의 량으로 존재할 수 있다.

Alkyl sulfosuccinate; General formula

Alkyl Sarcosinate Formula

Acetionic acid acyl; General formula

Alkyl methyl laurate; General formula

Fatty acid protein condensates; Carboxylic acid alcohol ether of the general formula RO (CH ₂ CH ₂ O) q-CH ₂ CO ₂ X; Wherein R is higher alkyl having 7 to 17 carbon atoms; R 'and R "are hydrogen, lower alkyl, hydroxy lower alkyl, thio lower alkyl, carboxy lower alkyl, amino lower alkyl, benzyl and P-hydride, respectively Selected from the group consisting of oxybenzyl; X is an alkali metal ion, alkaline earth metal ion, ammonium ion and ammonium ion substituted with 1 to 3 lower alkyl; P is an integer from about 3 to about 6; q is And an analog thereof, and an analog thereof, and the like. Preferred forms of the anionic surfactants are alkyl sulfates, more preferably P is 1-5. Sodium tridecyl alcohol ether Anionic detergent may be present in an amount of about 2 to 10% by weight of the total composition.

Examples of useful nonionic detergents include phenol and alkylene oxide ethers of fatty alcohols and alkyl mercaptans; Alkylene oxide esters of fatty acid amides; Condensation products of partial fatty acid esters with ethylene oxide and mixtures thereof. The polyoxyalkylene chains of such cleaners may contain 5 to 100 alkylene oxide units, with each alkylene unit having from 2 to 3 carbon atoms.

Preferred nonionic surfactants in the compositions of the present invention are water-soluble polyoxyethylene derivatives of hydrophobic bases, which are members of the group consisting of reaction products of 9-20 carbon atom fatty acid monoesters of aliphatic polyhydric alcohols. The alcohol contains at least 3 hydroxyls and at least 10 moles of ethylene oxide and preferably about 10 to about 100 moles of ethylene oxide.

The nonionic surfactant may be present in an amount of about 2 to 30 weight percent of the total composition.

Suitable cationic surfactants for these compositions include stearyl dimethylbenzylammonium chloride, cetyltrimethylammonium chloride, N bromide, N-dioctadecyl-N, N, N ', N'-tetramethyl-1,5 (3oxaphene). Mono and bis-4-tertiary ammonium halides such as styrene) di-ammonium; Tertiary salts such as hydrochloric acid cochamidopropyldimethylamine and citric acid stearylamidopropyldimethylamine; Cationic polymers such as hydroxyethylcellulose reacted with epichlorohydrin and then quaternized with trimethylamine (polymers of this type are sold by Union Carbide under the trade name polymer JR). Can be.

Cationic surfactant should be present in an amount of about 1 to 5% by weight of the total composition.

The total amount of the active surfactant components of the present invention should not exceed 50% by weight, preferably 10-30% by weight of the total composition to avoid irritation problems, wherein the total amount of the anionic surfactant and amphoteric surfactant is 15% of the total composition. It should not exceed weight percent.

In addition, small amounts of other conventional ingredients added to body surfactant compositions, such as paints, preservatives, incense burners, milk whites, thickening agents, modifiers, thickeners, buffers and the like, may also be added.

Ingredients such as paints, preservatives and fragrances all together typically comprise less than 2% by weight of the total composition. The thickener can also be added to the composition in an amount of about 1 to about 3 weight percent of the total composition.

The cleaning and hair surfactant composition of the present invention may be a composition that will result in a final composition that can be used by dilution with water or other diluent, or a final cleaning composition that can be used without modification at all.

The composition of the present invention is useful as a hair dressing composition, a shampoo treatment and a hair dressing agent and a cream rinsing agent, and these compositions can be used as liquid soaps and tablets, such as a composition for baby baths, and as a bubble bath composition and a composition suitable for cleaning animals and abiotic animals. Can be.

The above-described cleaning and hair-forming surfactants mix the phosphate triester with other surfactants at room temperature or slightly higher (about 50 ° C.) and then add sufficiently desalted water to prepare the composition at about four quarters of the desired weight. To produce.

The pH is adjusted within the range of 4-9, preferably 6-8 by addition of strong acid HCl or asbestos NaOH if necessary.

Other ingredients such as viscosity enhancers, preservatives, paints, fragrances and the like are mixed before adjusting the pH and adding excess water.

The cleaning and hair-styling surfactant compositions of the present invention are described in the following, published in May 1952 by the following modified Draize Test (JH Draize) et al. Can be tested for irritation.

0.1 ml of the neutral composition sample under test was placed in one eye of the albino rabbit and the other eye was observed as a control. Six rabbits were used for each composition test. Observations were made after 1, 24, 48, 72 and 96 hours and 7 days of initial eye drops; Second and third eye drops were performed after 24 and 48 hours observation. The results after seven days ranged from no change or only mild to a slight stimulus to the appearance of the rabbit's eye, to severe irritation and / or complete corneal haze.

Ocular injury was recorded as a large number indicating more severe stimulation of the eye on the cornea, iris and connective membrane, and the results were summed up to obtain a total value of 6 rabbits and averaged.

Average values represent the stimulating ability of the composition under test. Based on this average value, the degree of stimulation can be described as nothing, slightly, normal, or extreme.

After combing the wet hair, the hairdressing characteristics of hair trimming, gloss, body and dry hair sensation were evaluated as a hair salon study as follows.

The hair of the panelist was washed and divided into two equal parts, starting from the center of the forehead and softening to the center of the back of the neck.

A specific amount of test composition was used for one part of the hair of the two meals described above and an equivalent amount of control composition was used for the hair of the other part. The compositions penetrated into the hair and the features appeared and the hair was carefully washed so that water from one hair would not mix into the hair of the other. The cleaning characteristics were carefully observed.

Wet hair combing was evaluated by passing different combs through each part from the center to the end of the hair. After the hair was dried, the degree of combing of the dried hair, the degree of curling of the hair, the degree of handling of the hair, the degree of gloss, body and dry hair were evaluated. All these characteristics were subjectively assessed by trained and experienced evaluators based on ratios 1 (very bad) to 7 (excellent).

Specific examples of cleaning and hairdressing compositions prepared according to the present invention are described as the following representative examples. However, it should be noted that the present invention is not limited to the details described in the individual embodiments, but is limited by the claims.

Example 1

200 g of demineralized water is placed in a container with a stirrer, and 10 g of hydroxyethyl cellulose is added thereto, followed by heating the mixture to 70 ° C. to prepare a hair cream composition. Then 20 g of Compound A were added followed by 5 g of stearyl alcohol and 0.2 g of paint. The mixture was cooled to 30 ° C. and citric acid was used to adjust the pH to 5.0. 2 g of aroma and sufficient demineralized water were added so that the total mixture was 1000 g, resulting in a composition consisting of the following components.

% W / W% W / W

Compound A 2.00 Paint .02

50 Stearyl Alcohol .20

Hydroxyethyl cellulose 1.00 demineralized water q.s.to 100%

The pH was adjusted to 5.0 using citric acid. Hairdresser studies have shown that wet hair combing is a good hair cream composition that is repelled.

Example 2

A hair shampoo composition was prepared according to the general method of Example 1, and the composition consisted of the following components.

% W / W% W / W

Compound A 0.10 Paint .01

Stearyl Alcohol 2.00 Direction .20

Sodium lauryl ether 12.00 demineralized q.s.to 100%

Lauric acid diethanolamide 4.00

The pH was adjusted to 7.5 using HC1.

Hairdressing studies have shown that it is an excellent hairdressing shampoo composition that is well bubbled, washed and well-dressed.

Example 3

A cream liquid shampoo composition was prepared according to the general method of Example 1, and the composition consisted of the following components.

% W / W

Compound C 3.00

Polymer JR-4-(trademark of union carbide; .50 quaternary ammonium substituent

With chains of anhydroglucose units with a constituent axis

Water soluble cationic cellulose ether)

Amidobetaine 5.00

Sodium Tridecyl Sulfate (4) Ether 5.00

Paint .02

Dowicil 200 (trademark 1- (3-chloroalkyl) of the Dow Chemical Company 0.20

Cis-isomer of -3,5,7-triaza-1-chloride azone adamantine)

Direction .20

Demineralized q.s.to 100%

The pH was adjusted to 6.5 using Stric Acid.

Hairdresser studies have shown that this composition is an excellent composition that cleans the hair well and eliminates tangles.

Example 4

The chief cream wash composition was prepared according to the general method of Example 1 and consisted of the following ingredients.

% W / W% W / W

Compound C 1.10 Isostearyl Alcohol 0.33

Ethyl, n, n-dihydroxypropyl 0.55 hydroxyethyl cellulose 0.88

4-Aminobenzoate Sodium Hydroxide 0.02

Benzyl alcohol0.55 demineralized q.s.to 100%

Stearyl Alcohol 0.88

The ocular stimulation was tested by the modified Draze test described above and it was confirmed that the composition described above had some irritation.

Example 5

Fine compositions of fabric cleaners and softeners were prepared consisting of the following components:

% W / W% W / W

Sulfonic acid linear dodecylbenzene 8.00 Isopropar 1.00

Compound C 3.00 Paint .02

Coconut monoethanolamide 2.00 direction .10

Citric acid 10.00 demineralized water q.s.to 100%

Optical Brightener .50

The pH was adjusted to 5.0 using citric acid.

The composition of Example 5 was evaluated for cleaning power and softening property using the following method:

Test Fabrics Inc. The standard fouling wool of was used to evaluate the relative cleanability of a given composition.

The cleaning behavior was tested using Terg-O-Tometer model 7243. The conditions were adjusted as follows:

1. Washing time (5 minutes) 4. Marching speed (100 rpm)

2. Washing speed (100rpm) 5. Washing and marching speed (105 ℉)

3. March time (5 minutes)

The test fabric was made of wool chalis and made of 10 yards.

A contaminant mixture, primarily lamp black and oil and commercial solvents, was applied to the printing rolls so that only half of the 8-inch-wide fabrics were contaminated.

Since the test fabric was cut into 4 × 8 inch pieces, half of each of the three pieces described above was contaminated and the other half was not contaminated. A Gardner Color Difference Meter was used to measure the initial color (pure whiteness) of the contaminated and uncontaminated portions of each piece.

These three fragments, such as three 4 × 8 inch cotton filled fragments, were placed in a Terg-O-Tometer beaker with 1000 ml of 10% aqueous solution of the test composition.

Prior to this, the solution was stirred for 2 minutes and equilibrated at 105 ° F. The samples were stirred for 5 minutes, taken out and pressed and returned to a stirring beaker containing 1000 ml of clean 105 ° F tap water.

After stirring for 5 minutes, these three pieces were taken out, compressed, and spread to dryness. The dried was again evaluated using a sector difference meter to determine how much contamination was removed and how much contamination was attached to the uncontaminated portion of the woven fabric. This relative cleaning effectiveness was expressed according to the distribution of initial and pure whiteness measurements characterized by ΔR.

Two units of ΔR were considered to be excellent. To measure the flexibility, the measurers were asked to select a more flexible fabric in hand from a pair of groups containing fabrics treated with the test composition and fabrics treated with the control composition. This sample composition was evaluated as described above and found to provide excellent cleaning and flexibility for the test fabric.

Example 6

Gentle shampoos and hairdressing compositions were prepared containing the following ingredients:

% W / W% W / W

Compound E 1.00 Dowicil 200 .10

Polymer JR-400 .20 Paint .02

Betaine 5.00 direction .03

Lauryl (3) ether sodium sulfate 5.00 demineralized water q.s.to 100%

Polyoxyethylene 80 SML 10.00

The pH was adjusted to 7.0 using citric acid. It was confirmed that the above-mentioned composition was a good shampoo and hair dressing composition.

Example 7

Soft gelled shampoos and hairdressing compositions were prepared containing the following ingredients:

% W / W% W / W

Amino Sultine 5.0 Compound D 1.0

Betaine 5.0 Dowicil 200 .10

Tridecyl sulfate (4) ether 10.0 paint .02

Monopalmitic acid polyoxyethylene (80) sorbitan 20.0 direction .20

Paints, preservatives Demineralized water q.s.to 100%

Compound a 1.0

pH was adjusted to 7.0 using citric acid. The above-mentioned composition was confirmed to be an excellent shampoo and hair dressing composition.

Claims (1)

Consists of at least one surfactant selected from the group consisting of anionic, nonionic, cationic and zwitterionic surfactants and phosphate triesters of the following general formula (I), phosphate triester content based on the total weight of the composition: About 0.5 to 10% by weight, anionic and zwitterionic surfactant content is less than about 15% by weight, and the total amount of the active surfactant is less than 50% by weight.

In Formula (I), R ₁ , R ₂ , and R ₃ are the same or different groups selected from the group represented by the following Formulas (II) and (III), wherein R ₄ , R ₅ , and R ₆ is the same or different alkyl, alkenyl, hydroxyalkyl, arylalkyl or polyoxyalkylated ether from each other containing 1 to about 22 carbon atoms, provided that at least one of them contains 8 or more carbon atoms, And R ₅ and R ₆ together with the nitrogen atom to which they are attached may form heterocyclic structures such as morpholine, thiomorpholine, indole and the like; R ₇ is alkylene or mono or polyoxyalkylene of 2 to 12 carbon atoms which may be substituted with alkyl, alkoxy, hydroxy or hydroxyalkyl groups of up to about 10 carbon atoms; R ₈ is hydrogen, alkyl up to 7 carbon atoms, hydroxyalkyl, alkenyl or cycloalkyl or polyoxyalkylated hydroxyalkyl up to 10 carbon atoms; n is an integer from about 1 to 10; Further X is C1 ^- is an anion, or the like ^-, Br.