JP4972395B2 - Solid detergent composition - Google Patents

Description

  The present invention relates to a solid detergent composition, and more specifically, it has excellent solid physical properties that are not influenced by external factors, have excellent foam performance, yet are not easily swollen with water, and are not easily melted down. The present invention relates to a solid detergent composition obtained at low cost.

  Conventionally, solid detergents are required to give excellent foaming and a favorable feeling of use. The generally used solid soap mainly composed of an alkali metal salt of a higher fatty acid is excellent in foaming and detergency when using soft water and in normal times. However, it is known that when high hardness water is used or when it is used during perspiration, its foaming and detergency are extremely reduced. For this reason, not only a preferable feeling of use is not obtained, but also the use of an activator more than necessary increases the skin irritation due to alkali, and the soap scum remains on the skin during rinsing, resulting in a feeling of tension was there. In order to solve this problem, a combination bar in which a higher fatty acid and a synthetic surfactant are blended, a cinderette bar in which a synthetic surfactant is hardened with an additive, and the like have been studied. In addition, attempts have been made to mix solid fat components such as higher alcohols and hydrocarbon waxes and humectants such as propylene glycol as components other than higher fatty acids.

  However, even if a synthetic surfactant is added to soap, the desired effect cannot be obtained in a small amount, and the solid physical properties are adversely affected. In addition, the combination bar and the cinder bar have the drawback that they melt and break down during use.

As a solid detergent containing a relatively large amount of a synthetic surfactant, a hard crystalline phase skeleton structure comprising a meshed open three-dimensional mesh of neutralized mono- and / or di-carboxylic acid and a water-soluble anion Cleansing solids (Patent Documents 1 to 3) containing a soft phase containing an activator and a stiffness aid, 5 to 30% by weight of a surfactant having a Kraft point of 0 ° C. or less, 5 to 30% by weight of a higher fatty acid salt, Solid detergent composition (Patent Document 4) containing 5 to 30% by weight of solid fat, 20 to 55% by weight of poorly water-soluble filler, 1 to 3% by weight of inorganic salt and 1 to 15% by weight of water, surfactant 35 Solid detergent composition (Patent Document 5) containing ˜98 wt%, liquid or semi-solid oil 1-30 wt%, and gelling agent 0.01-5 wt%, solid phosphate ester surfactant Polyoxyethylene alkyl ether Ether sulfate, a solid detergent composition containing a fatty acid (Patent Document 6) are known.
JP-T 6-503122 Japanese National Patent Publication No. 7-505157 JP 7-82139 JP-A-10-183171 Japanese Patent Laid-Open No. 7-34100 JP-A-8-73891

  However, the inventions described in Patent Documents 1 to 4 do not satisfy the foam quality and the amount of foam, although stable solids can be obtained. Moreover, since the thing of patent document 5 solidifies liquid or semi-solid oil with a gelatinizer, it was not fully satisfied with the foaming power and the point of touch. Furthermore, in the thing of patent document 6, since expensive phosphate ester is used as a solidifying agent, manufacturing cost becomes high. In addition, fatty acid forms scum under high hardness water, and polyoxyethylene alkyl ether sulfate alone produces light and rough foam (also called bubble foam), which is insufficient in terms of foam performance and feel. there were.

  The present invention is intended to solve the problems of the prior art as described above, and has no foaming deterioration in the presence of sweat or high hardness water, which is a defect of fatty acid soap, and has excellent foaming power. An object of the present invention is to provide a solid detergent composition that has a foam quality equivalent to or higher than that of a fatty acid soap, and that provides a preferable feel, and that does not easily melt in water and does not melt.

  The present inventors have found that the above-mentioned object can be achieved by using polyoxyethylene alkyl ether sulfate, higher alcohol, glyceryl ether, higher fatty acid salt and inorganic salt in a specific ratio, and to complete the present invention. It came.

That is, the present invention includes the following components (A), (B), (C), (D) and (E):
(A) General formula (1)
R ¹ O (CH ₂ CH ₂ O) _n SO ₃ M (1)
(Wherein R ¹ represents a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, n represents an average addition mole number, represents a number of 0 to 5, M represents an alkali metal atom, an alkanol. A sulfate represented by the formula:
(B) General formula (2)
R ² —OH (2)
(Wherein R ² represents a linear or branched alkyl group having 12 to 22 carbon atoms),
(C) General formula (3)
R ³ —OCH ₂ —CH (OH) —CH ₂ —OH (3)
(Wherein R ³ represents a linear or branched alkyl group or alkenyl group having 6 to 14 carbon atoms),
(D) General formula (4)
R ⁴ -COOM (4)
(Wherein R ⁴ represents a linear alkyl group having 11 to 23 carbon atoms, and M represents an alkali metal atom, magnesium, alkanolamine or ammonium),
(E) contains an inorganic salt,
The sum total of the component (A), the component (B) and the component (C) is 25 to 40% by weight,
[Component (A) + Component (B) + Component (C)] / [Component (D) + Component (E)] = 2.0 to 0.5, and the water content is 50% by weight or less. A solid detergent composition is provided.

  The solid detergent composition of the present invention does not depend on external factors such as sweat and hardness, has excellent foaming power and foam quality, and does not swell or melt during use.

  Hereafter, it demonstrates for every component which comprises the solid cleaning composition of this invention.

  In the present invention, polyoxyethylene alkyl (or alkenyl) ether sulfate or alkyl (or alkenyl) sulfate of the formula (1) is used. This compound is a surfactant that exhibits excellent foaming power, detergency and hard water resistance, and has low irritation to the skin, but it can be solidified while realizing practical solid properties. This is something that could not be done before. Therefore, when this compound is used as a main base to form a solid detergent composition, preferred foaming power, detergency and hard water resistance can be imparted to the solid detergent composition.

In the sulfate of the formula (1), R ¹ is a linear or branched alkyl group or alkenyl group, but those having less than 8 carbon atoms are difficult to obtain, have a low detergency, and exceed 20 Are difficult to obtain and have low foaming properties. Therefore, R ¹ has 8 to 20 carbon atoms. Examples of the linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms include octyl group, isooctyl group, decyl group, lauryl group, myristyl group, palmityl group, stearyl group, isostearyl group, An oleyl group, a docosyl group, etc. can be mentioned as a preferable thing, Especially a C11-C13 saturated alkyl group, especially a lauryl group can be mentioned as a preferable thing. Examples of the alkali metal of M include lithium, sodium, potassium and the like. As the aliphatic alkanol ammonium of M, mono-, di- or trialkanol ammonium having a C2-C3 hydroxyalkyl group such as hydroxyethyl group or hydroxypropyl group can be preferably exemplified. Moreover, since the foamability falls when the range of preferable n is too large, it is 0-5.

  As particularly preferred specific examples of the sulfate of the formula (1) defined as described above, polyoxyethylene (2) sodium lauryl ether sulfate, polyoxyethylene (3) sodium lauryl ether sulfate, polyoxyethylene (2) myristyl Examples thereof include sodium ether sulfate, polyoxyethylene (2-5) sodium magnesium lauryl ether sulfate.

  In addition, the sulfate of formula (1) may be used alone or in combination of two or more.

  In the present invention, a commercially available 20 to 70% by weight aqueous solution can be used as a feedstock for the sulfate of formula (1), but a 60 to 70% by weight aqueous solution is used because of the productivity of the solid detergent composition. Is preferred.

  The content of the component (A) is preferably 5 to 40% by weight, more preferably 10 to 35% by weight, particularly 20 to 32% by weight in the solid detergent composition of the present invention in terms of foamability. It is preferable to do.

  In this invention, the higher alcohol of Formula (2) is contained. Although this higher alcohol functions as a solidifying agent for the surfactant of component (A), it also functions as a surfactant and has a function of improving the foam quality of component (A) in a creamy manner.

In the higher alcohol of the formula (2), R ² is a linear or branched alkyl group, but when its carbon number is less than 12, it does not work as a solidifying agent, and the foam quality improving effect is also reduced. Moreover, what exceeds 22 becomes difficult to obtain, and foam quality improvement effect falls. Therefore, the number of carbon atoms in R ² is a 12 to 22.

  As a particularly preferable specific example of the higher alcohol of the formula (2) defined as described above, myristyl alcohol, lauryl alcohol, and cetyl alcohol can be exemplified. Particularly preferred is myristyl alcohol.

  In addition, the higher alcohol of Formula (2) may be used alone or in combination of two or more.

  The content of the component (B) is preferably 0.1 to 15% by weight, more preferably 0.1 to 10% by weight in the solid detergent composition of the present invention, from the viewpoint of obtaining the foam amount and creamy foam quality. %, Particularly 1.2 to 10% by weight is preferred.

  In this invention, the glyceryl ether of Formula (3) is contained. This glyceryl ether functions as a foam increasing agent that supplements the function of the component (A) surfactant.

In the glyceryl ether of the formula (3), R ³ represents a linear or branched alkyl group or alkenyl group having 6 to 14 carbon atoms. For example, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group An alkyl group having 4 to 12 carbon atoms such as a group, 2-ethylhexyl group, n-nonyl group, n-decyl group, isodecyl group, n-lauryl group, etc., preferably 6 to 11 carbon atoms, and more preferably 6 to 10 carbon atoms. Of these, an alkyl group having 8 to 10 carbon atoms (particularly a 2-ethylhexyl group or an isodecyl group) is preferable.

  As a particularly preferred specific example of the glyceryl ether of the formula (3) defined as described above, 2-ethylhexyl glyceryl ether or isodecyl glyceryl ether can be exemplified from the viewpoint of foam quality improvement or storage stability.

  Component (C) is preferably contained in the solid detergent composition of the present invention in an amount of 0.1 to 15% by weight from the viewpoint of quick foaming and storage stability of the solid detergent composition. It is preferable to contain 1 to 12% by weight, particularly 0.5 to 12% by weight.

  In this invention, the higher fatty acid salt of Formula (4) is contained. This higher fatty acid salt functions as a solidifying agent for the surfactant of component (A).

In the higher fatty acid salt of the formula (4), R ⁴ is a linear alkyl group. However, when the carbon number is less than 11, the solid physical properties are insufficient, and when it exceeds 23, it is difficult to obtain. The foam increasing effect is reduced. Accordingly, the carbon number of R ⁴ is 11 to 23.

  In view of solidification of the solid detergent composition, the component (D) is preferably contained in the solid detergent composition of the present invention in an amount of 5 to 80% by weight, more preferably 10 to 50% by weight, particularly 12 to It is preferable to contain 40% by weight.

  In this invention, the inorganic salt of a component (E) is contained. This inorganic salt functions as a solidifying agent for component (D). Examples of such inorganic salts include sodium chloride, potassium chloride, sodium sulfate and the like, and among them, sodium chloride is preferable.

  Component (E) is 0.01 to 10.0% by weight, more preferably 0.5 to 8.0% by weight, in the solid detergent composition of the present invention, from the viewpoint of solidification of the solid detergent composition. It is particularly preferable to contain 1.0 to 5.0% by weight.

  In the solid detergent composition of the present invention, in order to achieve sufficient foam strength and high foamability and creamy foam quality, the sum of components (A), (B) and (C) is 25 to 40% by weight, [component (A) + component (B) + component (C)] / [component (D) + component (E)] = 2.0 to 0.5, and water It is important that the content is 50% by weight or less.

  The solid detergent composition of the present invention can further improve the foam viscosity and foam quality by further blending the cationic polymer (F). Examples of the cationic polymer include one or more selected from the group consisting of the following (a) to (d).

  (A) at least one nonionic group-containing vinyl monomer represented by the general formula (I) or (II) and a cationic group-containing vinyl monomer represented by the general formula (III) or (IV) And at least one kind of cross-linkable vinyl monomer having at least two groups selected from vinyl group, acryloyl group, methacryloyl group and allyl group in the molecule as an essential constituent monomer, Cationic group-containing copolymer obtained by radical polymerization

[Wherein, R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² and R ¹³ are the same or different and represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms. ]

[Wherein, R ¹¹ represents the same meaning as described above, and A ¹ and A ² are the same or different and each represents a group represented by the formula — (CH ₂ ) m — (m represents an integer of 2 to 6). B represents —O— or —CH ₂ — group. ]

[Wherein, R ¹¹ has the same meaning as described above, R ¹⁴ and R ¹⁵ are the same or different and each represents an alkyl group or alkenyl group having 1 to 4 carbon atoms, and R ¹⁶ represents a hydrogen atom or 1 to 4 carbon atoms. Y represents —O—, —NH—, —CH ₂ — or —O—CH ₂ CH (OH) —, and Z represents a carbon number of 1 to 4 (Y is —CH ₂ —). Is a linear or branched alkylene group having 0 to 3 carbon atoms, and X is an acid conjugate base, a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms. ]

[Wherein, R ¹⁷ and R ¹⁸ are the same or different and each represents a hydrogen atom or a methyl group; R ¹⁹ and R ²⁰ represent the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; The same meaning as above is shown. ],

(B) cationized cellulose derivative (c) cationized guar gum derivative (d) diallyl quaternary ammonium salt polymer or diallyl quaternary ammonium salt / acrylamide copolymer

The (a) cationic group-containing copolymer of component (F) is described in detail below.
(I) Nonionic group-containing vinyl monomer Specific examples of the monomer represented by the general formula (I) include (meth) acrylamide, N-methyl (meth) acrylamide, and N, N-dimethyl (meth). Acrylamide, N, N-diethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N- Examples include hydroxypropyl (meth) acrylamide. Examples of the monomer represented by the general formula (II) include N- (meth) acryloylmorpholine.

(B) Cationic group-containing vinyl monomer Specific examples of the monomer represented by the general formula (III) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl ( (Meth) acrylate, diisopropylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl ( (Meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropylaminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) Quaternary with acid neutralized products or quaternizing agents neutralized with (meth) acrylic acid esters or (meth) acrylamides having dialkylamino groups such as acrylamide and di-t-butylaminopropyl (meth) acrylamide Quaternary ammonium salts.

  Specific examples of the monomer represented by the general formula (IV) include diallyl-type quaternary ammonium salts such as dimethyldiallylammonium chloride and diethyldiallylammonium chloride.

  Preferred acids for obtaining the above acid neutralized product include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; and acetic acid, formic acid, maleic acid, fumaric acid, citric acid, tartaric acid, adipic acid, sulfamic acid, Examples thereof include organic acids having 1 to 22 carbon atoms such as toluenesulfonic acid, lactic acid, pyrrolidone-2-carboxylic acid, succinic acid, propionic acid and glycolic acid. Preferred quaternizing agents for obtaining the quaternary ammonium salts include alkyl halides having 1 to 8 carbon atoms such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide, dimethyl sulfate, diethyl sulfate, disulfate sulfate. Common alkylating agents such as -n-propyl can be mentioned.

  Among the monomers represented by the general formula (III) or (IV), dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, or A quaternary ammonium salt obtained by quaternizing diethylaminopropyl (meth) acrylamide with the above quaternizing agent, or dimethyl diallyl ammonium chloride can be used. Here, the acid neutralized monomer has a disadvantage that the stability of viscosity is low because dissociation of the neutralized acid occurs due to the pH of the system and the polymer structure changes. From this point, a quaternary ammonium salt monomer is more preferable.

(C) Crosslinkable vinyl monomer Examples of the crosslinkable vinyl monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,2-butylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin (Meth) acrylic polyhydric alcohols such as di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Luric acid esters; acrylamides such as N-methylallylacrylamide, N-vinylacrylamide, N, N′-methylenebis (meth) acrylamide, bisacrylamideacetic acid; divinyl compounds such as divinylbenzene, divinyl ether, divinylethyleneurea; diallyl Polyallyl compounds such as phthalates, diallyl malates, diallylamines, triallylamines, triallyl ammonium salts, allyl ethers of pentaerythritol, allyl ethers of sucrose having at least two allyl ether units in the molecule; vinyl (meta ) Acrylate, allyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate (Meth) acrylic acid esters of unsaturated alcohols such as cartons.
Among these crosslinkable monomers, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, divinylbenzene, pentaerythritol triallyl ether, or pentaerythritol tetraallyl ether is preferable.

(D) Other vinyl monomers The cationic group-containing copolymer (a) is not limited to the above three types of vinyl monomers, which are essential structural units, but other vinyl monomers that can be copolymerized therewith. A monomer can be a constituent component. Other vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t -Butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, cyclopentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (Meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, xylyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate And (meth) acrylic acid derivatives such as 2-butoxy (meth) acrylate, 2-phenoxy (meth) acrylate, 3-methoxypropyl (meth) acrylate, and 3-ethoxypropyl (meth) acrylate.
The other vinyl monomer is preferably used in an amount of not more than 30% by weight, particularly preferably not more than 15% by weight, based on the total monomers constituting the cationic group-containing copolymer.

(E) Cationic group-containing copolymer Nonionic group-containing vinyl monomer (a ₁ ) and cationic group-containing vinyl monomer (a ₂ ), which are monomers forming a cationic group-containing copolymer The preferable blending ratio is 2/98 to 98/2, and more preferably 40/60 to 97/3 in terms of a molar ratio of (a ₁ ) / (a ₂ ). When the molar ratio is large, the expression of thixotropy is facilitated, and when the molar ratio is small, the viscosity can be easily maintained at a low share rate. However, it is preferable that both characteristics are within the above ranges.
The proportion of the crosslinkable vinyl monomer (a ₃ ) is preferably 0.002 to 5% by weight, particularly preferably 0.002% by weight or more and less than 0.1% by weight, based on the total amount of the monomers. If the proportion of the monomer (a ₃ ) is 0.002% by weight or more, the viscosity of the hydrogel formed from the cationic group-containing copolymer is sufficient. The feel of the gel is soft and slippery.
As a preferable embodiment of the component (F) (a) cationic group-containing copolymer of the present invention, N, N-dimethylaminoethyl diethyl methacrylate sulfate-N, N-dimethylacrylamide represented by the following formula: Examples thereof include a polyethylene glycol dimethacrylate copolymer.

(In the formula, x / y = 1/9 to 5/5 and (x + y + z) /z=1/0.1 to 1 / 0.002 in molar ratio.)
For example, as a commercial item, Sofcare KG-301W [manufactured by Kao Corporation] or Sofcare KG-101E [manufactured by Kao Corporation] can be mentioned.

The (b) cationized cellulose derivative of component (F) is described in detail below.
(B) As a cationized cellulose derivative, what is represented by the following general formula (VI) is preferable.

In formula (I), A represents a residue of an anhydroglucose unit, a is an integer of 50 to 20000, and each R ²¹ represents a substituent represented by the following general formula (VII).

In the formula (VII), R ′ and R ″ are alkylene groups having 2 or 3 carbon atoms, b is an integer of 0 to 10, c is an integer of 0 to 3, d is an integer of 0 to 10, and R ′ ″ is An alkylene or hydroxyalkylene group having 1 to 3 carbon atoms, R ²² , R ²³ and R ²⁴ are the same or different and each represents an alkyl group, an aryl group or an aralkyl group having up to 10 carbon atoms, or It may contain a nitrogen atom to form a chlorine ring, and X ₁ represents an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfuric acid, phosphoric acid, nitric acid, etc.).
The degree of cation substitution of the cationized cellulose is 0.01 to 1, that is, the average value of c per anhydroglucose unit is 0.01 to 1, preferably 0.02 to 0.5. Moreover, the sum total of b + d is 1-3 on average. A degree of substitution of 0.01 or less is not sufficient, and may be 1 or more, but 1 or less is preferable from the viewpoint of reaction yield. For example, R ²² , R ²³ and R ²⁴ are preferably CH ₃ groups or short chain alkyl groups such as two CH ₃ groups, and the remaining one is a long chain alkyl group having 10 to 20 carbon atoms. The molecular weight of the cationized cellulose used here is between about 100,000 and 8000000.
For example, as a commercial item, Poise C-80H [manufactured by Kao Corporation], polymer JR-400 (manufactured by Dow Chemical Co., Ltd.) and the like can be mentioned.

The (c) cationized guar gum derivative of component (F) is described in detail below.
(C) As a cationized guar gum derivative, what is represented by the following general formula (VIII) is preferable.

In the formula (VIII), D is a guar gum residue, R ²⁵ is an alkylene group or a hydroxyalkylene group, R ²⁶ , R ²⁷ and R ²⁸ are the same or different, and an alkyl group having 10 or less carbon atoms, an aryl group, or It may represent an aralkyl group or may contain a nitrogen atom in the formula to form a heterocyclic ring, and X ₃ is an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methylsulfuric acid, phosphoric acid, sulfuric acid, etc.) , And f represents a positive integer.
The degree of cation substitution of the cationized guar gum derivative is preferably 0.01 to 1, particularly 0.02 to 0.5 in which cation groups are introduced into the sugar unit. This type of cationic polymer is described in JP-B-58-35640, JP-B-60-46158, and JP-A-58-53996. For example, commercially available products include Rhodia (Rhodia). Inc.) under the trade name Jaguar, including Jaguar C-13C.

The component (F) (d) diallyl quaternary ammonium salt polymer or diallyl quaternary ammonium salt / acrylamide copolymer is described in detail below.
As (d) diallyl quaternary ammonium salt polymer or diallyl quaternary ammonium salt / acrylamide copolymer, those represented by the following general formula (IX) or (X) are preferable.

In the formulas (IX) and (X), R ³³ and R ³⁴ are the same or different, and are hydrogen, alkyl group (1 to 18 carbon atoms), phenyl group, aryl group, hydroxyalkyl group, amidoalkyl group, cyano. An alkyl group, an alkoxyalkyl group, or a carboalkoxyalkyl group, R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are the same or different, and are a hydrogen atom, a lower alkyl group (1 to 3 carbon atoms), a phenyl group, X ₄ is an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfuric acid, sulfuric acid, etc.), g is an integer of 1-50, h is an integer of 0-50, and i is an integer of 150-8000. .
The molecular weight of the diallyl quaternary ammonium salt / acrylamide copolymer is about 30,000 to 2,000,000, preferably 100,000 to 1,000,000.
For example, as a commercial item, it is marketed by the brand name Marcoat from Nalco Corporation, and Marcoat 100, Marcoat 550, etc. are mentioned.

  One or more components (F) can be used. The content of the component (F) in the solid detergent composition of the present invention is preferably 0.01 to 5% by weight, more preferably 0.05 to 1% by weight in the total composition from the viewpoint of the effect of improving foam quality. Particularly preferred is 0.1 to 0.5% by weight.

  The solid detergent composition of the present invention is used by being wetted with water. For example, it can be used as a skin cleanser such as a facial cleanser or a body cleanser, and these cleaning compositions can be blended with optional components depending on the purpose. Here, as optional components, anionic surfactants other than components (A) and (D), nonionic surfactants other than component (C), and amphoteric surfactants, which are usually blended in these detergents. Conditioning agents other than the agent, the cationic surfactant and the component (B).

  Examples of anionic surfactants other than components (A) and (D) include phosphate ester salts, sulfosuccinic acid surfactants, polyoxyalkylene alkylamide ether sulfates, monoglyceride sulfates, olefin sulfonates, and alkane sulfones. And acid salts, acylated isethionate salts, acylated amino acid salts, polyoxyalkylene alkyl ether phosphates, polyoxyalkylene alkyl ether acetates, and the like.

  Examples of the nonionic surfactant other than the component (C) include alkyl polyglycosides, sucrose fatty acid esters, polyglycerin fatty acid esters, fatty acid alkanolamides, alkylamine oxides, fatty acid polyhydric alcohol esters, alkoxylates, and the like.

  Amphoteric surfactants include amide betaine surfactants, amide amino acid surfactants, carbobetaine surfactants, sulfobetaine surfactants, amide sulfobetaine surfactants, imidazolinium betaine surfactants. Agents, phosphobetaine surfactants, and the like. Of these, alkylcarboxymethylhydroxyethyl imidazolium betaine, fatty acid amidopropyl betaine and alkylhydroxysulfobetaine are particularly preferred. The fatty acid amidopropyl betaine and the alkylhydroxysulfobetaine are preferably those having an alkyl group having 8 to 18 carbon atoms, particularly 10 to 16 carbon atoms, and particularly amide propyl betaine laurate, palm kernel oil fatty acid amidopropyl betaine, and coconut oil fatty acid. Amidopropyl betaine, lauryl hydroxysulfobetaine and the like are preferred. These amphoteric surfactants are preferably contained in the solid detergent composition of the present invention in an amount of 0.5 to 40% by weight, more preferably 1 to 30% by weight, and particularly 2 to 25% by weight from the viewpoint of foamability. .

  As a cationic surfactant, the following general formula (5)

[In the formula, at least one of R ³⁸ , R ³⁹ , R ⁴⁰ and R ⁴¹ may be substituted with an alkoxy group having 8 to 28 carbon atoms, an alkenyloxy group, an alkanoylamino group or an alkenoylamino group. Represents a good alkyl group or alkenyl group, the remainder represents a benzyl group, an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group or a polyoxyethylene group having a total number of added moles of 10 or less, Z ⁻ represents a halogen ion or an organic anion. Show. A quaternary ammonium salt represented by the formula:

  Examples of conditioning components include higher alcohols such as lauryl alcohol, cetyl alcohol, and stearyl alcohol, silicones and silicone derivatives, lanolin, squalene, hydrocarbons, protein derivatives, and oil agents such as fatty acid esters of polyethylene glycol. These conditioning components are added in the solid detergent composition of the present invention in an amount of 0.05 to 20% by weight, more preferably 0.1 to 15% by weight, especially 0.1 to 12%, from the viewpoint of improving the feeling of foam and storage stability. It is preferable to contain by weight.

  Other components usually used in cleaning compositions, for example, water-soluble polymers such as polysaccharides such as methylcellulose, hydroxyethylcellulose, carboxyvinyl polymer, xanthan gum; polyoxyalkylene sorbitan ester, polyoxyethylene glycol distearate Viscosity modifiers such as ethanol, chelating agents such as ethylenediaminetetraacetic acid (EDTA) and phosphonates, preservatives such as methylparaben and butylparaben, active ingredients such as vitamins and their precursors, and animal and plant extracts such as lecithin and gelatin Or its derivatives; fine polymer powders such as nylon and polyethylene; anti-inflammatory agents such as dipotassium glycyrrhizinate; bactericides and antidandruff agents such as triclosan, trichlorocarban, octopirox, zinc pyrithione; dibutylhydroxytoluene, etc. Antioxidants; pearling agents, ultraviolet absorbers, pH adjusting agents, dyes, perfumes, water can be optionally added within the range not damaging the effects of the present invention.

  Hereinafter, an example is given and it demonstrates in detail.

Invention products 1-7 and comparative products 1-9
<Production method>
Each component shown in Table 1 and Table 2 was mixed and heated to prepare a molten soap composition, which was poured into a mold and allowed to cool to solidify. In this way, solid detergent compositions described in Tables 1 and 2 were prepared.

<Evaluation method 1>
About the solid detergent composition of this invention products 1-7 and comparative products 1-7, it tested and evaluated as it demonstrates below regarding the hardness at the time of use, the amount of foaming, and foam quality. The obtained results are shown in Table 1.

(Hardness)
The hardness at the time of use was evaluated by actually using it by wetting with 4 ° DH hard water. The evaluation criteria were “◯” when it did not swell during use and did not melt, “△” when soft and soft when used, and “X” when the shape could not be maintained during use.

(Evaluation of foaming amount)
0.1 g of the produced detergent composition was weighed into a sample tube, and ion exchange water was added to make 10 mL. The sample tube descended up and down 20 times in 10 seconds, and then the amount of foaming was judged by the height of the foam from the tube bottom. According to the following evaluation criteria, 5 grades 1-5 were evaluated. It was set to “5” for very foaming, “4” for very foaming, “3” for slightly foaming, “2” for slightly foaming, and “1” for no foaming at all.

(Foam sensory evaluation)
The produced washed solid was wetted with 4 ° DH hard water, rubbed by hand for 10 seconds, and then bubbled for 30 seconds for sensory evaluation. The sensory evaluation was performed by 10 expert panelists, and the creamyness of the foam was evaluated in five stages of 1 to 5 and averaged. Based on soap (15% aqueous solution consisting of lauric acid / myristic acid / palmitic acid = 6 / 4.5 / 4.5), “5” if very creamy than soap foam, than soap foam "4" if slightly creamy, "3" if it is about the same as soap bubbles, "2" if it is slightly bubbly than soap bubbles, if very bubbly than soap bubbles Was “1”.

<Evaluation method 2>
The solid detergent compositions of Invention Product 3 and Comparative Products 8 and 9 were tested and evaluated as described below for sweat resistance and hardness resistance. The obtained results are shown in Table 2.

(Sweat resistance)
0.1 g of the produced washed solid was weighed into a sample tube, and various concentrations of saline were added to make 10 mL. The sample tube descended up and down 20 times in 10 seconds, and then the amount of foaming was judged by the height of the foam from the tube bottom. According to the following evaluation criteria, 5 grades 1-5 were evaluated. It was set to “5” for very foaming, “4” for very foaming, “3” for slightly foaming, “2” for slightly foaming, and “1” for no foaming at all.

(Hard water resistance)
0.1 g of the produced washed solid was weighed into a sample tube, and water of various hardness was added to make 10 mL. The sample tube descended up and down 20 times in 10 seconds, and then the amount of foaming was judged by the height of the foam from the tube bottom. According to the following evaluation criteria, 5 grades 1-5 were evaluated. It was set to “5” for very foaming, “4” for very foaming, “3” for slightly foaming, “2” for slightly foaming, and “1” for no foaming at all.

From the results shown in Table 1, it can be seen that the comparative product containing no component (A) has almost no foam. Moreover, it turns out that the product of this invention containing a component (B) becomes very creamy foam quality. However, in the case where the component (B) is not included, it has been found that even if only the cationic polymer is added, the foam quality improvement effect is not so much. When component (C) was not included, it was found that the foaming power was reduced. Moreover, it turns out that the comparative product which does not contain component (D) and (E) has a problem in hardness.

  From the results of Table 2, it can be seen that the comparative product 8 prepared with the composition of the general fatty acid soap has a good foaming power in the absence of stress, but once the sweat component is added or the hardness of the water is increased. As a result, it became clear that the foam performance was greatly reduced. In addition, it was found that the comparative product 9 made with the composition of “Cinderet Bar” mainly used in areas with high hardness also reduced foaming power, although not as much as general fatty acid soap. On the other hand, it was found that the product of the present invention exhibits a problem-free foaming force even in a harsh environment where the comparative products 8 and 9 hardly foam.

Claims (4)

The following components (A), (B), (C), (D) and (E):
(A) General formula (1)
R ¹ O (CH ₂ CH ₂ O) _n SO ₃ M (1)
(In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, n represents an average number of added moles, 2 to 5 and M represents an alkali metal atom or alkanol. A sulfate represented by the formula:
(B) myristyl alcohol ,
(C) General formula (3)
R ³ —OCH ₂ —CH (OH) —CH ₂ —OH (3)
(Wherein R ³ represents a linear or branched alkyl group or alkenyl group having 6 to 14 carbon atoms),
(D) General formula (4)
R ⁴ -COOM (4)
(Wherein R ⁴ represents a linear alkyl group having 11 to 23 carbon atoms, and M represents an alkali metal atom, magnesium, alkanolamine or ammonium),
(E) contains an inorganic salt,
The sum total of the component (A), the component (B) and the component (C) is 25 to 40% by weight,
[Component (A) + Component (B) + Component (C)] / [Component (D) + Component (E)] = 2.0 to 0.5, and the content of the component (A) is 22.0. Solid detergent composition which is -30.8 weight%, content of a component (B) is 2.2-3.0 weight%, and content of water is 50 weight% or less. Further, (F) a solid detergent composition according to claim 1, further comprising a cationic polymer. Claim 1 or 2 Solid detergent composition according content of 0.1 to 15 wt% of Ingredient (C). It is a skin cleaning composition, The solid cleaning composition in any one of Claims 1-3 .