JP2012131951A - Liquid detergent product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent product having excellent detergency, foaming tendency, rinsability, low-temperature stability, and foam discharging performance.SOLUTION: The liquid detergent product contains a liquid detergent composition in a foam discharging container. The liquid detergent composition contains (A) 0.1-5 mass% of at least one surfactant selected from amphoteric surfactants and semipolar surfactants, (B) 1.5-5 mass% of a fatty acid (salt), (C) 0.1-10 mass% of a non-soap anionic surfactant, (D) a chelating agent, and (E) a water-soluble solvent. The liquid detergent product is characterized in that the mass ratio (A/B) of the component (A) to the component (B) is 0.1-0.9 and that the mass ratio (B/[A+B+C]) of the component (B) to the sum of components (A) to (C) is 0.15-0.4.

Description

  The present invention relates to a liquid detergent product in which a liquid detergent composition is housed in a foam discharge type container.

Bathroom cleaners should be used to remove dirt that adheres to hard surfaces such as plastics, tiles, stainless steel, ceramics, and glass used in bathtubs, floors, walls, tools, etc. Therefore, detergency against scales and detergency against soap residue are required. The scale is mainly derived from sebum and protein from the human body and adheres to the water line of the bathtub. Soap residue is a fatty acid metal salt formed by combining fatty acids contained in soap or body shampoo and calcium in tap water, etc., and easily accumulates on the floor and accessories outside the bathtub.
In general, liquid detergents are used for bathrooms, and various kinds of compositions have been proposed. For example, Patent Document 1 discloses a bathroom liquid cleaning composition containing a surfactant, a chelating agent, a polymer compound, a solvent, and a fragrance. Patent Document 2 discloses a liquid detergent composition for bathrooms containing specific amounts of N-alkyl or N-alkenyl amino acids and / or salts thereof, nonionic surfactants, and fatty acids and / or salts thereof, respectively. ing.
The liquid cleaning agent is usually stored in a discharge container to form a liquid cleaning product, and sprayed toward the cleaning surface such as a wall surface in the form of mist, foam, or the like by the discharge container. As the discharge container, a discharge container of a type that discharges bubbles (foam discharge container) is widely used because of the excellent retention of the liquid detergent composition on the wall surface or the like. As the foam discharge container, a non-aerosol type foam discharge container such as a spray type foam container or a squeeze type foam container, an aerosol type foam discharge container or the like is used.

JP 2003-183698 A JP 2008-63372 A

The liquid detergent contained in the foam discharge container is required to have foaming properties such as ease of foaming during foam discharge and stability of the foam attached to the cleaning surface such as the wall as well as detergency against scales and soap scum . Such foamability is an important factor for determining the cleaning power, and is an important performance necessary for firmly retaining the liquid cleaning composition on the wall surface or the like. Further, from the viewpoint of convenience of cleaning and water saving, it is required that the rinsing property is good while sufficient foam is formed at the time of use (for example, when rubbing with a sponge).
Foaming property is improved, for example, by increasing the blending amount of the surfactant. However, in this case, there is a problem that the rinsing property is lowered.
As a method of improving rinsing properties, there is a method of blending a fatty acid (salt). However, when fatty acid (salt) is added, the low-temperature stability of the liquid is lowered, and turbidity and precipitation may occur when the temperature of the storage place is about 0 to -5 ° C.
Moreover, when a fatty acid (salt) is added, there is a problem that the foam dischargeability is lowered and the foam tends to remain at the tip of the foam discharge direction in the foam discharge container after spraying. 1-3 is a partial cross-sectional view showing an example of the structure near the foam outlet of each of the trigger spray former container, the squeeze former container, and the aerosol-type foam container. A trigger spray-type former container 100 shown in FIG. 1 has a structure in which a trigger spray-type injection nozzle 102 having a foam discharge port 101 is attached to an opening portion of a container main body 103 that stores a liquid cleaning agent. . The squeeze-type former container 110 shown in FIG. 2 has a structure in which a squeeze-type injection nozzle 112 having a foam discharge port 111 is attached to an opening portion of a container main body 113 that stores a liquid cleaning agent. The aerosol-type foam discharge container 120 shown in FIG. 3 has a structure in which an aerosol-type injection nozzle 122 is attached to an opening portion of a container main body 123 that stores a liquid cleaning agent. In these containers 100, 110, and 120, the nozzle tip portions 104, 114, and 124 (foam discharge ports 101, 111, and 121 and the vicinity thereof (for example, in the flow path near the foam discharge ports 101, 111, and 121, the foam discharge ports) 101 is likely to remain on the outer periphery of the opening 101))). The remaining foam may solidify as it is and cause clogging of the foam outlet. The problem of clogging tends to occur particularly when an amphoteric surfactant and a non-soap anionic surfactant are contained as surfactants other than fatty acids (salts).
This invention is made | formed in view of the said situation, and it aims at providing the liquid detergent product excellent in cleaning power, foaming property, rinse property, low-temperature stability, and foam discharge property.

The present invention for solving the above problems has the following aspects.
[1] A liquid detergent product containing a liquid detergent composition in a foam discharge container,
The liquid cleaning composition comprises (A) 0.1 to 5% by mass of at least one surfactant selected from (A) amphoteric surfactants and semipolar surfactants, and (B) fatty acid (salt) 1.5. Containing 5 mass%, (C) 0.1-10 mass% of non-soap anionic surfactant, (D) chelating agent, and (E) water-soluble solvent,
The mass ratio (A / B) of the component (A) to the component (B) is 0.1 to 0.9, and the mass ratio of the component (B) to the total of the components (A) to (C) (B / [A + B + C]) is 0.15-0.4, The liquid detergent product characterized by the above-mentioned.
[2] The liquid detergent product according to [1], wherein the component (B) contains a mixture of a fatty acid potassium salt having 12 carbons and a fatty acid potassium salt having 14 carbons.
[3] The liquid detergent product according to [1] or [2], wherein the component (A) contains an alkyldimethylamine oxide having an alkyl group having 12 to 14 carbon atoms.
[4] The liquid cleaning agent according to any one of [1] to [3], wherein the component (C) contains an alkylbenzene sulfonate having a linear alkyl group having 10 to 14 carbon atoms. Product.
[5] The liquid detergent product according to any one of [1] to [4], wherein the component (D) contains ethylenediaminetetraacetic acid (salt).
[6] The liquid detergent product according to any one of [1] to [5], wherein the component (E) contains diethylene glycol monobutyl ether.

  ADVANTAGE OF THE INVENTION According to this invention, the liquid detergent product excellent in the detergency, foaming property, rinse property, low-temperature stability, and foam discharge property can be provided.

It is a fragmentary sectional view showing an example of a trigger spray type former container. It is a fragmentary sectional view showing an example of a squeeze type former container. It is a fragmentary sectional view showing an example of an aerosol type foam discharge container. In one Embodiment of a foam discharge container, it is a perspective view from the foam discharge direction front of the nozzle front-end | tip part of an injection nozzle provided with a foam discharge outlet, and the nozzle cover attached there. It is the schematic explaining the positional relationship of the shape of the foam discharge direction front-end | tip part of the wall member with which the nozzle cover shown in FIG. 4 is provided, and this wall member and the track elliptical foam-forming cylinder with which an injection nozzle is provided.

  The liquid detergent product of the present invention is a liquid detergent product in which a liquid detergent composition (hereinafter sometimes simply referred to as a detergent composition) is housed in a foam discharge container, and the detergent composition (A) 0.1-5% by mass of at least one surfactant selected from amphoteric surfactants and semipolar surfactants, and (B) 1.5-5% by mass of fatty acid (salt), (C) 0.1 to 10% by weight of a non-soap anionic surfactant, (D) a chelating agent, and (E) a water-soluble solvent, and the component (A) relative to the component (B) The mass ratio (A / B) is 0.1 to 0.9, and the mass ratio (B / [A + B + C]) of the component (B) to the total of the components (A) to (C) is 0.15 to 0.15. 0.4.

≪Liquid detergent composition≫
<(A) component>
The component (A) is at least one surfactant selected from amphoteric surfactants and semipolar surfactants. The component (A) mainly contributes to the improvement of scale cleaning power and foamability.
(A) The kind of component is not specifically limited, It can select suitably from well-known amphoteric surfactant and semipolar surfactant. For example, specific examples of amphoteric surfactants include alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone betaine type, alkylaminocarboxylic acid type, alkylamidecarboxylic acid type, N-acyl amino acid salt, N-acyl. Examples include methyl taurate, alkyl amino acid type, and phosphate type. Specific examples of the semipolar surfactant include alkylamine oxide type and alkylamidoamine oxide type. These surfactants may be used alone or in combination of two or more.
As the component (A), among the above, an alkylaminocarboxylic acid type amphoteric surfactant and an alkylamine oxide type semipolar surfactant are preferable, and an alkylamine oxide type semipolar surfactant is particularly preferable.
As the alkylaminocarboxylic acid type amphoteric surfactant, those having an alkyl group having 12 to 14 carbon atoms are preferable. Specific examples thereof include amidepropyl laurate-N, N-dimethyl-betaine acetate, amidopropyl myristate. -N, N-dimethyl-acetic acid betaine, cocamidoamidopropyl-N, N-dimethylacetic acid betaine, etc. are mentioned.
The alkylamine oxide type semipolar surfactant is preferably an alkyldimethylamine oxide having an alkyl group having 8 to 18 carbon atoms, and more preferably an alkyldimethylamine oxide having an alkyl group having 12 to 14 carbon atoms. Specific examples thereof include lauryl dimethylamine oxide, myristyl dimethylamine oxide, coconut dimethylamine oxide, and the like.
In the cleaning composition, the blending amount of the component (A) is 0.1 to 5% by mass, and more preferably 0.5 to 3% by mass with respect to the total mass of the cleaning composition. When the blending amount is less than 0.1% by mass, the effect of improving the detergency and foaming ability is poor, and when the blending amount exceeds 5% by mass, the foam ejection property is lowered, and the foam ejection port of the foam ejection container is used at the time of use. There is a tendency to clog.

<(B) component>
(B) A component is a fatty acid (salt). The component (B) mainly contributes to improvement of rinsing properties and foam discharge properties.
“Fatty acid (salt)” means either or both of a fatty acid and a salt thereof. Hereinafter, "(salt)" has the same meaning.
The fatty acid may be a saturated fatty acid or an unsaturated fatty acid, and is preferably a saturated fatty acid. The number of carbon atoms is preferably 12-16 fatty acids, more preferably 12-14. Specific examples include lauric acid, myristic acid, palmitic acid, a mixture of two or more thereof (for example, coconut fatty acid), and the like.
Examples of the fatty acid salt include alkali metal salts such as sodium and potassium, ammonium salts, alkanolamine salts such as monoethanolamine, diethanolamine, and triethanolamine. Of these, potassium salts are preferred.
Component (B) may be a single type or a mixture of two or more types.
As the component (B), a mixture of a C12 fatty acid potassium salt and a C14 fatty acid potassium salt is particularly preferable. Especially, the thing of the ratio of the C12 fatty acid potassium salt in this mixture is less than the C14 fatty acid potassium salt (C14> C12) is preferable. When such a mixture is contained, the rinsing property is further improved.
In the cleaning composition, the blending amount of the component (B) is 1.5 to 5% by mass, and more preferably 2 to 4% by mass with respect to the total mass of the cleaning composition. When the blending amount is less than 1.5% by mass, the effect of improving rinsing properties and foam discharge properties is poor, and when the blending amount exceeds 5% by mass, the low-temperature stability may be lowered.

<(C) component>
Component (C) is a non-soap anionic surfactant. The component (C) mainly contributes to the improvement of scale cleaning power and foamability.
(C) The kind of component is not specifically limited, It can select suitably from well-known non-soap type | system | group anionic surfactant. Specifically, for example, alkylbenzene sulfonic acid (salt), alkane sulfonic acid (salt), alkyl sulfate (salt), alkyl polyoxyethylene sulfate (salt), α-olefin sulfonic acid (salt), alkylphenoxyphenyl disulfonic acid ( Salt), α-sulfo fatty acid (salt), ether carboxylic acid (salt), alkyl phosphate (salt), alkyl polyoxyethylene phosphate (salt), dialkyl sulfosuccinic acid ester (salt), alkyl sulfosuccinate (salt), An alkenyl succinic acid (salt) etc. are mentioned.
Examples of the salt include alkali metal salts such as sodium and potassium, ammonium salts, alkanolamine salts such as monoethanolamine, diethanolamine, and triethanolamine.
These surfactants may be used alone or in combination of two or more.
Among these, the component (C) is preferably an alkyl benzene sulfonate, an alkylene oxide-added alkyl or an alkenyl ether sulfate, and more preferably an alkyl benzene sulfonate. Of these, alkylbenzene sulfonates having a linear alkyl group having 10 to 14 carbon atoms are preferred.
In the cleaning composition, the blending amount of the component (C) is 0.1 to 10% by mass, and more preferably 2 to 6% by mass with respect to the total mass of the cleaning composition. If the blending amount is less than 0.1% by mass, the effect of improving the foaming property and scale cleaning power is poor, and if the blending amount exceeds 10% by mass, the rinsing property may be lowered.

<(D) component>
(D) A component is a chelating agent. (D) component mainly contributes to the improvement of soap residue cleaning power.
(D) The kind of component is not specifically limited, It can select suitably from well-known chelating agents. Specific examples include organic carboxylic acids, aminocarboxylic acids, phosphonic acids, phosphonocarboxylic acids, and phosphoric acids.
The organic carboxylic acid is a compound having a carboxy group, and the carboxy group may form a salt. The organic carboxylic acids may have only a carboxy group as a functional group, or may have a functional group other than a carboxy group. Examples of organic carboxylic acids having a functional group other than carboxy group include hydroxycarboxylic acid (salt). Specific examples of organic carboxylic acids include acetic acid, adipic acid, monochloroacetic acid, oxalic acid, succinic acid, oxydisuccinic acid, carboxymethyl succinic acid, carboxymethyloxysuccinic acid, glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxy Examples thereof include methyl tartaric acid, citric acid, malic acid, gluconic acid, and salts thereof.
Aminocarboxylic acids include nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminopentaacetic acid, N-hydroxyethylethylenediamineacetic acid, ethylenediaminetetrapropionic acid, triethylenetetrahexaacetic acid, ethylene glycol dietherdiaminetetraacetic acid, hydroxyethylimino Examples thereof include diacetate, cyclohexane-1,2-diaminetetraacetic acid, methylglycine diacetate, and salts thereof.
Examples of phosphonic acids include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and its derivatives, 1-hydroxyethane-1,1,2 -Triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminotrimethylenephosphonic acid, salts thereof and the like.
Examples of phosphonocarboxylic acids include 2-nosonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid, and salts thereof.
Examples of phosphoric acids include orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, hexametaphosphoric acid, condensed phosphoric acid such as phytic acid, and salts thereof.
Examples of the salt include alkali metal salts such as sodium and potassium, ammonium salts, alkanolamine salts such as monoethanolamine, diethanolamine, and triethanolamine.
These chelating agents may be used alone or in combination of two or more.
As the component (D), among the above, aminocarboxylic acids and phosphonic acids are preferable, and aminocarboxylic acids are more preferable. Of these, ethylenediaminetetraacetate is preferable.
Although the compounding quantity of (D) component in a cleaning composition is not specifically limited, Since it is excellent in soap residue cleaning power, 0.5-10 mass% is preferable with respect to the total mass of a cleaning composition. When the blending amount is less than 0.5% by mass, the effect of improving the foaming property and the scale cleaning power is poor, and when the blending amount exceeds 10% by mass, the rinsing property may be lowered.

<(E) component>
(E) A component is a water-soluble solvent. The component (E) mainly contributes to an improvement in detergency against scale, low temperature stability and the like. Moreover, it contributes to the improvement of the detergency with respect to soap residue with (D) component.
The “water-soluble solvent” refers to a compound that is liquid at 20 ° C. and dissolves 1 g or more in 1000 g of distilled water at 20 ° C. “Dissolve” indicates that the solution is uniform.
As the component (E), any water-soluble solvent that is generally used for dissolving other substances can be used, and examples thereof include alcohols and ethers.
Alcohols include monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, s-butanol, and t-butanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene. And glycols such as glycol, glycerin, and the like.
Examples of ethers include alkyl glycol ethers such as diethylene glycol monoethyl ether, diethylene glycol monopropyl ether and diethylene glycol monobutyl ether, alkyl glyceryl ethers such as isostearyl glyceryl ether, alkyl ether carboxylic acid amide alcohols, and phenoxyethanol.
These solvents may be used alone or in combination of two or more.
Among the above, the component (E) is preferably an ether, and more preferably an alkyl glycol ether. Of these, diethylene glycol monobutyl ether is preferable.
Although the compounding quantity of (E) component in a cleaning composition is not specifically limited, 2-10 mass% is preferable with respect to the total mass of a cleaning composition, and 5-10 mass% is more preferable. If the blending amount is too small, the effect of improving soap residue cleaning power and low-temperature stability is poor, and if the blending amount exceeds 10% by mass, foaming properties may be lowered.

In the cleaning composition, the mass ratio (A / B) of the component (A) to the component (B) is 0.1 to 0.9, and preferably 0.2 to 0.6.
When A / B is more than 0.9, the foam ejection property and the low temperature stability are deteriorated. This is considered because the detergent composition is easily gelled. Gelation causes clogging in the vicinity of the foam discharge port when, for example, the liquid accumulated in the vicinity of the foam discharge port is dried. By containing the component (B) so that A / B is 0.9 or less, it is considered that gelation is suppressed, leading to improvement in foam discharge properties and low-temperature stability.
On the other hand, when A / B is less than 0.1, the foam ejection property and the low temperature stability are also deteriorated. This is presumably because the proportion of the component (B) increases and the component (B) itself has the property of being easily gelled.

In the cleaning composition, the mass ratio (B / [A + B + C]) of the component (B) to the sum of the components (A) to (C) is 0.15 to 0.4, and 0.3 to 0.4. Is preferred.
When B / [A + B + C] is less than 0.15, the rinsing property tends to be lowered. When B / [A + B + C] exceeds 4, although the rinsing property is good, the low-temperature stability tends to deteriorate and the foaming property tends to decrease.

The cleaning composition may contain components other than the components (A) to (E) as long as the effects of the present invention are not impaired. Examples of the other components include those shown below.
[A. Nonionic surfactant]
A nonionic surfactant may be further contained for the purpose of improving scale cleaning power.
The kind of nonionic surfactant is not specifically limited, It can select suitably from well-known nonionic surfactants. Specific examples include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, alkyl polyglucoside, fatty acid polyglycerin ester, fatty acid sucrose ester, fatty acid alkanolamide and the like. These nonionic surfactants may be used alone or in combination of two or more.

[B. Polymer compound]
For the purpose of viscosity adjustment, foam adjustment, surface modification, etc., a nonionic surfactant may be further contained.
The type of the polymer compound is not particularly limited, and can be appropriately selected from known polymer compounds according to the compounding purpose. As the polymer compound, any of natural polymers, synthetic polymers, and synthetic polymers can be used. Examples of natural polymers include gum arabic, tragacanth gum, xanthan gum, guar gum, locust bean gum, gellan gum, alginic acid, carrageenan and the like. It is done. Examples of the semi-synthetic polymer include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, human roxypropyl cellulose, methyl hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, and cationized cellulose. Synthetic polymers include polyacrylic acid, poly-α-hydroxyacrylic acid, acrylic copolymer, acrylic ester copolymer, methacrylic ester nonionic polyacrylamide, anionic polyacrylamide, cationic Examples include polyacrylamide, polyaminoalkyl methacrylate, acrylamide / acrylic acid copolymer, polyvinyl sulfonic acid, polystyrene sulfonic acid, sulfonated maleic acid, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyvinyl methyl ether, and polyether-modified silicon.

[C. Other ingredients]
Furthermore, a fragrance | flavor, a pigment | dye, disinfectant | microbicide, antioxidant, a ultraviolet absorber, a solubilizer, a pH adjuster etc. can be mix | blended as needed. Any of these components may be used as long as they are usually used for cleaning agents, and is not particularly limited.

The method for preparing the cleaning composition is not particularly limited, and the cleaning composition can be prepared according to a conventional method in the same manner as a normal liquid cleaning composition. For example, it can be prepared by blending the above components (A) to (E) and other optional components and water as appropriate.
The pH of the cleaning composition is not particularly limited, but it is preferable that the pH at 25 ° C. is 5 to 9 in consideration of environmental influences and user safety. The pH of the cleaning composition can be adjusted with a pH adjuster or the like.

<Foam discharge container>
The foam discharge container for storing the cleaning composition is not particularly limited as long as it has a foam discharge mechanism for discharging the liquid cleaning composition as a content in a foam form, and a known foam discharge container is used. For example, an aerosol-type foam discharge container that discharges bubbles with high-pressure gas, a non-aerosol-type foam discharge container, and the like can be given. Among these, non-aerosol type foam discharge containers are preferable from the viewpoint of usability and environmental impact.
The non-aerosol type foam discharge container is a container that discharges the contents in a foam form by mixing with air, and is also referred to as a former container. A non-aerosol type foam discharge container is usually attached to a container body that contains a cleaning composition and an opening of the container body, and a jet that discharges the cleaning composition contained in the container body in the form of foam. And a nozzle.
As a mechanism in which the spray nozzle foams the cleaning composition in the container body, a liquid is introduced from the container body into the foam-forming cylinder portion incorporated at the tip of the spray nozzle, and the liquid is introduced into the wall of the foam-forming cylinder. In general, those that collide with each other to generate turbulent flow and promote mixing with air, or those that form a foam by placing a barrier or mesh on the front surface of the injection nozzle, etc. Air for generating bubbles is introduced from the outside of the container. As the detailed structure of these mechanisms, conventionally known ones can be applied and are not particularly limited.
Examples of the non-aerosol type foam discharge container include a spray-type former container, a squeeze-type former container, and a pump-type former container. Among these, a spray-type former container is preferable from the viewpoint of usability when washing the bathroom and bathtub. Examples of the spray-type former container include a trigger spray type and a pump spray type. Among them, the trigger spray type is preferable.
The foam discharge form of the foam discharge container is not particularly limited, and any one proposed so far can be used, for example, various discharge forms such as a substantially perfect circle shape, an elliptical shape, and a belt shape are used. it can. Here, the “discharge 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 discharged cleaning composition. Among these, the discharge form is preferably an elliptical shape or a band shape. In this case, for example, the foam can be discharged so as to adhere horizontally to the position of the water line on the inner side surface of the bathtub, and the liquid detergent composition can be effectively applied to dirt accumulated on the water line.

As a specific example of a particularly preferred spray-type foam discharge container, a container body containing a liquid (detergent composition) as disclosed in JP-A-2008-63372, and a liquid contained in the container body are used. A liquid ejection container including an ejection nozzle provided with an ejection port (foam ejection port) that discharges to the outside and a nozzle cover attached to an outer wall of the ejection nozzle is exemplified. The nozzle cover includes a tubular cover main body having a fitting portion that fits to an outer wall of the injection nozzle and an opening that exposes a jet outlet of the injection nozzle, and a wall member that surrounds the periphery of the cover main body. The wall member has a shape that expands the ejection range of the liquid discharged from the ejection port. By providing this nozzle cover, when the cleaning composition is sprayed onto the object to be cleaned, the adhesion thereof becomes wide and uniform.
FIG. 4 is a perspective view from the front of the bubble discharge direction of the nozzle tip of the spray nozzle and the nozzle cover attached thereto in one embodiment of the liquid spray container. In FIG. 4, reference numeral 1 denotes an injection nozzle, and reference numeral 2 denotes a nozzle cover.
The injection nozzle 1 shown in FIG. 4 has a foam discharge port 1a and an elliptical bubble-forming cylinder 1b extending in the foam discharge direction from the opening surface of the foam discharge port 1a so as to surround the foam discharge port 1a. .
The foam-forming cylinder 1b is provided in order to realize a predetermined discharge form, and the discharge form by the injection nozzle 1 is a wide track elliptical shape similar to the shape of the foam-forming cylinder 1b.
A plurality of air introduction holes (not shown) are provided inside the foam-forming cylinder 1b. The air introduction hole communicates with an air introduction part 1c that opens on the outer wall of the injection nozzle 1, and air for forming bubbles is formed inside the foam-forming cylinder 1b via the air introduction part 1c and the air introduction hole. It has been introduced.
The nozzle cover 2 has a structure in which a cylindrical cover body 2b having an elliptical opening that exposes the foam discharge port 1a of the spray nozzle 1 and a wall member 2c surrounding the cover body 2b are integrated.
A notch 3 is formed on the wall surface of the rear end portion of the cover main body 2 b, and a convex portion 4 is formed on the outer wall of the injection nozzle 1. The nozzle cover 2 is attached to the injection nozzle 1 by engaging the notch 3 with the convex portion 4.
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.
When such a wall member 2c is attached, due to the Coanda effect, the flow direction of bubbles discharged from the spray nozzle 1 changes to a direction closer to the wall member 2c direction than the direction immediately after discharge, and the wall member 2c. The area of bubbles adhering to the surface of the object to be cleaned is increased as compared with the case where is not attached.

The shape of the front-end | tip part of the foam discharge direction of the wall member 1c with which the nozzle cover 2 is provided using FIG. 5, and the positional relationship of this wall member 1c and the foam-forming cylinder 1b are demonstrated. 5A is a top view of the bubble discharge direction front end of the nozzle cover 2 as viewed from the front of the discharge direction, and FIG. 5B is a longitudinal section of the wall member 1c at the front end of the discharge direction in the major axis direction. FIG. 5C is a longitudinal sectional view in the minor axis direction of the front end portion of the wall member 1c in the discharge direction.
In FIG. 5A, Y is the inner diameter in the long side direction of the foam-forming cylinder 1b, and Z is the inner diameter in the short-side direction of the foam-forming cylinder 1b. In FIG. 5B, p is the inner diameter in the long side direction of the wall member 2c at the tip in the discharge direction, and q is the long side direction of the wall member 2c on the same plane as the plane including the opening of the cover body 2b. The inner diameter, r is the height from the opening surface of the cover body 2b to the front end surface of the wall member 2c in the discharge direction. In FIG. 5C, s is the inner diameter in the short side direction of the wall member 2c at the tip in the discharge direction, and t is in the short side direction of the wall member 2c on the same plane as the plane including the opening of the cover body 2b. The inner diameter.
The values of Y and Z are not particularly limited, but usually Y is in the range of 7 to 10 mm, and Z is in the range of 3 to 4 mm.
When Y and Z are within the above range, p is preferably within the range of +1 to +8 mm of q. Within this range, the Coanda effect is likely to occur, and the effect of increasing the bubble adhesion area is excellent.
When Y and Z are within the above ranges, p is preferably within a range of 30 to 37 mm, and more preferably within a range of 35 to 37 mm.
q is preferably in the range of 26 to 32 mm, more preferably in the range of 28 to 30 mm, when Y and Z are within the above range.
r is preferably in the range of 2 to 8 mm, more preferably in the range of 4 to 5.5 mm, when Y and Z are within the above range.
Although s is not specifically limited, When Y and Z are in the said range, it is preferable to exist in the range of 18-22 mm.
Although t is not specifically limited, When Y and Z are in the said range, it is preferable to exist in the range of 17-21 mm.
In the above-described embodiment, an example in which the foam-forming cylinder has an elliptical shape has been described. However, the shape of the foam-forming cylinder can be determined according to a desired discharge form, and may be, for example, a band shape or a substantially circular shape.

The liquid detergent product of the present invention can be produced by storing the detergent composition in a foam discharge container.
The usage method of the liquid detergent product of this invention is not specifically limited, It can use by the method similar to a general liquid detergent product.

In the liquid detergent product of the present invention, the liquid detergent composition housed in the foam discharge container is excellent in cleaning power against foam and soap residue, foaming property, rinsing property, low temperature stability and foam discharging property. It is considered that the components (A) to (E) act synergistically to improve these properties, but the components (A) and (C) mainly contribute to the improvement of the scale cleaning power, soap. Components (D) and (E) contribute mainly to the improvement of debris cleaning power, components (A) to (C) mainly contribute to the improvement of foaming properties, and mainly (B) to the rinsing properties. The components contribute, and it is considered that the components A / B, B / [A + B + C], (E), etc. contribute mainly to the low temperature stability and the foam dischargeability.
For example, in the present invention, the component (B) is contained in a large amount in the range of 1.5% to 5% compared to the conventional case, and B / [A + B + C] is in the range of 0.15 to 0.4. Low temperature stability (simultaneously foam dischargeability) is improved. If the amount of component (B) is simply increased, the rinsing property is improved, but the low temperature stability is deteriorated. Although the low temperature stability tends to be improved by the addition of the component (A) or the solubilization by the addition of the component (E), it is not sufficient.
In addition, when a foam discharge container is used, as described above, the foam of the cleaning composition remains in the foam discharge port and the vicinity thereof (in the flow path near the foam discharge port, the opening periphery of the foam discharge port, etc.) after the foam discharge. However, solidifying as it is may cause clogging. (B) Component itself has the property of easily solidifying when water is volatilized after being discharged from the discharge container, but in particular, (A) component and (B) component in order to improve detergency, foaming and rinsing properties. And when the cleaning composition which mix | blended a large amount of (C) component was accommodated in the foam discharge container, a discharge outlet tends to be clogged after spraying. This phenomenon is not so much a problem when the component (B) is not blended, but in particular, when the component (B) is blended for improving rinsing, the phenomenon of clogging in the vicinity of the bubble discharge port tends to become remarkable. In the present invention, in the composition containing a relatively large amount of the component (B) as described above, the A / B ratio is 0.1 to 0.9, and B / [A + B + C] is 0.15 to 0.4. By doing so, stability at low temperature is improved and clogging of the foam discharge port is dramatically reduced. Although details are unknown, it is known that the component (A) has an interaction (forms a complex) with the component (B) or the component (C), and is gelled or thickened. ) In the range of the specific amount containing 1.5% or more of the component and in the range of the specific ratio with these surfactants, the formation of the complex is inhibited, and one of the causes of the discharge port clogging It is estimated that gelation and thickening of the composition are less likely to occur due to volatilization of water after ejection. However, when the component (B) is contained in a proportion exceeding 1.5% by mass, even if A / B or B / [A + B + C] is within the above range, the effect of suppressing clogging of the foam discharge port is obtained. Absent.
When such a liquid cleaning composition is stored in a foam discharge container, discharged in the form of foam, and attached to the cleaning surface, the attached liquid cleaning composition stays on the cleaning surface for a long time in the form of bubbles. The cleaning power of the liquid detergent composition is sufficiently exhibited. In addition, since the foam discharge container is used, the liquid cleaning composition can be easily attached to a wide area in the bathroom, which is highly convenient. After washing, rinsing can be completed in a short time, which is useful in terms of convenience of bathroom cleaning and water saving.
Further, since the liquid detergent product of the present invention is excellent in low-temperature stability and foam dischargeability, turbidity and precipitation of the liquid detergent composition in the foam discharge container during storage and after use, clogging of the foam discharge container, etc. Is suppressed.
The liquid detergent product of the present invention is particularly useful for bathrooms. However, this invention is not limited to this, You may be used for uses other than the object for bathrooms. Examples of uses other than for bathrooms include a washstand and a toilet bowl.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
The raw materials used in the following examples are shown below.

[Raw materials]
<(A) component>
Alkyldimethylamine oxide: n-dodecyldimethylamine oxide (Alomox DM12D-W manufactured by Lion Akzo Co., Ltd.).
Alkyldimethylamidopropylamine oxide: Lauryldimethylamidopropylamine oxide (synthetic product synthesized in Synthesis Example 1 below).
Acylamidopropyl betaine: Amidopropyl betaine laurate (LPB-30, manufactured by Yushi Kogyo Co., Ltd.).
Alkylhydroxysulfobetaine: Laurylhydroxysulfobetaine (Amphitol 20HD manufactured by Kao Corporation).
Alkylaminopropionic acid Na: sodium laurylaminopropionate (Amforak L-18, manufactured by Yushi Kogyo Co., Ltd.).

[Synthesis Example 1]
(1-1. Synthesis of lauric acid dimethylaminopropylamide)
A 1 liter four-necked flask equipped with a stirrer, thermometer, and reflux condenser was charged with 300 g of lauric acid methyl ester (Lion Chemical, Pastel M12, molecular weight 214) as a fatty acid ester, and purged with nitrogen at 60 ° C. (After depressurizing to 13 kPa, normal pressure and returning to nitrogen) were performed twice, the temperature was raised to 180 ° C., and 186 g of dimethylaminopropylamine (manufactured by BASF, hereinafter abbreviated as “DMAPA”) Ratio: 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 of 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.

(1-2. Synthesis of lauryldimethylamidopropylamine oxide)
In a 1 liter four-necked flask equipped with a stirrer, thermometer, and reflux condenser, 200 g of lauric acid dimethylaminopropylamide synthesized above (calculated from the amine value) so that the active ingredient is 30%. Molecular weight 286), 200 g of purified water were charged, and 8 g of hydrogen peroxide (Mitsubishi Gas Chemical, 45% product diluted with purified water, 1.05 mole ratio of amine to 2% 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 lauryldimethylamidopropylamine oxide having an active ingredient of 30.1%.

<(B) component>
Lauric acid K: potassium laurate (NIKKOL LK-120 manufactured by Nikko Chemicals).
Myristic acid K: Potassium myristic acid (neutralized coconut fatty acid manufactured by Nippon Oil & Fats with an aqueous potassium hydroxide solution).
Coconut Fatty Acid K: Palm Fatty Acid Potassium (Lion Chemical's Palm Fatty Acid Potassium (30% aqueous solution)).
Myristic acid Na: sodium myristic acid (NIKKOL MK-140 manufactured by Nikko Chemicals).

<(C) component>
(C1): Teicapol NE1230 (polyoxyethylene (average 3 mol) alkyl ether sulfate ester sodium having an alkyl group having 12 to 14 carbon atoms) manufactured by Teika.
(C2): Sodium alkylbenzenesulfonate having a linear alkyl group having 10 to 14 carbon atoms (linear alkylbenzenesulfonic acid (Taika Power L121 manufactured by Taika) neutralized with sodium hydroxide).
(C3): Lion's Lipolane LJ-443 (C14, sodium α-olefin sulfonate).

<(D) component>
EDTA: disodium ethylenediaminetetraacetic acid (dizorubin NA2 manufactured by Akzo Nobel).
MGDA: Methylglycine diacetate / sodium (BASF Trilon M Powder).
HEDP: 1-hydroxyethane-1,1-diphosphonate sodium (BRIQUEST ADPA-60SH manufactured by Rhodia).

<(E) component>
DEMB: Diethylene glycol monobutyl ether (Butyl diglycol (95) manufactured by Nippon Emulsifier).
Phenoxyethanol: Phenoxyethanol (Phenyl glycol manufactured by Japan Emulsifier).
Alkyl glyceryl ether: Isostearyl glyceryl ether (Benator GE-IS manufactured by Kao).

<Examples 1-34, Comparative Examples 1-15>
By mixing the components (A) to (E) shown in Tables 1 to 5 and a balance amount of water, cleaning compositions having the compositions shown in Tables 1 to 5 were prepared.
In Tables 1-5, the compounding quantity of each component is the ratio (mass%) in a cleaning composition (100 mass%). The balance amount of water is such that the total amount of the cleaning composition is 100% by mass.
The following evaluation was performed about the obtained cleaning composition. The results are shown in Tables 1-5.

<Evaluation of foaming and rinsing properties>
A urethane sponge was allowed to contain 10 g (normal use amount setting) or 30 g (excess use amount setting) of the cleaning composition and 40 g of tap water. Using this sponge, while applying a load of about 10 g / cm ² , the entire inner surface of the fiber reinforced plastic (FRP) bathtub (hereinafter referred to as the FRP bathtub; inner dimensions of the FRP bathtub: 100 × 75 × 65 cm) is circular. I rubbed like drawing.
After the entire inner surface of the FRP bathtub was rubbed, the foaming property was evaluated according to the following evaluation criteria from the state of the foam adhered to the rubbed place. In addition, evaluation of foaming property was performed only in the case of normal usage amount setting, and was not performed in the case of excessive usage amount setting.
Then, the inside rinse was started in the state which opened the drain outlet of the FRP bathtub. Rinsing was performed with tap water (temperature 20 ° C., flow rate 10 L / min) using a shower.
The time from the start of rinsing until the bubbles completely disappeared around the drain outlet was measured, and this was defined as the rinsing time. From this rinse time, the rinse property was evaluated according to the following evaluation criteria.

[Evaluation criteria for foaming properties]
A: Bubbles remain throughout the rubbed area.
○: Bubbles are uneven, but bubbles remain throughout.
Δ: Slight bubbles remain in some places.
X: Almost no bubbles remain.

[Evaluation criteria for rinsability]
A: Rinsing time is less than 30 seconds.
○: Rinse time is 30 seconds or more and less than 45 seconds.
Δ: Rinse time is 45 or more and less than 60 seconds.
X: Bubbles do not disappear even after 60 seconds.

<Evaluation of cleaning power>
{A. Observation of removal of scale stains}
After fixing an 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 (one bath per day, two days) Repeatedly, the bath water was re-boiled and used without changing it), and dirt (scale stain) was attached. After sufficiently drying the test piece to which the scale stain has adhered, spray about 20 g (Lion Co., Ltd., using the trigger spray of the product name “Otoro Look”) so that the cleaning composition (stock solution) gets wet all over, After leaving it for 30 seconds, it was rinsed with tap water (15 ° C.). Next, after sufficiently drying, the removal state of scale dirt on the surface of the test piece was visually observed.

{B. Observation of the state of soap residue removal}
Using a urethane basin with soap debris that cannot be easily removed for 3 months in a general household bathroom, using a urethane sponge impregnated with 5 g of a detergent composition (stock solution), about 20 g / After being rubbed 5 times with a weight of cm ² , it was rinsed with tap water (20 ° C.). Next, after sufficiently drying, the state of removal of soap residue on the surface of the basin was visually observed.

From the observation results of the two types of soil removal, the cleaning power was evaluated according to the following evaluation criteria.
[Evaluation criteria for cleaning power]
A: Both dirt stains and soap residue stains are removed.
○: Slight dirt remains on either the scale stain or soap residue.
Δ: Either dirt stains or soap residue stains remain in some places.
X: Soil stains and soap residue stains are hardly removed.

<Foam ejection properties>
As the foam discharge container, a trigger spray type foam discharge container provided with an injection nozzle B among the injection nozzles A to H described in Examples of Japanese Patent Application Laid-Open No. 2008-63372 was prepared. In the ejection nozzle B shown in FIG. 5, Y is 8.5 mm, Z is 3.5 mm, p is 36 mm, r is 4.5 mm, q is 29.0 mm, and s is 19. 2 mm and t is 18.2 mm.
The trigger spray type foam discharge container accommodated the cleaning composition of each example to obtain a liquid cleaning product.
After spraying 10 times continuously using the obtained liquid detergent product, the liquid detergent product was directly placed in a dryer at 50 ° C. and dried for 2 hours. This series of operations was repeated five times, and after the fifth operation, the liquid detergent product was removed from the dryer and allowed to stand at room temperature for 1 hour. Then, while observing visually the adhesion state of the solid substance around a foam discharge port, spraying was performed again and the clogged state of the foam discharge port was confirmed. From the results, the foam dischargeability was evaluated according to the following evaluation criteria. In addition, when the disorder | damage of the spray pattern has generate | occur | produced in the following evaluation criteria, it has shown that it is the state in which the solid substance adhered partially inside the discharge outlet.

[Evaluation criteria for foam ejection properties]
(Double-circle): Solid substance adhesion is not seen around a bubble discharge outlet. Moreover, foam is discharged and the spray pattern is also normal.
○: No solid matter is observed around the foam discharge port. Moreover, although foam is discharged, the spray pattern is disturbed.
(Triangle | delta): Solid substance adhesion is seen around a bubble discharge outlet. Moreover, although foam is discharged, the spray pattern is disturbed.
X: Adhesion of solid matter is observed around the foam discharge port. Moreover, it is clogged and a bubble is not discharged.

<Low temperature stability>
100 mL of each cleaning composition is put in a container with a capacity of 100 mL and stored at −5 ° C. for 7 days, and then the liquid appearance of each cleaning composition is visually observed. Stability was evaluated.
[Evaluation criteria for low-temperature stability]
A: No change in appearance.
○: Turbidity occurs but returns to transparency when left at room temperature.
Δ: A white precipitate is formed.
X: A white precipitate is formed even at room temperature.

As shown in the above results, in Examples 1 to 34, good (◎ or ○) results were obtained in all evaluations of foaming property, rinsing property, cleaning power, foam dischargeability, and low temperature stability.
On the other hand, Comparative Example 1 containing no component (A) has poor detergency, poor foam ejection properties and low-temperature stability, and Comparative Example 2 having a component (A) content of 6% by mass has poor foam ejection properties. Also, the low temperature stability was poor. Comparative Example 3 having a component (B) content of 1% by mass was poor in rinsing properties and foam ejection properties, and Comparative Example 4 having a component (B) content of 7% by mass was poor in low-temperature stability. Comparative Example 5 containing no component (C) has poor detergency and low-temperature stability, and Comparative Example 6 having a content of component (C) of 12% by mass is a rinsing property at the time of setting an excessive amount, a foam ejection property, Low temperature stability was poor. Comparative Example 7 not containing component (E) had poor detergency and low-temperature stability, and Comparative Example 8 not containing component (D) had poor detergency.
Further, Comparative Example 9 having an A / B ratio of 0.03 has poor detergency, foam ejection properties, and low temperature stability, and Comparative Example 10 having an A / B ratio of 1.3 has poor foam ejection properties and is stable at low temperatures. The sex was also poor. Comparative Example 11 with B / [A + B + C] of 0.60 had poor low-temperature stability, and Comparative Example 12 with B / [A + B + C] of 0.12 had poor rinsing properties.
Further, Comparative Example 13 had low detergency, poor foam dischargeability and low-temperature stability, and Comparative Examples 14 to 15 had poor foam dischargeability. This is because B / [A + B + C] or A / B is large, and the ratio of C12 in palm fatty acid (mixture of C12 fatty acid potassium salt and C14 fatty acid potassium salt) used as component (B) is higher than C14. It is speculated that it is because there are many.

  DESCRIPTION OF SYMBOLS 1 ... Injection nozzle, 1a ... Foam discharge port, 1b ... Foam tube, 1c ... Air introduction part, 2 ... Nozzle cover, 2b ... Cover main body, 2c ... Wall member, 3 ... Notch, 4 ... Convex part, 101 ... Foam Discharge port, 102 ... foam discharge port, 103 ... foam discharge port

Claims (6)

A liquid detergent product containing a liquid detergent composition in a foam discharge container,
The liquid cleaning composition comprises (A) 0.1 to 5% by mass of at least one surfactant selected from (A) amphoteric surfactants and semipolar surfactants, and (B) fatty acid (salt) 1.5. Containing 5 mass%, (C) 0.1-10 mass% of non-soap anionic surfactant, (D) chelating agent, and (E) water-soluble solvent,
The mass ratio (A / B) of the component (A) to the component (B) is 0.1 to 0.9, and the mass ratio of the component (B) to the total of the components (A) to (C) (B / [A + B + C]) is 0.15-0.4, The liquid detergent product characterized by the above-mentioned.   The liquid detergent product according to claim 1, wherein the component (B) contains a mixture of a fatty acid potassium salt having 12 carbon atoms and a fatty acid potassium salt having 14 carbon atoms.   The liquid detergent product according to claim 1 or 2, wherein the component (A) contains an alkyldimethylamine oxide having an alkyl group having 12 to 14 carbon atoms.   The liquid detergent product according to any one of claims 1 to 3, wherein the component (C) contains an alkylbenzene sulfonate having a linear alkyl group having 10 to 14 carbon atoms.   The liquid detergent product according to any one of claims 1 to 4, wherein the component (D) contains ethylenediaminetetraacetic acid (salt).   The liquid detergent product according to any one of claims 1 to 5, wherein the component (E) contains diethylene glycol monobutyl ether.

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