JPH01144496A - Detergent composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having rinsing effect, giving low irritation to the skin and suitable as a shampoo for hair and body and detergent for clothes and tableware, by compounding a nonionic surfactant, specific cationic surfactant and a specific anionic surfactant at specific ratios. CONSTITUTION:The objective composition is composed of (A) a nonionic surfactant, (B) a cationic surfactant comprising (i) an imidazoline-type quaternary ammonium salt cationic surfactant of formula I (R1 is 12-22C alkyl or alkenyl; X is halogen or 1-2C lower alkyl sulfate) and/or (ii) a quaternary ammonium salt-type cationic surfactant of formula II (R2 is 16-22C alkyl; R3 is 1-2C alkyl or 16-22C alkyl; X is halogen or 1-2C lower alkyl sulfate; m and n are >=1; m+n is 2-30) and (C) a carboxylic acid salt-type anionic surfactant at a molar ratio (B/C) of 4/6-8/2.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is directed to a nonionic surfactant, an equally Dublin type or EO-added quaternary ammonium salt type cationic surfactant, and a carboxylate type anion. The present invention relates to a detergent composition that contains a surfactant and is used for hair or body shampoo, clothing or dishwashing detergent, etc.

[Prior Art] Generally, anionic surfactants and nonionic surfactants are used as the main ingredients in detergents for hair or clothing, but these surfactants alone do not have the ability to clean fabrics. However, it was not possible to impart a finish, especially a rinsing effect (softness) to the cloth. To impart this flexibility, attempts have been made to incorporate cationic surfactants, but since cationic surfactants are irritating to the skin, the amount that can be incorporated during washing has been limited. Therefore, although there is a demand for a product with a high rinsing effect, a cleaning composition with a sufficient rinsing effect has not been obtained so far.

[Problems to be Solved by the Invention] Therefore, the present inventors conducted intensive research to obtain a detergent that has a rinsing effect and is less irritating to the skin. Alternatively, it has been found that a composition obtained by combining an EO-attached quaternary ammonium salt type cationic surfactant and a carboxylate type anionic surfactant in a specific ratio is a cleaning composition that satisfies the above objectives. .

Generally, when an anionic surfactant and a cationic surfactant coexist in an aqueous solution, a complex is formed in the crystal phase, the complex becomes a precipitate, and the aqueous solution becomes cloudy or separates. That is, imidazoline type or E
The O-addition type quaternary ammonium salt type cationic surfactant is a sulfonate type such as a higher furkyl sulfonate, a sulfate ester salt type such as a higher alcohol sulfate ester salt, or a polyoxyethylene alkyl ether phosphate ester salt, etc. When mixed in an aqueous solution with an anionic surfactant such as a phosphate ester salt of imidazoline, a complex is formed in the crystal phase at any molar ratio, and the complex becomes a precipitate, making the aqueous solution cloudy or separated. For the combination of a quaternary ammonium salt type cationic surfactant or an EO addition type quaternary ammonium salt type cationic surfactant and a carboxylate type anionic surfactant, when they are made to coexist in a specific molar ratio in an aqueous solution, in the crystal phase. form a complex in solution. This complex is transparent, has an excellent rinsing effect, and is less irritating to the skin. However, although this complex has the above-mentioned advantages, it has the disadvantage that its cleaning power is inferior to that of a general cleaning agent.As a result of extensive research, the present inventors found that this composition By adding nonionic surfactant, rinsing effect,
The present invention was completed based on the discovery that detergency and foaming power can be imparted to the composition without sacrificing the advantage of skin safety.

[Means for Solving the Problems 1] That is, the present invention comprises: (1) one or more nonionic surfactants; and (2) an imidazoline quaternary ammonium salt cation represented by the following general formula (A). Surfactant and the following general formula (
B) contains one or more selected from the group consisting of quaternary ammonium salt type cationic surfactants and one or more carboxylate type anionic surfactants. , the molar ratio of [2]/[3] is 4/6
8/2.

(In the formula, R1 represents an alkyl group or alkenyl group having 12 to 22 carbon atoms, and X represents an anionic group selected from a halogen atom or a lower alkyl sulfate group in which the alkyl group has 1 to 2 carbon atoms.) (The following and Mihaku) (In the formula, R2 is an alkyl group having 16 to 22 carbon atoms, R3
is an alkyl group having 1 to 2 carbon atoms or 16 to 2 carbon atoms
2 represents an alkyl group, and X represents an anionic group selected from a halogen atom and a lower alkyl sulfate group in which the alkyl group has 1 to 2 carbon atoms.

As the nonionic surfactant used in the present invention, all nonionic surfactants used in ordinary detergents can be used. Specific examples include sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, venter 2
- Sorbitan fatty acid esters such as diglycerol sorbitan ethylhexylate, diglycerol tetra-2-ethylhexylate, glycerin monocottonseed oil fatty acid, glycerin monoerucate, glycerin sesquioleate, glycerin monostearate, α, α′-olein Examples include glycerin polyglycerin fatty acids such as glycerin acid pyroglutamate, glycerin monostearate malic acid, propylene glycol fatty acid esters such as propylene glycol monostearate, hydrogenated castor oil derivatives, and glycerin alkyl ethers.

Examples of the hydrophilic nonionic surfactant include POE sorbitan fatty acid esters such as POE sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, and POE sorbitan tetraoleate, and POE-POP hydrogenated lanolin. , POE-P
POE-POP alkyl ethers such as OP glycerin ether, tetra-POE and tetra-PO such as Tetronic
P-ethylenediamine condensates, POE castor oil, POE
Hydrogenated castor oil, POE hardened castor monoisostearate OE hydrogenated castor oil isostearate, POE
Cured and cured Castor monopyroglutamic acid monoisostearic acid diester OE Cured and cured Castor shimaleic acid PO
E castor oil hardened oil castor oil derivatives OE sorbitol POE beeswax lanolin derivatives such as beeswax, alkanolamides such as coconut oil fatty acid jetanolamide, lauric acid monoethanolamide, fatty acid isopropanol amide, POE propylene glycol fatty acid ester, P
Examples include OE alkylamine, POE fatty acid amide, trisaccharide fatty acid ester, POE nonylphenyl formaldehyde condensate, alkyl ethoxydimethylamine oxide, trioleyl phosphoric acid, and the like.

In the present invention, one or more of these nonionic surfactants may be selected and used. The blending amount is generally 5 to 40% by weight, preferably 8 to 30% by weight.

The quaternary ammonium salt type cationic surfactant used as a component of the composition of the present invention has the general formula (wherein R1 is an alkyl group or alkenyl group having 12 to 22 carbon atoms, and X is a halogen atom or represents an anionic group selected from lower alkyl sulfate groups whose alkyl group has 1 to 2 carbon atoms.
class ammonium salt type cationic surfactants, and general formula (wherein R2 is an alkyl group having 16 to 22 carbon atoms, R3
is an alkyl group having 1 to 2 carbon atoms or 16 to 2 carbon atoms
2 represents an alkyl group, and X represents an anionic group selected from a halogen atom and a lower alkyl sulfate group in which the alkyl group has 1 to 2 carbon atoms, and is one or more of m and ion surfactants.

The carboxylate type anionic surfactant used as a component of the composition of the present invention has, for example, the general formula (wherein R is an alkyl group or alkenyl group having 8 to 18 carbon atoms, M is an alkali metal, 11) A fatty acid soap type anionic surfactant represented by the general formula % formula % (wherein R is an alkyl group having 8 to 22 carbon atoms or An ether carboxylate type anionic surfactant represented by an alkylaryl group, n is O or an integer of 1 to 16, or represents two or more types, [1[) general formula % formula % (in the formula , R represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, and M represents one or more types of alkali metals, organic amines, and basic amino acids). Or, iv) represented by the general formula % formula % (wherein R represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, and M represents one or more types of an alkali metal, an organic amine, or a basic amino acid). In the general formula represented by a condensate of a higher fatty acid and an amino acid such as N-acylglutamate, anionic surfactants having a -COO- group can be mentioned.

In the present invention, one or more of these may be used.

In the present invention, the molar ratio of [2]/[3] is from 4/6 to
It is in the range of 8/2, preferably in the range of 515 to 7/3. In this composition, if the molar ratio is less than 4/6, the rinsing effect will be poor, and if the molar ratio is more than 8/2, the rinsing effect will be poor.
It is undesirable because it causes strong irritation to the skin. As for the blending amount, the total of (1) + (2) is 0.5 to 20 M%, preferably 1 to 15 M%, based on the total amount of the composition. If the amount is less than 0.5% by weight, sufficient rinsing effect cannot be obtained due to insufficient surfactant, and if the amount is more than 20% by weight, irritation to the skin becomes undesirable.

In the present invention, in addition to the above-mentioned essential components, an amphoteric surfactant can be added to the cleaning composition to improve low-temperature stability, and depending on the use, it is desirable to add an amphoteric surfactant. These amphoteric surfactants include 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium, 2-cocoyl-
Imidazoline amphoteric surfactants such as 2-imidazolinium hydroxide-1-carboxyethyloxy-2-sodium, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, etc. Examples include betaine-based amphoteric surfactants, alkylbetaines, aminobetaines, amine oxides, and sulfobetaines. Although there is no particular limit to the amount, it is generally 0.
．． It is 1 to 20% by weight, preferably 5 to 15% by weight.

Furthermore, the cleaning composition of the present invention may contain components and additives commonly used in cleaning agents. That is, oils such as higher alcohols, silicone oils, liquid paraffin, and ester oils, lustering agents such as polyethylene glycol fatty acid diesters, water-soluble polymers such as methyl cellulose and hydroxyethyl cellulose, and cation-modified cellulose ether derivatives [Polymer JR (Union Carbide Corporation)] cationic polymers such as polyglycol/polyamine condensates [Polycoat H (manufactured by Henkel Hakusuisha)], polyoxyethylene (hereinafter referred to as POE
Hydrogenated castor oil, nonionic surfactants such as POE alkyl ether, natural extracts of plants and animals and their derivatives, specific examples include licorice, paprika, linseed linseed, barberry, melaloo, mistletoe, malva, echinacea, and echinacea. , fucus, horsetail, oat, oakmoss, green mint, oak moss, Japanese elm, Japanese cypress, hemruta, bayberry, silverberry, cabbage, hayflower, baxen, elderberry, dust crocodile, cattail, pineapple, cabbage, bald oak, honey ginger, mafunori, black cabbage. Japanese moji, papaya, milesia, mandarin orange, mulberry, black-and-white violet, clara, camphor, parinsi, chichinori, banana, kouhone, black egret, chickweed, araria, hectodium, azuki bean, dog pomegranate, yellow dog, eggplant, cherry, juniper, shibari, shea, iris , honeysuckle, sorrel, sagebrush, melid, celery, geranium, yellowtail, Dutch strawberry, chinsai, Japanese pine,
Turmeric, dead nettle, tea, orange, sage, Japanese ivy, Japanese elderberry, Japanese juniper, Japanese yarrow, Japanese herb, Japanese mistletoe, mallow, nebula, thyme, Japanese cabbage, thyme, clove, chimpi, seaweed, chlorella, toki extract , calendula, spruce, tomato, hypericum, perforatum, perforatum, tormentilla, carrot, garlic, wild rose, birch, parsley, gentian, horsetail, ononis, hamamelis, para, fennel, horsetail, saffron, mustard, soapwort, hawthorn, saffron, Loquat, Sankuchisou, Butcher bloom, Grape, Butouri, Ivy, Loofah, Water-soluble lily, Nettle, Bodaiju, Hop,
Japanese cabbage, shiitake, pine casa, horse chestnut, Japanese horse chestnut, sapinosa, meritsa, melilot, peach, cornflower, eucalyptus, rhododendron, cypress, saxifrage, oil-soluble arnica, oil-soluble calendula, oil-soluble horsetail, oil-soluble nopara, brown algae, Valerian, oil-soluble yokuinin, lily, iodized garlic, mugwort, perilla, chinensis,
Chamomile, meadowsweet, apple, oat, peonies,
Apricot, lettuce, rosemary, lemon, Roman chamomile, ginger, amitsu, scallion, birch,
Kinotchigo, stevia, water-soluble arnica, scutellariae, ivy, cinchona, cucumber, aloe, burdock, gardenia, grapefruit, burdock, orensis, anthracola, red grape, acacia, althea, amacha, ginger, capsicum tincture, rosin, natural rubber Latex, gum arabic, ictamol, cantharis tincture, bukuriyo, sarunokoshikake, chorei, persimmon, collagen, bifidobacteria, pectin, yeast, royal jelly, water-soluble placenta extract, honey, shellac, etc., organic acids such as citric acid, lactic acid, chloride Sodium, sodium hydroxide, potassium hydroxide, monoethanolamine,
Basic compounds such as triethanolamine, inorganic salts such as potassium chloride, sodium carbonate, sodium phosphate, and sodium sulfate, inorganic builders, antioxidants, fragrances, coloring agents, preservatives, chelating agents, ultraviolet absorbers, etc. They can be blended as appropriate within a range that does not impair the effects of the invention.

[Example] Next, the present invention will be explained in more detail with reference to Examples. The present invention is not limited thereby. The effects were measured using the following test methods and evaluation methods.

Test method, evaluation method (1) Rinse effect Rinse effect is "smoothing", "gloss", "combability"
The survey was conducted using a panel of 15 women for each of the three items.

12 g of the sample was actually applied directly to the hair, rinsed with warm water, air-dried, and evaluated by sensory evaluation. Evaluation was performed on a four-level scale. o1 if extremely good
If it is good, it is indicated as 0, if it is fair, it is indicated as Δ, and if it is poor, it is indicated as X.

(2) Skin irritation It is known that skin irritation can be evaluated by the strength of the protein denaturation power (protein denaturation rate) of surfactants and surfactant compositions (Japanese Patent Publication No. 59-42038).
1. The skin irritation of the composition of the present invention was evaluated based on the protein denaturation rate based on this evaluation method.

Protein Denaturation Rate Utilizing aqueous high-performance liquid chromatography, the ovalbumin denaturation rate was measured using an absorption peak at 220 nm when a sample was added to an ovalbumin pH 7 buffered solvent at a sample concentration of 1%.

HO: 220 nn of ovalbumin + height of absorption peak H8: 22 when sample is added to ovalbumin buffer solvent
A high evaluation of the 0 nm absorption peak was performed using the following four-level evaluation.

0...Very low skin irritation - Ovalbumin denaturation rate less than 30% O...Low skin irritation - Ovalbumin denaturation rate 30% or more and less than 60% △... ... Moderate skin irritation - Ovalbumin denaturation rate of 60% or more and less than 80% × ... Strong skin irritation - Ovalbumin denaturation rate of 80% or more - N - - N - ) A cleaning composition having the composition described in Table 1 was prepared, and its rinsing effect and skin irritation were evaluated (Table 1).
is shown together with a comparative example. Examples in which additives and the like were added are also described.

(Left below) 1 U cover [1] Prepare a shampoo consisting of the following composition: cationic surfactant/anionic surfactant molar ratio 6/4),
Evaluation was performed in the same manner as in Examples 1 to 7.

(% by weight) Polyoxyethylene dodecyl ether (EO=12) 15.0 Polymer J R-4000,2 (manufactured by Union Carbide) Compound of general formula (B) [R2=18, R3=1, m10 =2, average molecular weight 41
6,
Appropriate amount of ion exchange water
Residue This shampoo had an excellent rinsing effect and was less irritating to the skin.

Kazumi JJLj1 Prepare a body shampoo with the following composition.Molar ratio of cationic surfactant/anionic surfactant is 7/3.
), and evaluated in the same manner as in Examples 1 to 8.

(% by weight) Polyoxyethylene octylphenyl ether (EO=10) 10.0 Compound of general formula (B) [R2=18, R3=1, m+n=2, average molecular weight 416, X=CL] 2.19 Lauroyl Sodium sarcosine (average molecular weight 310) 0.93 Dipropylene glycol 8.0 Aloe extract 0.5 Coloring agent, fragrance
Appropriate amount of preservatives and chelating agents
Appropriate amount of ion exchange water
Residue This body shampoo had an excellent rinsing effect and was less irritating to the skin.

Prepare a body shampoo with the following composition: cationic surfactant/anionic surfactant molar ratio 7/3
), and evaluated in the same manner as in Examples 1 to 9.

(% by weight) Polyoxyethylene oleyl ether (EO=8) 20.0 Polycoat H2.0 Coconut fatty acid jetanolamide 5.0 Compound of general formula (B) [R2=18, R3=1, m+n=4, average Molecular weight 5
04,
Appropriate amount of ion exchange water
Residue: This shampoo for hair had an excellent rinsing effect and was less irritating to the skin.

Example 1 - Prepare a body shampoo with the following composition: cationic surfactant/anionic surfactant molar ratio 6/4
) was evaluated in the same manner as in Examples 1 to 10.

(% by weight) 2-Undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium 2.0 Polycoat H1,0 Coconut fatty acid jetanolamide 0.5 Compound of general formula (B) [R2= 20, R3=1, m+n=10, average molecular weight 796, X=CL co 4.78 sodium lauroyl sarcosine (average molecular weight 310) 1.24 polyoxyethylene dodecyl ether (EO=14) 10.0 dipropylene glycol 1. 0 Coloring agent, fragrance Appropriate amount of ion exchange water
Residue This body shampoo had an excellent rinsing effect and was less irritating to the skin.

111L A liquid detergent for laundry was prepared with the following composition: cationic surfactant/anionic surfactant molar ratio 515)
The flexibility after the washing test was evaluated by sensory evaluation.

(% by weight) Polyoxyethylene dodecyl ether (EO=14), 30.0 Compound of general formula (B) [R2=18, R3=1, m+n=4, average molecular weight 5
04,
8.0 Coloring agent, fragrance
Appropriate amount of sodium hydroxide
Appropriate amount of ion exchange water
This liquid laundry detergent had excellent softening and cleaning effects.

[Effects of the Invention] The cleaning composition of the present invention has an excellent rinsing effect and is less irritating to the skin.

Patent applicant: Shiseido Co., Ltd.

Claims (1)

[Claims] (1) [1] One or more nonionic surfactants, [2] An imidazoline quaternary ammonium salt type cationic surfactant represented by the following general formula (A) and the following general formula (B). ); and [3] one or more carboxylic acid salt type anionic surfactants. So, the molar ratio of [2]/[3] is 4
A cleaning composition characterized in that the cleaning composition has a cleaning composition in the range of /6 to 8/2. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) (In the formula, R_1 is an alkyl group or alkenyl group having 12 to 22 carbon atoms, and X is a halogen atom or lower alkyl group having 1 to 2 carbon atoms. Represents an anionic group selected from sulfate groups.) ▲Mathematical formulas, chemical formulas, tables, etc. are available▼(B) (In the formula, R_2 represents an alkyl group with 16 to 22 carbon atoms, R
_3 is an alkyl group having 1 to 2 carbon atoms or 16 carbon atoms
~22 alkyl group, X represents an anionic group selected from a halogen atom and a lower alkyl sulfate group in which the alkyl group has 1 to 2 carbon atoms, m and n are each an integer of 1 or more, and the sum is 2 An integer from 30 to 30. )