JP2000351990A - Solid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in resistance to loss of shape by dissolution, improved in surface gloss and having a feeling of use close to that of soap by including an N-acyl acidic amino acid type surfactant, a specific alkyl or alkenyl ethercarboxylic acid type surfactant, etc., in a specified proportion. SOLUTION: This composition is obtained by including (A) 50-90 wt.% of one or more kinds of N-acyl acidic amino acid type surfactants (e.g. a sodium N-mixed fatty acid glutamate), (B) 10-30 wt.% of one or more kinds of alkyl or alkenyl ethercarboxylic acid type surfactants represented by the formula [R1 is a 6-22C alkyl or a 6-22C alkenyl which can be substituted by one or more OHs; EO is oxyethylene; PO is oxypropylene; n and m are each 0-5; (m+n)>1; M3 is H, an alkali(ne earth) metal or the like] and (C) 3-15 wt.% of purified water. A lauryl ethercarboxylic acid, etc., made from lauryl alcohol as a raw material are used as the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention comprises a component (A) comprising an N-acyl acidic amino acid and a salt thereof and a component (B) comprising an alkyl ether carboxylic acid and a salt thereof.
The present invention relates to a solid detergent composition having excellent erosion resistance. More specifically, the present invention relates to the above-mentioned component (A).
The present invention relates to a solid detergent composition comprising (B), (B), an improved surface gloss, a solubility in water that is closer to that of soaps, a refreshing feel, a low irritation property, and an excellent erosion resistance. .

[0002]

2. Description of the Related Art In recent years, detergent compositions are strongly required to have low irritation. Soap composed of fatty acid salt solids has been used as a solid detergent for a long time. The reason why such a soap has surface activity is that its pH is in an alkaline region of 9 or more based on its structure. is important. However, soap users with weak skin have a problem that their alkalinity causes irritation to the skin. Therefore, a less irritating solid detergent is desired.
For example, Japanese Patent Publication No. 48-11805 discloses a solid detergent containing an N-acyl acidic amino acid salt as a main component.

[0003] However, a solid detergent containing an N-acyl acidic amino acid salt as a main component has a drawback that it absorbs water, oozes out, and easily disintegrates (hereinafter referred to as disintegrable).
In addition, soap made of a fatty acid salt gives a refreshing feeling, while giving a moist feeling, which gives an uncomfortable feeling to the feeling of a soap that has been used until then.
Therefore, if it is still used for hand washing, but it is used for body washing, this moist feeling is negatively evaluated as a slimy feeling. Therefore, there has been a demand for the development of a new solid detergent composition containing an N-acyl acidic amino acid salt as a main component and giving a refreshing feel like soap.

Regarding the improvement of the disintegration property of a solid detergent, N
Various studies have been made on mixing acyl-acid amino acid salts with a detergent component having a lower solubility in water as a modifier. For example, JP-A-54-39408
Japanese Patent Application Laid-Open No. 57-167 describes the effect of adding N-long-chain acylimino dibasic acids.
No. 398 discloses the effect of adding behenyl alcohol. Each of these modifiers exhibited some improvement effects, but was not sufficiently satisfactory.

[0005] Regarding the feel when using a solid detergent,
JP-A-51-48768 discloses a method of mixing a pyrrolidone carboxylate.
No. 039 introduces a method of mixing a quaternary ammonium salt type cation. These additives include:
In each case, improvement in the usability was observed, but it was not possible to say that it became equivalent to the refreshing usability of the soap, and all the effects were insufficient.

When a solid detergent containing an N-acyl acidic amino acid salt as a main component is manufactured by mechanical kneading, stickiness of a bar detergent extruded from an extruder is poor.
Surface gloss tends to be inferior to soap. In order to improve such productivity, mixing of cetyl alcohol with N-acyl acidic amino acid salt and addition of dextrin disclosed in Japanese Patent Publication No. 60-18716 have been tried. The composition was susceptible to the extrusion temperature and extrusion rate of the obtained composition, and was not always sufficient.

On the other hand, alkyl ether carboxylate is a long-known low-irritant surfactant, and is blended in liquid detergent compositions, gel detergent compositions and the like.
For example, JP-A-6-25695 discloses a combination of an alkyl ether carboxylate and an N-acyl acidic amino acid salt. Solids of the same combination as above are not known at all. That is, N-
A solid detergent composition in which an alkyl ether carboxylic acid is mixed at a high ratio with a solid detergent composition containing an acyl acidic amino acid salt is not known.

[0008]

DISCLOSURE OF THE INVENTION The present invention relates to a solid detergent composition containing an N-acyl acidic amino acid type surfactant which is excellent in erosion resistance, has improved surface gloss, and has a usability similar to that of soap. It is something to offer.

[0009]

According to the present invention, there is provided a solid detergent composition having excellent resistance to disintegration, comprising the following components: (A) 50 to 90% by weight of one or more N-acyl acidic amino acid type interfaces; An activator and (B) 10-30% by weight of
The following general formula (I):

Embedded image [Wherein, in the formula (I), R ¹ is a straight-chain or branched-chain alkyl group or alkenyl containing 6 to 22 carbon atoms, and is unsubstituted or substituted by at least one hydroxyl group. EO represents an oxyethylene group,
PO represents an oxypropylene group, n and m each independently represent an integer of 0 to 5, provided that the relational formula:
n + m ≧ 1 and-(EO) n-
Group, and - (PO) m-group may be arranged in at random, and these groups may be random polymerization or block polymerization, M ³ represents a hydrogen atom, an alkali metal atom, At least one alkyl or alkenyl ether carboxylic acid type interface represented by the following formula: an alkaline earth metal atom, an alkanolamine residue containing 2 to 6 carbon atoms, and a member selected from basic amino acid residues. An activator, and (C) 3 to 15% by weight of purified water;
It is characterized by including. The solid detergent composition according to the present invention, which has excellent resistance to disintegration, comprises the component (A).
The N-acyl acidic amino acid type surfactant for use has the following general formula (II):

Embedded image [However, in the above (II), R ² —CO— is 8 to 20.
Represents a straight-chain or branched-chain saturated or unsaturated fatty acid residue containing carbon atoms, and M ¹ and M ² each independently represent a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, Represents an alkanolamine residue containing up to 6 carbon atoms, and one member selected from basic amino acid residues] and N-acylglutamic acid and salts thereof. In the solid detergent composition having excellent resistance to disintegration of the present invention, the alkyl or alkenyl ether carboxylic acid type surfactant for the component (B) may have an addition mole number m of PO group in the above formula (I). Is 0, and the average value n1 of the number of moles n of the EO group added is n1
Satisfies the relational expression: 0 <n1 ≦ 5, the total weight of the compound of the formula (I) in this component (B), wherein the value of n is in the range of n1-1 to n1 + 1, Formula (I)
Is preferably 50% or more with respect to the total weight of the component (B) composed of the compound of the formula (1). In the following description, the alkyl or alkenyl ether carboxylic acid of the formula (I) or a salt thereof is simply referred to as an alkyl ether carboxylic acid.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have continued experiments to improve the collapse resistance of solid N-acyl acidic amino acid salts by changing the types of additives. When an alkyl ether carboxylic acid having a low-temperature solubility higher than that of the acyl acidic amino acid salt and a salt thereof are blended in a specific amount or more, the disintegration resistance is improved, and the surface gloss of the solid is increased, and at the same time, the usability is close to that of soap. The present inventors have found that the effect of the present invention can be achieved, and completed the present invention.

The N-acyl acidic amino acids and salts thereof constituting the component (A) of the present invention are preferably selected from the surfactant compounds represented by the general formula (II). In the formula (II), the acyl group represented by the formula R ² —CO—
A linear or branched, saturated or unsaturated fatty acid residue having up to 20 carbon atoms, and an acidic amino acid and a salt thereof for binding to the fatty acid residue to form a hydrophilic group Is aspartic acid, glutamic acid, cysteic acid,
Homocysteic acid and alkali metal salts of these amino acids such as sodium and potassium; alkaline earth metal salts such as calcium and magnesium; ammonium salts;
Alkanolamine salts such as triethanolamine and monoethanolamine; basic amino acid salts such as arginine and lysine; and the like.

In the present invention for providing a solid detergent composition in a weakly acidic to neutral range, the degree of neutralization of N-acyl acidic amino acids is 0.1 to 1 mol of N-acyl acidic amino acids. It is preferably neutralized at a ratio of 7 to 1.5 mol, and in order to improve the extrudability of mechanical kneading, the ratio is preferably 0.7 to 1.2 mol in terms of monoacid base. Preferably neutralized, 0.8 mol or more 1.2
More preferably, it is neutralized in a proportion of less than mole,
More preferably, it is 0.8 to 1.15 mol. By controlling the degree of neutralization in this way, the resulting solid can be made excellent in the amount of foam generated, the rate of foam rise, and the like. In the solid detergent composition of the present invention, the content of the N-acyl acidic amino acid surfactant component (A) is 50 to 90% by weight, and 70 to 85% by weight.
% By weight. When the content of the component (A) is
When the amount is less than 50% by weight, the obtained cleaning composition does not solidify and becomes in a paste state, and when it exceeds 90% by weight, the obtained cleaning composition becomes excessively hard. When the molded article of the detergent composition is stored at room temperature, cracks or cracks are generated by drying, and the commercial value is lost.

Specific examples of the N-acyl acidic amino acid salt which is the main ingredient of the composition of the present invention include sodium N-lauroyl aspartate, sodium N-palm fatty acid aspartate, N-mixed fatty acids (coco fatty acid, hardened tallow fatty acid). ) Sodium aspartate, N-lauroyl sodium glutamate, N-palm fatty acid sodium glutamate, N-mixed fatty acid (coconut fatty acid, hardened tallow fatty acid) sodium glutamate, N-lauroyl aspartate, N-palm fatty acid potassium aspartate, N- Mixed fatty acids (coconut fatty acids, hardened tallow fatty acids)
Potassium aspartate, potassium N-lauroyl glutamate, potassium N-palm fatty acid glutamate, N
-Mixed fatty acids (coconut fatty acid, hardened tallow fatty acid), potassium glutamate and the like, and these may be used as a mixture of two or more thereof. Generally available,
It is particularly preferable to use N-acylglutamic acid sodium salt from the viewpoints of low price and the like.

The alkyl or alkenyl ether carboxylic acid and its salt used as the component (B) of the composition of the present invention are those represented by the formula (I). The compounds of formula (I) are higher alcohols having a straight-chain or branched alkyl or alkenyl group, unsubstituted or substituted by at least one hydroxyl group, containing 6 to 22 carbon atoms. Is subjected to addition polymerization of ethylene oxide and / or propylene oxide in the presence of a basic catalyst such as potassium hydroxide to oxidize terminal hydroxyl groups of the resulting reaction product compound, or to convert chloroacetic acid or the like to terminal hydroxyl groups. Obtained by condensation. As the higher aliphatic alcohol used, lauryl alcohol, myristyl alcohol, palmityl alcohol,
Oleyl alcohol and a mixture of two or more of these are used. Alkyl ether carboxylic acids obtained from a single higher fatty alcohol as the raw material show the most remarkable improvement in the collapse resistance. Of these, lauryl is preferred because of its availability and low cost. It is most preferable to use lauryl ether carboxylic acid made from alcohol.

The average number of moles of the alkylene oxide (EO and / or PO) added to the alkyl ether carboxylic acid is preferably 1 to 10, more preferably about 3 to 5. When the addition average number of moles of the alkylene oxide is less than 1, the resulting alkyl ether carboxylic acid acts to inhibit the foaming properties of the resulting detergent composition and impairs the performance of the resulting composition. When the average number of moles exceeds 10, not only the improvement of the insolubility resistance of the obtained composition is not recognized, but also the viscoelasticity such that the composition becomes excessively soft during mechanical kneading and does not advance on the screw. As a result, it is difficult to form a solid.

Further, when addition polymerization of alkylene oxide to higher aliphatic alcohol is carried out, if a catalyst containing dehydrated hydrotalcite and / or aluminum oxide-magnesium oxide composite oxide is used instead of the base catalyst, The additional distribution approaches the normal distribution, and the distribution curve becomes sharp. In a so-called narrowed ether carboxylate, that is, particularly in the general formula (I), the addition mole number m of PO is 0, and the average value n1 of the addition mole number n of the EO group is 0 <n1 ≦ 5. When satisfied, the ratio of the total weight of the compound of the formula (I) in which the value of the number of moles of addition n is in the range of n1-1 to n1 + 1 with respect to the total weight of the component (B) comprising the mixture of the compound of the general formula (I) Is 50% or more of the alkyl ether carboxylate-containing component (B),
Addition is most effective in improving the collapse resistance.

Next, the composition of the composition of the present invention will be described in detail. Component (B) in the solid detergent composition of the present invention.
The ratio of the alkyl ether carboxylic acid or a salt thereof is 10
-30%, preferably 10-20%. 10
When the component (B) is added in an amount of less than 10%, no improvement in the degree of erosion resistance is observed, and the feeling in use is equivalent to that of the N-acyl acidic amino acid salt. If the amount exceeds 30%, the viscoelasticity of the obtained composition changes, and the composition slides on the screw of the extruder, making solidification molding difficult.

The amount of water, which is the component (C) of the composition of the present invention, needs to be increased or decreased in proportion to the amount of the N-acyl acidic amino acid salt (component (A)) in the composition. Become. When the alkyl ether carboxylate (component (B)) is not blended, about 15 to 13% of water is required,
As the addition ratio of the alkyl ether carboxylate (component (B)) increases, the optimal water content decreases. 3
When 0% by weight of alkyl ether carboxylic acid is mixed,
Extrusion can be sufficiently performed with about 1 to 3% of water. If the amount of water is more than the upper limit of 15% by weight, the resulting composition will be excessively soft and solidification molding will be difficult. If the amount of water is less than the lower limit of 3% by weight, the amount of the solid extruded from the extruder will be reduced. The shape retention is reduced, and the obtained solid cannot maintain its shape.

In the composition of the present invention, the amount of water is N-
Since it is set so as to be proportional to the amount of the acyl acidic amino acid salt, it is used as the component (B). Although it is advantageous that the alkyl ether carboxylate does not contain water, it is usually prepared containing 5 to 10% of water. As a specific method for preparing a high-concentration alkyl ether carboxylate, an alkyl ether carboxylic acid whose pH has been adjusted to an acid form is subjected to a treatment such as decompression and dehydration, and the base is gradually added until a desired pH value is reached. A method of adding an active substance can be used. Usually, it is preferable to adjust the pH of the composition so as to be equal to the pH of the N-acyl acidic amino acid salt component (A) mixed with water. At this time, if the alkyl ether carboxylic acid (component (B)) is not sufficiently dehydrated, the composition gels during the neutralization and the neutralization becomes difficult.

The solid detergent composition of the present invention may contain, as long as solidification of the solid detergent composition is not impaired, additives usually used in cosmetics, for example, extracts and powdery components derived from animals, plants, fish and shellfish, or microorganisms. Including various pigments, liquid fats and oils, solid fats and oils,
Wax, hydrocarbon, higher fatty acid, higher alcohol, ester, silicone, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, humectant, water-soluble polymer, thickener, coating Agents, ultraviolet absorbers, anti-inflammatory agents, sequestering agents, lower alcohols, sugars, amino acids, organic amines, synthetic resin emulsions, pH adjusters, skin nutritional agents, vitamins, antioxidants, antioxidants, fragrances One or two or more of these may be used as necessary. However, since the water content of these additives also affects the solidification, it is necessary to use additives having a low water content and to maintain the total water content of the composition at a desired value.

The extracts derived from animals, plants, fish and shellfish, and microorganisms include, for example, tea extract, aloe extract, ginkgo extract, assembly extract, mugwort extract, garlic extract,
Includes extracts such as ogre extract, rosemary extract, carrot extract, loofah extract, placenta extract, lactic acid bacteria culture extract, seaweed extract, etc., and purified products of those medicinal ingredients.

In the above-mentioned powder component, the inorganic powder includes, for example, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, phlogopite, biotite,
Lithia mica, vercumulite, magnesium carbonate, zirconium silicate, aluminum silicate, barium silicate, calcium silicate, zinc silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate Gypsum), calcium phosphate, fluorapatite,
Hydroxyapatite, ceramic powder, metal soap (zinc myristate, calcium palmitate, aluminum stearate, etc.), boron nitride, etc. are included. Organic powders include, for example, polyamide resin powder (nylon powder), polyethylene powder, poly Examples include methyl methacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, and the like.

Of the above-mentioned pigments, inorganic pigments include, for example, titanium dioxide, zinc oxide, iron oxide (iron oxide), iron titanate, γ-iron oxide, yellow iron oxide, loess, black iron oxide, carbon black, Examples include titanium oxide, mango violet, cobalt violet, chromium oxide, chromium hydroxide, cobalt titanate, ultramarine, navy blue, and the like. Examples of pearl pigments include, for example, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil, and the like, and metal powder pigments include, for example, aluminum powder. , Copper powder, and organic pigments such as red 2
No. 01, Red No. 202, Red No. 204, Red No. 205,
Red 220, Red 226, Red 228, Red 40
No. 5, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401 and Blue No. 404. Examples of organic pigments such as zirconium, barium or aluminum chelate include, for example, Red No. 3, Red No. 104, Red No. 106 , Red 22
No. 7, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3, and Blue No. 1. For example, chlorophyll and β-carotene are exemplified.

These powder materials can be used as they are in the solid detergent composition of the present invention, but they can be treated with silicone using methyl hydrogen polysiloxane or silane coupling agent, metal soap, perfluoroalkyl Subjected to fluorination treatment using diethanolamine phosphate or perfluoroalkylsilane, etc.
These may be used as a hydrophobic treatment powder.

The liquid oils and fats include avocado oil, camellia oil, grape seed oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, sunflower oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, Wheat germ oil, sasanqua oil, castor oil, linseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, teaseed oil, kaya oil, rice bran oil, sinagiri oil, Japanese kiri oil, jojoba oil, germ oil , Triglycerin, glycerin trioctanoate and glycerin triisopalmitate can be used.

Examples of the solid fats and oils include cocoa butter, coconut oil, horse fat, hardened coconut oil, palm oil, tallow, sheep butter, hardened tallow, palm kernel oil, lard, beef bone fat, mokuro kernel fat, hardened oil , Beef tallow, mocro, and hydrogenated castor oil.

The waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, isopropyl lanolin fatty acid, hexyl laurate, Reduced lanolin, jojoba wax, hard lanolin,
Shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, and POE hydrogenated lanolin alcohol ether.

Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalene, pristane, paraffin, ceresin, squalane, petrolatum, and microcrystalline wax. Further, as the higher fatty acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, 12-
Hydroxystearic acid, undecylenic acid, tall oil fatty acid, coconut oil fatty acid, palm fatty acid, palm kernel fatty acid,
Examples include isostearic acid, linoleic acid, linoleic acid, eicosapentaenoic acid, and docosahexaenoic acid.

Examples of the synthetic ester oils include isopropyl myristate, cetyl octanoate, octyl dodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyl octanoate, lactic acid Cetyl, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate,
Cholesteryl 12-hydroxystearate, di-2-
Ethylene glycol ethylhexylate, fatty acid ester of dipentaerythritol, neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexylate, trimethylolpropane triisostearate, tetra Pentaerythritol-2-ethylhexylate, glycerin tri-2-ethylhexylate, trimethylolpropane triisostearate, cetyl-2-ethylhexanoate, 2-ethylhexyl palmitate, glycerin trimmyristate, tri-2-heptylundecanoic acid Glyceride, castor oil fatty acid methyl ester, oleic acid oil, cetostearyl alcohol, acetoglyceride, palmitic acid
2-heptylundecyl, diisobutyl adipate, N
-Lauroyl-L-glutamic acid-2-octyldodecyl ester, adipic acid-2-heptylundecyl, ethyl laurate, di-2-ethylhexyl sebacate,
2-hexyldecyl myristate, palmitic acid-2
-Hexyldecyl, 2-hexyldecyl adipate,
Examples thereof include diisopropyl sebacate, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, and triethyl citrate.

Examples of the silicone include dimethyl silicone oils such as methylpolysiloxane, octamethyltrisiloxane, and highly polymerized methylpolysiloxane; cyclic polysiloxanes such as decamethylpolysiloxane, dodecamethylpolysiloxane, and tetramethyltetrahydro Genpolysiloxane; polyether-modified silicone, for example, dimethylsiloxane / methyl (polyoxyethylene) siloxane copolymer, and dimethylsiloxane / methyl (polyoxyethylene) siloxane / methyl (polyoxypropylene) siloxane copolymer; amino-modified Silicones, such as amodimethicone; and other methylphenylpolysiloxanes, methylhydrogenpolysiloxanes, trimethylsiloxysilicic acid, three-dimensional networks Silicon resin forming the structure,
And silicon rubber.

Examples of the anionic activator include fatty acid soaps such as soap base, sodium laurate, sodium palmitate, and coconut soap; higher alkyl sulfates such as sodium lauryl sulfate, potassium lauryl sulfate, and triethanol lauryl sulfate. Amines; alkyl ether sulfates such as POE lauryl sulfate triethanolamine and sodium POE lauryl sulfate; N-acyl amino acid salts such as sodium lauroyl sarcosine, sodium lauroyl glycine, sodium lauroyl-β-alanine, lauroyl-N-methyl- β-alanine sodium and coconut fatty acid silk peptide; higher fatty acid amide sulfonate, such as sodium N-myristoyl-N-methyltaurine Sodium coconut fatty acid methyltaurine, sodium lauroylmethyltaurine, and sodium POE laurylamide ether sulfonate;
Phosphate salts, such as sodium POE oleyl ether phosphate, POE stearyl ether phosphoric acid, and sodium POE lauryl amide ether phosphate; sulfosuccinates, such as sodium di-2-ethylhexyl sulfosuccinate, monolauroyl monoethanolamide polyoxy Sodium ethylene sulfosuccinate and sodium lauryl polypropylene glycol sulfosuccinate; alkylbenzene sulfonates, such as sodium linear dodecylbenzene sulfonate;
Linear dodecylbenzenesulfonic acid triethanolamine and linear dodecylbenzenesulfonic acid; higher fatty acid ester sulfates, for example, sulfated oils such as hydrogenated coconut oil fatty acid sodium glycerin sulfate and funnel oil;
α-olefin sulfonate, higher fatty acid ester sulfonate, secondary alcohol sulfate, higher fatty acid alkylolamide sulfate, sodium lauroyl monoethanolamide succinate, sodium caseinate and the like.

Examples of the cationic surfactant include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, and lauryltrimethylammonium bromide; dialkyldimethylammonium salts such as distearyldimethylammonium chloride; And dialkyl salts such as cetylpyridium chloride; and alkyldimethylbenzylammonium salts, benzethonium chloride, and benzalkonium chloride.

Examples of the amphoteric surfactant include amidoamine-based amphoteric surfactants such as 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine and N-lauroyl-N'-carboxymethyl-.
N'-hydroxyethylethylenediamine sodium,
And N-coco fatty acid acyl-N'-carboxyethyl-
Sodium N'-hydroxyethylethylenediamine;
Amidoacetate betaine type amphoteric surfactants, such as coconut fatty acid amidopropyl betaine and myristate amidopropyl betaine; Amidosulfobetaine type amphoteric surfactants, such as lauric acid amidopropylhydroxysulfobetaine; Amine oxide type amphoteric surfactant, such as lauryl Trimethylamine oxide and lauric amide propylamine oxide; and alkyl acetate betaine-type amphoteric surfactants and alkylsulfobetaine-type amphoteric surfactants.

Examples of the nonionic surfactant include glycerin fatty acid esters such as glyceryl monostearate, self-emulsifying glyceryl monostearate and glyceryl monoisostearate; polyoxyethylene glycerin fatty acid esters such as POE glyceryl monostearate. And POE glyceryl monooleate; polyglycerin fatty acid esters such as diglyceryl monostearate, tetraglyceryl tristearate and decaglyceryl pentastearate; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan sesquistearate and monooleic acid Sorbitan; polyoxyethylene sorbitan fatty acid esters such as monococonut fatty acid POE sorbitan;
POE sorbitan tristearate and POE sorbitan trioleate; polyoxyethylene sorbite fatty acid esters, such as POE sorbitol monolaurate, and POE sorbite tetraoleate; polyethylene glycol fatty acid esters, such as polyethylene glycol monolaurate, polyethylene glycol monostearate Polyethylene glycol monooleate and polyethylene glycol distearate; polyoxyethylene alkyl ethers such as POE lauryl ether, POE cetyl ether, and POE stearyl ether; polyoxyethylene polyoxypropylene alkyl ethers such as POE.POP cetyl ether; POE / POP Decyl tetradecyl ether, polyoxyethylene alkyl Ruphenyl ethers, POE
Nonylphenyl ether, POE octyl phenyl ether, and POE branched octyl phenyl ether; polyoxyethylene alkylamines such as POE stearylamine and POE oleylamine; fatty acid alkanolamides such as coconut fatty acid diethanolamide, coconut fatty acid monoethanolamide; Lauric acid diethanolamide and palm kernel oil fatty acid diethanolamide; polyoxyethylene alkanolamides such as POE lauric acid monoethanolamide, POE
Coconut fatty acid monoethanolamide and POE tallow fatty acid monoethanolamide; and other acetylene glycol, POE acetylene glycol, POE lanolin, POE lanolin alcohol, POE castor oil, POE
E hydrogenated castor oil, POE phytosterol, POE cholestanol, and POE nonylphenylformaldehyde condensate.

These additives are simultaneously mixed with an N-acyl acidic amino acid salt (component (A)), an alkyl ether carboxylate (component (B)) and water using a mixer mixer, and the whole is uniformly mixed. After mixing so as to be mixed, the mixture is rolled and put into an extruder to form a bar-shaped solid detergent, which is cut into a predetermined size and press-molded to obtain a solid detergent composition having a target shape and dimensions. To form At this time, if the melting point of the additive is high or if the additive has a high crystallinity, the additive is heated and dissolved in a solution of the alkyl ether carboxylate (component (B)) to be charged, and then mixed and mixed. , The mixture can be uniformly and quickly mixed.

Originally, when an alkyl ether carboxylate (component (B)), which is more water-soluble than the base N-acyl acidic amino acid salt (component (A)), is added at a high concentration, the disintegration resistance becomes poor. This phenomenon should be considered to be reduced, which is rather improved in the present invention, and it is difficult to dismiss this mechanism. FIG. 1 shows the composition of the composition when the alkyl ether carboxylate (component (B)) was blended with 0%, 5%, 10% and 15% of the N-acyl acidic amino acid (component (A)). The X-ray diffraction diagram is shown. Component (B)
Are 0% and 5%, the X-ray diffraction pattern (Cu
l. 54 Å), a clear peak is observed at around 2θ = 20 °, but the compounding amount of the component (B) is 10
%, The peak becomes unclear and disappears. This seems to mean that the diffraction surface of about 5 angstroms has disappeared. This is because the incorporated ether carboxylic acid is successfully incorporated into the bulky hydrophilic group portion of the N-acyl acidic amino acid salt, and a specific amount or more of the alkyl ether carboxylate is converted into the bulky hydrophilicity of the N-acyl acidic amino acid salt. It is presumed that the continuous absorption of water was prevented when it was taken into the part.

[0037]

The present invention will be described more specifically with reference to the following examples. Production Example 1 (Preparation of catalyst for synthesis of alkyl ether carboxylic acid)
The Ltd.) coordination chemical sol-gel method, amorphous magnesium / aluminum mixed oxide (Mg: Al = 2: was prepared by a type 1) as follows. 150 g of a 9.5 wt% methanol solution of Mg (OMe) ₂ and 16.9 g of Al (O _i Pr) ₃ powder (the molar ratio of Mg: Al is
2: 1) and 150 g of hexylene glycol were placed in a 500 ml four-necked flask equipped with a distillation head, and the mixture was heated and stirred at 120 ° C. for 2 hours while distilling off methanol and isopropanol. And a ligand exchange reaction.
30 g of hexylene glycol and water
Pour into 20 g of the mixture and stir the mixture overnight,
A hydrolysis reaction was performed. The next day, the solvent was distilled off from this sol solution using an evaporator to obtain 17.6 g of a dry gel. The obtained dry gel was calcined in an annular electric furnace at 400 ° C. for 3 hours in a flowing air to obtain 9.1 g of an amorphous magnesium / aluminum composite oxide.

Production Example 2 (concentrated narrow range type high concentration PO
E (3) Preparation of sodium lauryl ether carboxylate
Made in a 200 ml autoclave, 62 g of lauryl alcohol
And 62 mg of an amorphous magnesium / aluminum composite oxide produced by the coordination chemical sol-gel method produced in Production Example 1, and the inside of the autoclave was replaced with nitrogen three times, and then 59 g of ethylene oxide was introduced into the autoclave. The reaction was carried out at 150 ° C. Two hours after the start of the reaction, the pressure reduction stopped, and the mixture was further aged for 1 hour to terminate the reaction. After cooling the reaction product to room temperature, the magnesium / aluminum composite oxide in an amorphous state by a coordination chemical sol-gel method was separated and removed by filtration to obtain 121 g of POE (4) lauryl ether in a narrow range.

In a 200 ml autoclave were charged 40 g of a narrow range product of POE (4) lauryl ether, 60 g of water and 1 g of a 5% platinum carbon catalyst, and the inside of the autoclave was replaced with oxygen three times. ^{2. The} reaction was carried out at 110 ° C. for 4.5 hours. After cooling the reaction mixture to 90 degrees, the oxygen in the autoclave was blown off and the autoclave was opened, the catalyst was separated and removed by filtration and washed with water, and the filtrate was dried under reduced pressure to narrow the POE (3) lauryl ether acetic acid narrow range. 41g
I got Subsequently, the temperature of the product was raised to 80 ° C., and 6.89 g of 48% (w / w) sodium hydroxide was added.
(Degree of neutralization: 74.1%). Prepared concentrated POE
(3) Lauryl ether acetate has an active ingredient content of 85.
6%, and the pH of the aqueous solution when diluted 100-fold was 6.07.

Production Example 3 (concentrated broad range type high concentration P
Preparation of OE (3) sodium lauryl ether carboxylate
Made in a 200 ml autoclave, 62 g of lauryl alcohol
And 0.6 g of KOH, and the inside of the autoclave is
After the substitution, 59 g of ethylene oxide was introduced therein, and the reaction was carried out at 150 ° C. Two hours after the start of the reaction,
Since the pressure reduction stopped, this was further aged for 1 hour to complete the reaction. After the reaction mixture was cooled to room temperature, insolubles were separated and removed by filtration to obtain 121 g of a broad-range POE (4) lauryl ether.

In a 200 ml autoclave, 40 g of a broad range POE (4) lauryl ether, 60 g of water, and 1 g of a 5% platinum carbon catalyst were charged, and the inside of the autoclave was charged with nitrogen by 3 g.
After the substitution, the reaction was carried out at 110 ° C. and an oxygen pressure of 30 kg / cm ² for 4.5 hours. After the reaction mixture was cooled to room temperature, the oxygen in the autoclave was blown off and the autoclave was opened.The catalyst was separated by filtration and washed with water, and the filtrate was dried under reduced pressure to broaden the POE (3) lauryl ether acetic acid. Article 41
g. The temperature of the reaction product was subsequently raised to 60 ° C., and 6.8% of 48% (w / w) sodium hydroxide was added thereto.
9 g (degree of neutralization: 74.1%) were added. Prepared concentrate
The active ingredient of POE (3) lauryl ether acetate is 85.6
%, And the pH of an aqueous solution obtained by diluting it 100-fold was 6.07.

[0042] In each of Examples 1-8 and Comparative Examples 1-7 Examples 1-8 and Comparative Examples 1-7, the components shown in Tables 1 and 2, the blending ratio (wt%) shown in Table 1
After the mixture was rolled 5 times, the mixture was put into an extruder after being rolled 5 times, and after confirming that air was removed from the extruded solid cleaning agent, the extrusion mold was heated at a temperature of 50 ° C. 50 kg of bar-shaped solid detergent composition
/ Cm ² under pressure. Tables 1 and 2 show the performance of the obtained solid detergent composition.

[0043]

[Table 1]

[0044]

[Table 2]

Notes in Tables 1 and 2 (Note 1) * ₁ ... Amisoft GS-11 manufactured by Ajinomoto Co., Inc. (Note 2) * ₂ ... Destruction resistance test 1 Each solid detergent whose weight has been measured in a petri dish with a diameter of 18 cm. , And water was poured in with distilled water until the thickness became の of the thickness of the solid matter. Each sample was placed in a thermo-hygrostat set at 30 ° C. and a relative humidity of 80%. After 20 hours, the state of the solid detergent in the petri dish was visually checked and evaluated according to the following evaluation criteria. ：: There is no change in the outer shape of the water, and the portion below the water surface is relatively firm. ：: There is no change in the outer shape of the upper part of the water, and a part below the water surface is partially creamed. The creaming is progressing below the water surface. ×: Water is absorbed up to the water surface, and the outer shape is expanded. Under the water, most parts are creamed

(Note 3): * ₃ ... Test for erosion resistance 2 The sample for erosion resistance test 1 was taken out of the Petri dish, the creamed portion was washed away in cold running water, and the weight was measured after drying. The percentage of the weight measured at this time with respect to the initial weight is measured. (Note 4): * ₄ Surface gloss test The surface gloss of each sample was evaluated by visual observation. Evaluation criteria: O when gloss was felt, and X when gloss was not felt. (Note 5): * ₅ Use test The sample of Comparative Example 1 was determined to be the worst, the solidified soap tip pressurized product was the best, the evaluation of Comparative Example 1 was set to 1 point, and the evaluation score of the standard soap tip solid was 5 points. As a point, each sample was evaluated for refreshing feeling by a hand washing test of 30 monitors. Tables 1 and 2 show the average evaluation points of each sample. The larger the evaluation score, the better the feeling of use.

Example 9 A solid detergent was prepared according to the following formulation. In this production method, the components denoted by the symbol b were mixed in the following composition ratio, and the mixture was stirred and cooled to prepare a paste-like mixture. Subsequently, in the following composition table, the component with the symbol a was put into a mixer blender and dry-blended, and this was added to the previously prepared paste of the component with the symbol b and blended until uniform. Thereafter, the mixture was pressed three times by three rolls, and the mixture was put into an extruder. The extruded solid was cut into a predetermined size and molded to obtain a solid detergent composition. When this molded article was distributed to 10 monitors and used in a bathroom in a normal state, there was no problem of disintegration, it could be used up to the end, and the amount of waste used in ordinary fatty acid soap was reduced. No decrease in foaming property was observed at the time, and the feeling of use was close to that of soap, and it was confirmed that the body was refreshing even when the body was washed. a Amisoft GS-11 70.60% a Arginine myristate (1.0 neutralized product) 5.00% b Cetanol 3.00% a Allantoin 0.20% b Ether carboxylic acid Na of Production Example 3 15.00% b EDTA.2Na 0.10% b Titanium oxide 0.10 % b Purified water 6.00%

Example 10 A molded article of a solid detergent composition having the following composition was prepared in the same manner as in Example 9. Its performance was similar to that of Example 9. a Amisoft GS-11 68.80% b Cetanol 3.00% b PPG3000 5.00% b Ether carboxylate Na 15.00% of Production Example 2 a Calcium chloride 3.00% b Glycyrrhizic acid 2K 0.10% b Titanium oxide 0.10% b Purified water 5.00%

Example 11 In the same manner as in Example 9, a molded article of a solid detergent composition having the following composition was prepared. Its performance was similar to that of Example 9. a Amisoft GS-11 72.70% b Cetanol 3.00% a Monostearyl ammonium chloride (50%) 1.00% a Laurylamidopropyldimethylamine oxide (30%) 3.00% b Ether carboxylic acid Na of Preparation Example 2 15.00% b Glycyrrhizic acid 2K 0.20% b Titanium oxide 0.10% b Purified water 5.00%

Example 12 In the same manner as in Example 9, a molded product of a solid detergent composition having the following composition was prepared. Its performance was similar to that of Example 9. a Amisoft GS-11 49.10% a Amisoft CK-11 25.00% b Behenyl alcohol 2.00% b Isostearyl alcohol 3.00% a Allantoin 0.20% b Ether carboxylic acid of production example 3 Na 15.00% b EDTA · 2Na 0.10% b Titanium oxide 0.10% b. Purified water 5.50%

[0051]

Industrial Applicability According to the present invention, a solid detergent which is excellent in erosion resistance, has high surface gloss, and has a feel similar to that of soap, despite containing an N-acyl acidic amino acid type surfactant as a main component. A composition is obtained.

[Brief description of the drawings]

FIG. 1 shows a blending ratio of an alkyl ether carboxylic acid type surfactant (0 to 15% by weight) in an N-acyl acidic amino acid type surfactant / alkyl ether carboxylic acid type surfactant / purified water-containing solid detergent composition. ) Changes,
7 is a graph showing a change in an X-ray diffraction diagram.

Claims (3)

[Claims] 1. The following components: (A) 50 to 90% by weight of one or more N-acyl acidic amino acid type surfactants; and (B) 10 to 30% by weight of the following general formula (I): Embedded image [Wherein, in the formula (I), R ¹ is a straight-chain or branched-chain alkyl group or alkenyl containing 6 to 22 carbon atoms, and is unsubstituted or substituted by at least one hydroxyl group. EO represents an oxyethylene group,
PO represents an oxypropylene group, n and m each independently represent an integer of 0 to 5, provided that the relational formula:
n + m> 1 and-(EO) n-
Group, and - (PO) m-group may be arranged in at random, and these groups may be random polymerization or block polymerization, M ³ represents a hydrogen atom, an alkali metal atom, At least one alkyl or alkenyl ether carboxylic acid type interface represented by the following formula: an alkaline earth metal atom, an alkanolamine residue containing 2 to 6 carbon atoms, and a member selected from basic amino acid residues. A solid detergent composition excellent in erosion resistance, comprising: an activator; and (C) 3 to 15% by weight of purified water. 2. The N-acyl acidic amino acid type surfactant for component (A) is represented by the following general formula (II): [However, in the above (II), R ² —CO— is 8 to 20.
Represents a straight-chain or branched-chain saturated or unsaturated fatty acid residue containing carbon atoms, and M ¹ and M ² each independently represent a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, Represents an alkanolamine residue containing from 6 to 6 carbon atoms, and one member selected from basic amino acid residues], and N-acylglutamic acid and salts thereof. A solid detergent composition having excellent erosion resistance. 3. The alkyl or alkenyl ether carboxylic acid type surfactant for the component (B), wherein in the formula (I), the value of the number m of added PO groups is 0, and
The average value n1 of the number of added moles n of the O group is represented by the relational expression: 0 <n1
When satisfying ≦ 5, n in this component (B)
Is 50% or more by weight of the total weight of the compound of the formula (I) having a value of n1-1 to n1 + 1 with respect to the total weight of the component (B) composed of the compound of the formula (I). The solid detergent composition according to claim 1, which is excellent in erosion resistance.