JP4991217B2 - Liquid cleaning composition for bathroom and liquid cleaning product for bathroom - Google Patents

Description

  The present invention relates to a bathroom liquid detergent composition and a bathroom liquid detergent product.

In general, fatty acids and tap water contained in soap and body shampoos, etc. as dirt adhering to hard surfaces such as plastics, tiles, stainless steel, ceramics, glass, etc. used in bathtubs, bathroom floors, walls and utensils Fatty acid metal salt (soap residue) formed by combining calcium in water, organic compounds such as nitrogen-containing compounds such as proteins, free fatty acids, glycerides, fatty acid metal salts (soap residue), and inorganic substances such as mud There is red hot stains.
Conventionally, various cleaning compositions for removing dirt in the bathroom have been proposed. For example, Patent Document 1 discloses a bathroom liquid detergent composition containing a cationic surfactant, an anionic surfactant, a sequestering agent, and a water-soluble solvent. Patent Document 2 discloses a detergent composition containing an anionic surfactant or nonionic surfactant, a fatty acid or a salt thereof, a solvent, and a metal sequestering agent. Patent Document 3 discloses a cleaning composition containing a specific N-alkyl or alkenyl amino acid or a salt thereof and a specific N-alkyl-N, N-di (carboxyalkyl) amine or a salt thereof. Yes. Patent Document 4 discloses a liquid detergent composition containing a specific amine oxide and other surfactants. Patent Document 5 discloses a bathroom liquid detergent composition containing at least a surfactant, a chelating agent, a polymer compound, a solvent, and a fragrance. Patent Document 6 discloses a detergent composition containing an anionic surfactant, a nonionic surfactant and an amphoteric surfactant.
Japanese Patent No. 2952561 JP 11-335700 A JP 2000-328091 A JP 2001-329293 A JP 2003-183698 A JP-A-2005-008702

In recent years, many spray-type products have been proposed as liquid detergent products containing a bathroom liquid detergent composition in a container, including for bathrooms. Above all, liquid detergent products that appeal to being able to be cleaned without being rubbed after spraying are being developed because of their ease of use.
However, the conventional liquid detergent composition for bathrooms has a certain level of detergency against soap scum stains, but it does not have sufficient detergency against hot red stains, especially when "cleaning without rubbing". In addition, the surface of the bathtub or the like remains rough.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a bathroom liquid detergent composition and a bathroom liquid detergent product having an excellent cleaning effect against hot water stains in the bathroom. And

When the present inventor examined and analyzed the above problems, the roughness was mainly composed of proteins (such as keratin which is a waste product of skin) adsorbed hydrophobically on the surface of a bathtub or the like. I found out. That is, the conventional liquid detergent composition for bathrooms does not have a sufficient cleaning effect on the protein that adheres firmly to the surface of the bathtub as described above. The cleaning power was also insufficient. As a result of further investigation based on this knowledge, the present inventor found that the use of a specific amount of specific three kinds of components exerted an excellent detergency against proteins, and completed the present invention. It was.
That is, the first aspect of the present invention for solving the above problems is the following (A) component 0.05 to 10% by mass, the following (B) component 0.05 to 5% by mass, and the following (C) component 0: 0.1-5 mass%, the following (D) component 0.05-5 mass%, and the following (E) component 0.5-5 mass%, The liquid cleaning composition for bathrooms characterized by the above-mentioned It is.
(A) N-alkyl or N-alkenyl amino acids and / or salts thereof.
(B) Nonionic surfactant.
(C) Fatty acid and / or salt thereof.
(D) A surfactant having semipolarity.
(E) Linear alkylbenzene sulfonic acid and / or salt thereof.
According to a second aspect of the present invention, there is provided a liquid ejecting container comprising: a container main body that stores a liquid; and an injection nozzle that includes an ejection nozzle that discharges the liquid stored in the container main body to the outside. It is the liquid detergent product for bathrooms which stored the liquid detergent composition for bathrooms of one mode.

  ADVANTAGE OF THE INVENTION According to this invention, the liquid composition for bathrooms and the liquid detergent product for bathrooms which have the outstanding cleaning effect with respect to the hot water stain in a bathroom can be provided.

≪Liquid detergent composition for bathroom≫
The bathroom liquid cleaning composition of the present invention (hereinafter sometimes simply referred to as a cleaning composition) contains the component (A), the component (B) and the component (C) as essential components. Hereinafter, each component will be described in detail.

<(A) component>
In the present invention, the component (A) has an effect of improving the detergency against hot dirt with the components (B) and (C). In this effect, it is presumed that the component (A) mainly has an effect of adsorbing and peeling off the protein soil.
N-alkyl amino acids are compounds in which an alkyl group is bonded to the nitrogen atom of the amino acid, and N-alkenyl amino acids are compounds in which an alkenyl group is bonded to the nitrogen atom of the amino acid.
In the present specification and claims, an alkyl group may be linear or branched unless otherwise specified. Further, the alkenyl group may be linear or branched unless otherwise specified.
In the N-alkylamino acid, the alkyl group may be linear or branched. The alkyl group preferably has 8 to 26 carbon atoms, more preferably 10 to 20 carbon atoms, and still more preferably 10 to 16 carbon atoms.
In the N-alkenyl amino acid, the alkenyl group may be linear or branched. The alkenyl group preferably has 8 to 26 carbon atoms, more preferably 10 to 20 carbon atoms, and still more preferably 10 to 16 carbon atoms.
The amino acid to which the alkyl group or alkenyl group is bonded is not particularly limited as long as it is a known amino acid. Glycine or alanine is preferable in terms of manufacturability and detergency.
The salt of the N-alkylamino acid or N-alkenylamino acid is preferably an alkali metal salt such as sodium or potassium, and is preferably a sodium salt.

  Preferred examples of the component (A) include compounds represented by the following general formula (I) or (II). Hereinafter, the compound represented by the formula (I) may be referred to as a mono form, and the compound represented by the formula (II) may be referred to as a di form.

In formula (I), R ¹ is an alkyl group or alkenyl group having 10 to 20 carbon atoms, m is 1 or 2, and M ¹ is a hydrogen atom or an alkali metal ion.
In the formula (II), R ² is an alkyl group or alkenyl group having 10 to 20 carbon atoms, p and q are each independently 1 or 2, and M ² and M ³ are each independently a hydrogen atom or Alkali metal ions (sodium ion, potassium ion, etc.).

Preferred specific examples of the component (A) include N-decylglycine, N-laurylglycine, N-myristylglycine, N-palmitylglycine, N-decylβalanine, N-laurylβalanine, N-myristylβalanine, N-palmityl β-alanine and salts thereof can be mentioned.
As the component (A), a commercially available product may be used, and examples of the commercially available product include laurylaminopropionic acid Na (manufactured by Lion Akzo Co., Ltd.). This laurylaminopropionic acid Na is a mixture of a mono form and a di form.

  In the cleaning composition, the content of the component (A) is 0.05 to 10% by mass, preferably 0.05 to 5% by mass, based on the total mass of the cleaning composition. If it is less than 0.05% by mass, the detergency against hot dirt is not sufficiently exhibited, and if it is more than 10% by mass, the low-temperature stability is deteriorated and stored at a low temperature, for example, −10 to 5 ° C. There is a risk of precipitation.

<(B) component>
In this invention, (B) component is a component which bears a cleaning function, and cleaning power improves by containing (B) component. Moreover, (B) component has the effect of improving the detergency with respect to hot red dirt with (A) component and (C) component. In such an effect, it is presumed that the component (B) mainly has an effect of penetrating into the interface of protein stains that are hydrophobically adsorbed on the surface, such as a bathtub, to raise the stains.
As the component (B), known nonionic surfactants can be used. For example, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid methyl ether, fatty acid Examples include glycerin ester, fatty acid polyglycerin ester, fatty acid sucrose ester, fatty acid alkanolamide, and alkyl polyglucoside.
As the component (B), polyoxyethylene alkyl ether is preferable, and a compound represented by the following general formula (III) is particularly preferable.
R ⁴ —O— (CH ₂ CH ₂ O) _r —H (III)
In formula (III), R ⁴ is an alkyl group having 8 to 20 carbon atoms. The alkyl group may be linear or branched. As for carbon number of this alkyl group, 10-18 are more preferable.
r is an average addition mole number of ethylene oxide, 2-20 are preferable and 5-15 are more preferable.

  In the cleaning composition, the content of the component (B) is 0.05 to 5% by mass, preferably 0.1 to 5% by mass, based on the total mass of the cleaning composition. If it is less than 0.05% by mass, the detergency, particularly the detergency against hot red stains, is not fully exhibited, and if it is more than 5% by mass, the rinsing property is deteriorated, and it is easy to use as a liquid detergent product. May be worse.

<(C) component>
In the present invention, the component (C) has an effect of improving the detergency against hot dirt with the components (A) and (B). Moreover, there exists an effect which prevents the fall of the rinse property by containing (B) component.
In the component (C), the fatty acid may be saturated or unsaturated, preferably a linear or branched fatty acid having 6 to 22 carbon atoms, and a linear or branched chain having 10 to 20 carbon atoms. The fatty acid is more preferred. Specific examples of the fatty acid include capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, oleic acid, coconut oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid and the like. Among these, lauric acid or coconut oil fatty acid is preferable in that it exhibits high detergency.
The salt of the fatty acid salt is not particularly limited, and examples thereof include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; ammonium salt; monoethanolamine salt, diethanolamine salt and triethanol. Examples thereof include alkanolamine salts such as amine salts. Among these, alkali metal salts are preferable, and potassium salts are more preferable.

  In the cleaning composition, the content of the component (C) is 0.05 to 5% by mass, preferably 0.1 to 5% by mass, based on the total mass of the cleaning composition. If the amount is less than 0.05% by mass, the effect obtained by blending the component (C) cannot be sufficiently obtained. Precipitation may occur when stored underneath.

<(D) component and (E) component>
The cleaning composition of the present invention preferably further contains 0.05 to 5% by mass of the following (D) component and 0.5 to 5% by mass of the following (E) component.
(D) A surfactant having semipolarity.
(E) Linear alkylbenzene sulfonic acid and / or salt thereof.
By using the component (D) and the component (E) in combination, the detergency against sebum stain is improved, and the detergency against hot red stain is further improved.

  Examples of the component (D) include alkylamine oxide, alkylamidopropylamine oxide, a compound represented by the following general formula (IV), a compound represented by the following general formula (V), and the like.

［式（ＩＶ）中、Ｒ^１１は炭素数８〜２６のアルキル基、ヒドロキシアルキル基、アシルアミドアルキル基またはアルキルフェニル基であり、ＡＯは炭素数２〜４のオキシエチレン基であり、ｎは０〜３であり、Ｒ^１２及びＲ^１３は、それぞれ独立して炭素数１〜３のアルキル基、ヒドロキシアルキル基またはポリオキシアルキレン基である。］

[In the formula (IV), R ¹¹ is an alkyl group having 8 to 26 carbon atoms, a hydroxyalkyl group, an acylamidoalkyl group or an alkylphenyl group, AO is an oxyethylene group having 2 to 4 carbon atoms, and n is 0 to 3, and R ¹² and R ¹³ are each independently an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a polyoxyalkylene group. ]

［式（Ｖ）中、Ｒ^１４は炭素数８〜１６の直鎖のアルキル基またはアルケニル基であり、Ｒ^１５は炭素数１〜５のアルキレン基であり、Ｒ^１６、Ｒ^１７はそれぞれ独立して炭素数１〜３のアルキル基またはヒドロキシアルキル基であり、Ｘは−ＣＯＯ−、−ＣＯＮＨ−、−ＯＣＯ−、−ＮＨＣＯ−または−Ｏ−である。］

[In the formula (V), R ¹⁴ is a linear alkyl group or alkenyl group having 8 to 16 carbon atoms, R ¹⁵ is an alkylene group having 1 to 5 carbon atoms, and R ¹⁶ and R ¹⁷ are independent of each other. An alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and X is —COO—, —CONH—, —OCO—, —NHCO— or —O—. ]

In formula (IV), R ¹¹ is preferably an alkyl group, and the alkyl group may be linear or branched. 8-26 are preferable and, as for carbon number of this alkyl group, 10-20 are more preferable.
R ¹² and R ¹³ are preferably each independently an alkyl group having 1 to 3 carbon atoms.

In the formula (V), R ¹⁴ is preferably a linear alkyl group, and the alkyl group preferably has 8 to 16 carbon atoms, and more preferably 10 to 16 carbon atoms.
R ¹⁶ and R ¹⁷ are preferably each independently an alkyl group having 1 to 3 carbon atoms.

  In the cleaning composition, the content of the component (D) is 0.05 to 5% by mass, preferably 0.1 to 5% by mass, based on the total mass of the cleaning composition. If the content is less than 0.05% by mass, the effect of blending the component (D) cannot be sufficiently obtained. If the content is more than 5% by mass, the low-temperature stability deteriorates, and the Precipitation may occur when stored under the condition of ° C.

In the component (E), as the linear alkylbenzene sulfonic acid, the linear alkyl group preferably has 8 to 16 carbon atoms, and more preferably 10 to 14 carbon atoms.
The salt of the linear alkylbenzenesulfonic acid is not particularly limited, and examples thereof include alkali metal salts such as sodium salt and potassium salt; alkanolamine salts such as monoethanolamine salt and diethanolamine salt. Among these, alkali metal salts are preferable, and sodium salts are particularly preferable.

  In the cleaning composition, the content of the component (E) is 0.05 to 5% by mass, preferably 0.1 to 5% by mass, based on the total mass of the cleaning composition. When the amount is less than 0.05% by mass, the effect of blending the component (E) is not sufficiently obtained. When the amount is more than 5% by mass, roughening occurs when the cleaning composition adheres to the hand. There is a risk of adverse effects such as occurring.

  In the cleaning composition of the present invention, the content ratio of the component (D) and the component (E) is a mass ratio of (D) / (E) = 1/10 to 10/1. It is preferable that it is 1/9 to 5/5. When the content ratio of the component (D) and the component (E) is within the above range, the effect obtained by blending the component (D) and the component (E) is improved.

<Other optional components>
In the cleaning composition of the present invention, other optional components can be blended as necessary.
Examples of other optional components include fragrances. A list of perfume ingredients used as perfumes can be found in various publications such as “Perfume and Flavor Chemicals”, Vol. I and II, Stephen Arctander, Allured Pub. Co. (1994); “Synthetic fragrance chemistry and commercial knowledge”, Motoichi Into, Chemical Industry Daily (1996); “Perfume and Flavor Materials of Natural Origin”, Stephen Arctander, Allred Pub. Co. (1994); “Aroma Encyclopedia”, edited by Japan Fragrance Association, Asakura Shoten (1989); “Performer Material Performance V.3.3”, Bolens Aroma Chemical Information Service (1996); “Flower oil” Perfumery ", Dante Lajaujis Anonis, Allured Pub. Co. (1993) and the like, and these can be arbitrarily used.

Other optional components include water-soluble solvents. By blending a water-soluble solvent, it is possible to obtain an effect of improving the cleaning ability of hot water stains and speeding up foaming.
As the water-soluble solvent, a general-purpose water-soluble solvent can be used, and specific examples include ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monobutyl ether, triethylene glycol monophenyl, propylene glycol monomethyl ether and the like. . Of these, diethylene glycol monobutyl ether is preferred from the viewpoint of storage stability and detergency.
When mix | blending a water-soluble solvent, 1-15 mass% is preferable with respect to the total mass of a cleaning composition as content of the water-soluble solvent in a cleaning composition.

Examples of other optional components include chelating agents. By blending a chelating agent, an effect of removing soap residue that is important as a bathroom cleaning agent can be obtained.
As the chelating agent, general-purpose chelating agents such as aminocarboxylic acid, oxycarboxylic acid, and phosphonic acid can be used.
Specific examples of the aminocarboxylic acid chelating agent include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetrapropionic acid, and the like.
Specific examples of the oxycarboxylic acid chelating agent include glycolic acid, citric acid, malic acid, gluconic acid and the like.
Specific examples of the phosphonic acid chelating agent include ethane-1, 1-diphosphonic acid, 1-hydroxyethane-1, 1-diphosphonic acid, and the like.
These chelating agents can be used in the acid form, and can also be used as a salt with an alkali metal or an alkanolamine.
Of these, ethylenediaminetetraacetic acid is preferred from the viewpoints of storage stability and detergency.
When the chelating agent is blended, the content of the chelating agent in the cleaning composition is preferably 0.1 to 10% by mass with respect to the total mass of the cleaning composition.

The cleaning composition of the present invention can further contain optional components other than those described above. Examples of such optional components include bactericides, antiseptic or antifungal agents, dyes, antioxidants, thickeners, ultraviolet absorbers, solubilizers, acrylic acid / maleic acid copolymers, and the like.
Among the above, the acrylic acid / maleic acid copolymer is a copolymer having a structural unit derived from an acrylic acid monomer and a structural unit derived from a maleic acid monomer. By using this copolymer together, the detergency against protein stains is improved, and the detergency against hot red stains is further improved. Moreover, the recontamination prevention effect improves by containing this copolymer.
Here, the “structural unit derived from an acrylic acid monomer” is a structural unit formed by cleavage of an ethylenic double bond of an acrylic acid monomer (monomer) (hereinafter referred to as a structural unit (m1)). Means). The “structural unit derived from a maleic acid monomer” is a structural unit formed by cleavage of an ethylenic double bond of a maleic acid monomer (monomer) (hereinafter referred to as a structural unit (m2)). Means. In addition, the structural unit (m2) may include a structural unit of acid anhydride (maleic anhydride).
The acrylic acid / maleic acid copolymer may have a structural unit (m3) other than the structural unit (m1) and the structural unit (m2), if necessary.
The acrylic acid / maleic acid copolymer may form a salt. Examples of the salt include alkali metal salts such as sodium salt and potassium salt, and alkanolamine salts such as monoethanolamine salt and diethanolamine salt. Of these, alkali metal salts are preferable, and sodium salts are more preferable.
Commercially available products suitably used as the acrylic acid maleic acid copolymer include Socaran CP7 (trade name, manufactured by BASF Japan), Aqualic TL-400 (trade name, manufactured by Nippon Shokubai), carboxylate HM-80 (product) Name, manufactured by Toagosei Co., Ltd.).

Examples of the bactericides include cationic surfactants, amphoteric surfactants, phenolic antibacterial agents such as 4-isopropyl-3-methylphenol, aldehyde antibacterial agents such as glutaraldehyde, N-butyl-1,2- Antibacterial components described in “All about Antibacterial” (1997) pages 129 to 172 published by Textile Co., Ltd., such as isothiazolone antibacterial agents such as benzisolyazolone-3 and ester antibacterial agents such as methyl ester of parahydroxybenzoic acid Can be used.
Examples of commercially available products that are suitably used as the antibacterial agent include ARCARD CB-50 (manufactured by Lion Akzo) and PROXEL XL2 (S) (manufactured by Avicia).

The pH of the cleaning composition of the present invention is not particularly limited, but in consideration of usability and detergency, the pH at 25 ° C. is preferably in the range of 5-9, and in the range of 7-8. More preferably.
What is necessary is just to mix | blend a pH adjuster suitably in order to adjust pH to the said range. As a pH adjuster, as long as the effects of the present invention are not impaired, sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine, and the like are preferable from the viewpoint of blending stability.

  The preparation method of the cleaning composition of the present invention is not particularly limited, and in the same manner as a normal liquid cleaning composition, for example, the above essential components and, if necessary, the above optional components, It can prepare by mix | blending water suitably and mixing these.

The usage method of the cleaning composition of this invention is not specifically limited, It can be used by the method similar to a general liquid cleaning composition for bathrooms.
Since the cleaning composition of the present invention has a high detergency against hot dirt, even after being attached to an object to be cleaned (bathtub, floor, wall, etc.) in the bathroom and then washed without rubbing, A sufficient cleaning effect can be obtained.
The cleaning composition of the present invention can be used by being filled in a resin container such as a plastic container, and in particular, as will be described later, a container main body containing a liquid, and the container main body It is preferable that the liquid is stored in a liquid injection container provided with an injection nozzle having an outlet for discharging the stored liquid to the outside and used as a liquid cleaning product for bathrooms.

≪Liquid detergent products for bathrooms≫
The bathroom liquid detergent product of the present invention (hereinafter sometimes simply referred to as a detergent product) includes a container main body for storing a liquid and a spout for discharging the liquid stored in the container main body to the outside. The liquid detergent composition for bathrooms of the present invention is contained in a liquid jet container provided with a jet nozzle.
In such a cleaning product, the cleaning composition in the liquid injection container is made into a linear shape, a mist shape, a foam shape, or the like by the injection nozzle and ejected to the outside. Therefore, when used, the cleaning composition can be easily attached to a wide range in the bathroom, and the convenience is high.
As the injection nozzle, any of the nozzles proposed so far can be used. For example, nozzles having various injection shapes such as a substantially perfect circle shape, an elliptical shape, and a belt shape can be used. Here, the “spout form” is the shape of a pattern formed on the surface of an object to be cleaned (such as a bathtub, a floor in a bathroom, a wall, and tools) by the sprayed cleaning composition.

In the present invention, in particular, it is preferable that the liquid ejecting container includes a nozzle cover attached to the outer wall of the ejecting nozzle, and the nozzle cover is fitted into the outer wall of the ejecting nozzle. And a cylindrical cover body having an opening that exposes the ejection port of the ejection nozzle, and a wall member surrounding the periphery of the cover body, the wall member ejecting the liquid discharged from the ejection port It is preferable to have a shape that expands the range. By using the liquid jet container provided with such a nozzle cover, when the cleaning composition of the present invention is sprayed on the object to be cleaned, the adhesion thereof becomes wide and uniform.
Hereinafter, the nozzle cover will be described more specifically with reference to the drawings.

FIG. 1 is an external perspective view showing an injection nozzle 1 (FIG. 1B) and a nozzle cover 2 (FIG. 1A).
2A is an external perspective view showing a state in which the nozzle cover 2 shown in FIG. 1 is detachably attached to the injection nozzle 1, and FIG. 2B is a view in FIG. It is sectional drawing in position XX 'shown in FIG.
The injection nozzle 1 has a jet outlet 1a through which the contents in the container can be jetted. In the injection nozzle 1, in order to realize a predetermined ejection form, a wide track elliptical bubble-forming cylinder 1b extends forward in the ejection direction so as to surround the ejection outlet 1a, and the foam-forming cylinder 1b A plurality of air introduction holes that lead to the air introduction portion 1 c that opens to the outer wall of the injection nozzle 1 are provided on the inside.

The nozzle cover 2 includes a cylindrical cover body 2b provided with an opening 2a that exposes the ejection port 1a of the ejection nozzle 1 and a fitting portion 6 that fits on the outer wall of the ejection nozzle 1. Has a structure in which a wall member 2c surrounding the periphery is integrally attached.
The opening 2a is provided with a barrier h for positioning the spray nozzle 1 by contacting the edge of the front end surface of the spray nozzle 1 when the spray nozzle 1 is adapted to the cover body 2b.
Three cutouts 3 are formed on the wall surface of the rear end portion of the cover body 2b, and the cutouts 3 are adapted to the convex portions 4 provided integrally with the outer wall of the injection nozzle 1. ing. The presence of the notch 3 and the convex portion 4 prevents backlash when the nozzle cover 2 is fitted, and prevents the nozzle cover 2 from rotating when the outer wall of the injection nozzle 1 is a curved surface. It can be done.
Cutouts 5 are formed on the left and right sides of the cover body 2b from the front end to the rear. The notch 5 is formed so as to expose the air introduction part 1c of the injection nozzle 1 from the cover main body 2b, whereby the air for generating bubbles is smoothly passed through the air introduction part 1c of the injection nozzle 1. Can be introduced to.
The fitting part 6 is a convex part formed on the inner wall surface of the rear end of the cover body 2b. As shown in FIG. 2B, when the nozzle cover 2 is attached to the injection nozzle 1, the fitting portion 6 contacts the end surface of the step 1 ′ provided on the outer peripheral wall of the injection nozzle 1, thereby The nozzle cover 2 can be prevented from coming off from the injection nozzle 1.

The wall member 2c is configured so that when the nozzle cover 2 is attached to the spray nozzle 1, both the cover body 2b and the spray nozzle 1 are accommodated inside, and from the tip of the spray nozzle 1 toward the liquid ejection direction, It has a trumpet shape (elliptical shape) with different diameters (the upper and lower and left and right diameter dimensions are different) whose cross-sectional area gradually increases.
By attaching such a wall member 2c, the ejection range of the liquid ejected from the ejection nozzle 1 is expanded by the Coanda effect.
“Coanda effect” refers to the nature of a fluid that attempts to flow along an object when placed in the flow. When a jet (air flow, water, etc.) is sprayed along a surface due to the Coanda effect. The phenomenon of flowing along the surface occurs.
That is, when the cleaning composition is released together with air from the spray nozzle 1 equipped with the nozzle cover 2 to which the wall member 2c is attached, the jet flows along the wall member 2c.
When the cleaning composition is normally sprayed from the spray nozzle 1 as a mist, foam, or the like, it forms an injection pattern having a shape that matches the foam-forming cylinder 1b in the forward direction of the ejection. For example, in this example, since the foam-forming cylinder 1b has a track elliptical shape, a substantially conical injection pattern having a substantially track elliptical cross-sectional shape is formed (see FIG. 4).
At this time, when the wall member 2c having a shape that expands outward from the center of the injection direction rather than the substantially conical injection pattern is provided, as shown in FIG. The direction in which the jet flow immediately after changes in the direction of the wall member 2c, and the cross-sectional area of the injection pattern is larger than when the wall member 2c is not attached (see FIG. 4). As a result, the range to which the cleaning composition adheres when sprayed into the bathroom is increased.

FIG. 5 is a schematic diagram showing the shape of the end (the front end portion in the ejection direction) of the wall member 2c in this embodiment and the positional relationship between the wall member 2c and the foamed cylinder 1b having the track elliptical shape of the injection nozzle 1. .
5A is a top view showing the wall surface of the nozzle member 2 shown in FIGS. 1 and 2 from the tip in the liquid ejection direction to the same plane as the plane including the opening 2 of the cover body 2b. FIG. 5 (b) is a longitudinal sectional view in the major axis direction of the ejection direction tip shown in FIG. 5 (a), and FIG. 5 (c) is a short view of the ejection direction tip shown in FIG. 5 (a). It is a longitudinal cross-sectional view in radial direction.
In the embodiment shown in FIG. 5, the inner diameter Y in the long side direction of the foam-forming cylinder 1b is in the range of 7 to 10 mm, and the inner diameter Z in the short-side direction of the foam-forming cylinder 1b is in the range of 3 to 4 mm. In some cases, it is preferable that p in FIG. 5B is within the range of +1 to +8 mm of q. Within this range, the Coanda effect is likely to occur and the expansion effect of the injection pattern is improved.
Here, p is the inner diameter in the long side direction of the tip of the ejection direction of the wall member 2c. When Y and Z are in the above range, p is preferably in the range of 30 to 37 mm, and more preferably in the range of 35 to 37 mm.
q is an inner diameter in the long side direction of the wall member 2c on the same plane as the plane including the barrier h of the opening 2a of the cover body 2b. When Y and Z are in the above range, q is preferably in the range of 26 to 32 mm, and more preferably in the range of 28 to 30 mm.

In addition, r (the height from the barrier h of the opening 2a of the cover body 2b to the tip of the ejection direction of the wall member 2c) in FIG. 5B is 2 to 2 when Y and Z are within the above range. It is preferably within a range of 8 mm, and more preferably within a range of 4 to 5.5 mm.
In the present invention, s in FIG. 5C (inner diameter in the short side direction of the tip of the ejection direction of the wall member 2c) is not particularly limited, but when Y and Z are within the above ranges, 18 to 22 mm. It is preferable to be within the range.
Further, t (inner diameter in the short side direction of the wall member 2c on the same plane as the plane including the opening 2 of the cover body 2b) is not particularly limited, but when Y and Z are within the above ranges, 17 to 21 mm. It is preferable to be within the range.

In order to make the liquid in the container into a foam shape, the liquid is introduced from the container body into the foam-forming cylinder portion incorporated at the tip of the injection nozzle 1, and the liquid collides with the wall of the foam-forming cylinder to cause turbulent flow. And a method of promoting mixing with air, a method of arranging a barrier or mesh on the front surface of the injection nozzle 1 to make it foam, and the structure related to this point is a conventional structure Is done.
Air for generating bubbles is introduced through the air introduction part 1c and the air introduction hole of the injection nozzle 1 through the fitting gap between the cover main body 2b and the injection nozzle 1. Although not shown, for the purpose of securing an air flow path to the air introduction portion 1c of the injection nozzle 1 in the mounted state of the nozzle cover 2, either or both of the inner wall of the cover body 2b and the outer wall of the injection nozzle 1 are provided. A protrusion, a protrusion, or a concave groove can be formed.

The cover body 2b and the wall member 2c are preferably integrated from the viewpoint of reducing the number of parts and simplifying the assembly man-hour, but a separate structure may be adopted.
The shape of the wall member 2c is shown as a trumpet shape (elliptical shape) having a different diameter in FIGS. 1 and 2, but is not limited to the illustrated shape. Various changes are made according to the ejection form.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In the following examples, “%” means “% by mass” unless otherwise specified.
( Reference Examples 1-3, Examples 4-9 , Comparative Examples 1-6)
The components shown in Tables 1 to 3 were mixed to prepare a bathroom detergent composition.

<Description of components shown in Tables 1 to 3>
[(A) component]
A-1: Laurylaminopropionic acid Na (Lion Akzo, trade name: Amphorac L-18, also known as: N-lauryl-β-alanine Na salt).
A-2: N-laurylglycine Na salt (a synthetic product obtained by a usual method using monochloroacetic acid and laurylamine (Lion Akzo, trade name: Armin 12D)).
[Component (B)]
_{B-1: C n H 2n} + 1 O (CH 2 CH 2 O) 15 H (n = 12; that of ethylene oxide 15 mol naturally lauryl alcohol by addition polymerization with an alkali catalyst method).
_{B-2: C n H 2n} + 1 O (CH 2 CH 2 O) 15 H (n = 12/13 mixture (weight ratio 55/45), synthesized the synthetic product by synthesis method shown below).
_{B-3: C n H 2n} + 1 O (CH 2 CH 2 O) 5 H (n = 12/13 mixture (weight ratio 45/55), synthesized the synthetic product by synthesis method shown below).
[Component (C)]
C-1: Palm fatty acid potassium (manufactured by Lion Chemical).
[(D) component]
D-1: Lauryldimethylamine oxide (trade name: manufactured by Lion Akzo, trade name: Aromox DM12D-W (C)).
D-2: Lauryldimethylamidopropylamine oxide, a synthetic product synthesized by the synthesis method shown below).
[(E) component]
E-1: C10-C14 linear alkylbenzene sulfonic acid (manufactured by Lion Corporation).

(Synthesis method of B-2)
Product name Safol 23 alcohol (branch rate 50% ^{* 1} ) 224.4g, 30% NaOH aqueous solution 2.0g was extract | collected in the pressure | voltage resistant reaction container, and nitrogen substituted the inside of a container.
Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 763.6 g of ethylene oxide (gaseous) was gradually added to the alcohol liquid while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube.
After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% p-toluenesulfonic acid was added to neutralize so that the pH of the 1% aqueous solution of the reaction was about 7, to obtain B-2.
The “branch rate” of * 1 indicates the ratio of the number of carbon atoms constituting the alcohol having a branched chain to the total number of carbon atoms constituting the alcohol.

(Synthesis method of B-3)
388 g of trade name Neodol 23 alcohol manufactured by Shell Chemicals Co., Ltd., 0.4 g of Mg, Al and Mn composite oxidation catalyst described in Example 1 of Japanese Patent No. 3312883 were collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. .
Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 440 g of ethylene oxide (gaseous) was gradually added into the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube.
After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% p-toluenesulfonic acid was added to neutralize so that the pH of the 1% aqueous solution of the reaction was about 7, and the average number of moles of ethylene oxide added was 5 B-3 having a narrow rate of 86% was obtained. The narrow ratio is as described in JP-A-2005-132898 P4.

(Synthesis method of D-2)
<Production of raw material amine>
A 1 liter four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser is charged with 300 g of lauric acid methyl ester (Lion Chemical Co., Pastel M12, molecular weight 214) as a fatty acid ester, and nitrogen at 60 ° C. Substitution (reduced pressure to 13 kPa, normal pressure and nitrogen return) was performed twice, then the temperature was raised to 180 ° C., and 186 g of dimethylaminopropylamine (BASF, hereinafter abbreviated as “DMAPA”) (methyl laurate) The molar ratio with respect to: 1.3) was added dropwise over 3 hours. The reaction product was prepared by maintaining the temperature at 180 to 190 ° C. for 5 hours after the completion of the dropwise addition of DMAPA. Methanol produced as a by-product of the reaction was distilled out of the system by flowing warm water at 80 ° C. through the cooler, and DMAPA was refluxed. Thereafter, while maintaining at 180 to 190 ° C., the pressure was reduced to 4.0 kPa and maintained for 1 hour, whereby unreacted DMAPA was distilled off to obtain lauric acid dimethylaminopropylamide.
<Production of amidoamine oxide>
In a 1 liter four-necked flask equipped with a stirrer, thermometer and reflux condenser, 200 g of lauric acid dimethylaminopropylamide synthesized above (molecular weight calculated from amine value) so that the active ingredient is 30%. 286), 200 g of purified water was charged, and 8% of hydrogen peroxide (Mitsubishi Gas Chemical Co., Ltd., 45% diluted with purified water, 1.05 mol ratio of amine to 56% of amine) was added at 75 ° C. with stirring. It was added dropwise over time. After completion of dropping, the mixture was aged at 85 ° C. for 5 hours to obtain an amidoamine oxide having an active ingredient of 30.1%.

[Common composition]
<Common composition A>
Ethylenediaminetetraacetic acid: 1.5% by mass.
Diethylene glycol monobutyl ether: 8.0% by mass.
Citric acid: 1.2% by mass.
Sodium hydroxide: appropriate amount.
Purified water: balance.

<Common composition B>
Ethylenediaminetetraacetic acid: 2.0% by mass.
Diethylene glycol monobutyl ether: 8.0% by mass.
Citric acid: 1.5% by mass.
Xanthan gum: 0.1% by mass.
Sodium hydroxide: appropriate amount.
Purified water: balance.

[Perfume compositions A to D]

The pH (25 degreeC) of the obtained liquid cleaning composition for bathrooms is written together in Tables 1-3.
Further, in the obtained bathroom liquid detergent composition, in the terminal shape shown in FIG. 5, Y is 8.5 mm, Z is 3.5 mm, and p and r are values shown in Table 5, respectively. , Q was 29.0 mm, s was 19.2 mm, and t was 18.2 mm. The product was accommodated in a liquid jet container including jet nozzles A to H to obtain a bathroom liquid detergent product.

The following evaluation was performed about the obtained bathroom liquid detergent composition and bathroom liquid detergent product obtained. The results are also shown in Tables 1-3.
<Cleaning ability of hot water stains>
(Evaluation method)
After fixing a glass fiber reinforced plastic (FRP) test piece (3 x 10 cm) to the inner wall of a bathtub in a general household, one adult male, one female, and two elementary school boys each take two baths (per day The bath was taken once and repeated for 2 days, during which time the bath water was re-boiled without being replaced), and dirt was adhered.
After sufficiently drying the test piece on which the bath dirt is adhered, a liquid detergent composition (stock solution) is sprayed on the test piece so that the entire surface is wet, and left for 30 seconds, and then tap water (15 )). After sufficiently drying, the removed state of the test piece surface was visually evaluated according to the following evaluation criteria.
(Evaluation criteria)
5 points: Very good dirt removal.
4 points: Good stain removal.
3 points: Unevenness in removing dirt.
2 points: Slightly dirty.
1 point: Dirt is hardly removed.

<Sebum dirt cleaning power>
(Evaluation method)
As a model stain, 70 parts of an oily component (50 parts of oleic acid, 30 parts of triolein, 20 parts of cholesterol oleate) is added to 30 parts of a soap component (50 parts of calcium palmitate + 50 parts of calcium stearate) Mixed.
A 5 cm × 7 cm glass plate was placed in the model soil heated to 80 ° C., allowed to stand for 30 seconds, then slowly pulled up and left at 25 ° C. overnight to prepare a test sample.
To the above test sample, 1.0 mL of a liquid detergent composition (stock solution) was dropped and rubbed lightly with a sponge. After rinsing with tap water, stain removal was visually evaluated according to the following evaluation criteria.
(Evaluation criteria)
5 points: Very good dirt removal.
4 points: Good stain removal.
3 points: Unevenness in removing dirt.
2 points: Slightly dirty.
1 point: Dirt is hardly removed.

<Length of foam>
(Evaluation method)
Spray the liquid detergent product from the position 20 cm away from the jet outlet of the liquid jet container onto the vertical surface of the acrylic plate, and then determine the length of the major diameter of the foam formed on the vertical surface with a ruler. And measured visually using the following evaluation criteria.
(Evaluation criteria)
○: The length is 20 cm or more.
X: Length is less than 20 cm.

As is clear from the above results, the liquid detergent compositions for bathrooms of Reference Examples 1 to 3 and Examples 4 to 9 showed excellent cleaning power against hot red stains. Moreover, it was excellent also in the detergency with respect to sebum dirt, and especially the detergency was high in Examples 4-9 which used (D) component and (E) component together.
Moreover, the liquid detergent products for bathrooms of Reference Examples 1 to 3 and Examples 4 to 9 have long foams formed by spraying. For example, Reference Examples 1 to 3, Example 4 and Comparative Examples 1 to 4 When the same liquid jet container was used, the foam length was longer in the example.
On the other hand, the bathroom detergent compositions of Comparative Examples 1 to 6 that did not contain any of the component (A), the component (B), and the component (C) had low detergency against hot dirt. In addition, even when (D) component and (E) component were used in combination with sebum stain, sufficient detergency was not obtained. Moreover, the length of the foam formed by spraying was also short.
In addition, among Comparative Examples 1 to 6, Comparative Examples 1 to 4 using the injection nozzles A to C and E to G where p is 35 to 37 mm are comparisons using the injection nozzles D and H where p is 38 mm. It was longer than Examples 5-6. From this result, it has confirmed that the liquid spray container provided with the injection nozzle whose p is 35-37 mm is excellent in the expansion effect (Coanda effect) of the ejection form.

(Examples 10 to 11)
Each component shown in Table 6 was mixed to prepare a bathroom liquid detergent composition.
In the table, * 2 is a product name: Socaran CP5 manufactured by BASF.
* 3 is a product name: Kelzan T manufactured by Kelco.
* 4 is a product name: Proxel XL2 (S) manufactured by Abyssia.

Evaluation similar to the above was performed using the obtained liquid detergent composition for bathrooms. The results are also shown in Table 6.
As is clear from the above results, the liquid detergent composition for bathrooms of Examples 10 to 11 is excellent in both hot water scrub cleaning power and sebum dirt cleaning power, and the length of foam when used as a liquid cleaning product. It was enough.

It is the external appearance perspective view which showed the injection nozzle 1 and the nozzle cover 2, respectively. It is an external appearance perspective view of the injection nozzle 1 in the state where the nozzle cover 2 was attached. It is the schematic which shows the injection pattern in case there exists a wall member. It is the schematic which shows the injection pattern in case there is no wall member. It is the schematic which shows the terminal shape of a wall member.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Injection nozzle, 1a ... Outlet, 1b ... Foam tube, 1c ... Air introduction part, 2 ... Nozzle cover, 2a ... Opening part, 2b ... Cover main body, 2c ... Wall member, 3 ... Notch, 4 ... Convex part 5 ... Notch part, 6 ... Fitting part.

Claims (3)

The following (A) component 0.05-10 mass%, the following (B) component 0.05-5 mass%, the following (C) component 0.1-5 mass%, and the following (D) component 0.05 -5 mass%, and the following (E) component 0.5-5 mass% contains the liquid cleaning composition for bathrooms characterized by the above-mentioned.
(A) N-alkyl or N-alkenyl amino acids and / or salts thereof.
(B) Nonionic surfactant.
(C) Fatty acid and / or salt thereof.
(D) A surfactant having semipolarity.
(E) Linear alkylbenzene sulfonic acid and / or salt thereof. A container body containing a liquid, said liquid contained in the container body to a liquid ejecting a container equipped with an injection nozzle having a spout to release to the outside, claim 1 Symbol placement of bathroom liquid cleaning agent Liquid detergent product for bathrooms containing the composition. The liquid ejection container includes a nozzle cover attached to an outer wall of the ejection nozzle;
The nozzle cover includes a cylindrical cover main body having a fitting portion that fits to an outer wall of the spray nozzle and an opening that exposes a jet outlet of the spray nozzle; and a wall member that surrounds the periphery of the cover main body. Prepared,
The bathroom liquid detergent product according to claim 2 , wherein the wall member has a shape that expands an ejection range of the liquid discharged from the ejection port.

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