KR102468091B1 - Liquid detergent for bathroom - Google Patents

Abstract

Liquid detergent for bathroom of the present invention includes (A) component: 0.1 to 5.0% by mass of a surfactant containing a non-soap anionic surfactant, (B) component: a glycol-based solvent, and (C) component: aminocarboxylic acid type chelate agent, the mass ratio represented by the component (C)/component (A) is 0.6 to 6.0, and the pH at 25°C exceeds 10 and is less than 12.

Description

Liquid detergent for bathroom {LIQUID DETERGENT FOR BATHROOM}

The present invention relates to a liquid detergent for bathroom.

Bathroom cleaning is usually performed by rubbing and washing the bathroom wall surface, bathtub surface, and other bathroom accessory facilities with a sponge impregnated with a bathroom liquid detergent.

Since scrubbing involves directly rubbing the object to be cleaned with a sponge, for example, when cleaning a bathtub, the entire surface of the bathtub has to be rubbed with a sponge as it bends forward, slumps, or squats, which is time-consuming and physically burdensome. too big

Conventionally, detergents for reducing the time and physical burden of bathroom cleaning have been proposed. For example, Patent Document 1 proposes a bathtub aerosol cleaner containing a metal ion sequestering agent, a surfactant, an organic solvent having a water solubility of 10% or less at 20°C, and a propellant in a specific weight ratio, respectively. has been According to Patent Document 1, the aerosol cleaner for a bathtub is sprayed on the remaining hot water surface of the bathtub to spread on the hot water surface and adhere to the side surface of the bathtub. After that, a bathtub cleaning method in which the stopper of the bathtub is pulled out and the remaining hot water is discharged to adhere to the side surface and bottom of the bathtub while lowering the cleaning component diffused on the hot water surface along with the hot water surface, and then washed off with a shower etc. has been

Patent Literature 2 proposes a cleaning agent containing a specific aminocarboxylic acid salt and a carboxylic acid other than this in a specific weight ratio. Patent Document 2 discloses a bathroom cleaning method in which the cleaning agent is sprayed against light scale contamination and then left for a while to flow into the shower.

Further, Patent Document 3 describes a cleaning method in a bathroom in which a cleaning liquid containing a surfactant and a chelating agent is blown into a bathtub or the like by means of a discharge means such as a shower device, and then rinsed with tap water.

According to the cleaning agents or cleaning methods disclosed in Patent Literatures 1 to 3, washing time and physical burden are reduced because it is possible to wash a bathtub or the like without rubbing and washing.

However, in such a method of cleaning a bathtub or the like without scrubbing (cleaning without scrubbing), it is necessary to adhere the liquid detergent for bathroom to the entire surface of the object to be cleaned, such as a bathtub, and the amount of detergent used increases. When the usage amount of the liquid detergent for bathroom is increased, there is a problem that foam derived from components such as surfactant in the detergent is generated, and the rinseability (i.e., the property of being able to wash off the detergent with good foam removal) is deteriorated.

Regarding this problem, Patent Document 4 describes a liquid detergent for bathroom containing a fatty acid or a salt thereof, and discloses that the detergent has excellent rinseability. However, when the usage amount of the detergent is increased, such as in "cleaning without rubbing", sufficient rinsing properties cannot be obtained simply by blending a fatty acid or a salt thereof with the detergent.

In addition, in order to improve the rinsability of the detergent, it is considered to reduce the content of the surfactant in the detergent. However, surfactants are a major cleaning component of detergents, and if their content is simply reduced, sufficient cleaning power against metal salts of fatty acids such as calcium salts of fatty acids, sebum and protein stains adhered to bathtubs and the like cannot be obtained.

In this way, there is no liquid detergent for bathrooms that can achieve both sufficient detergency and rinseability when washing the bathtub without scrubbing.

In addition, liquid detergents are required to have low-temperature stability (that is, properties that do not cause phase separation or cloudiness under low-temperature conditions of, for example, -5°C).

In addition, in the techniques of Patent Literatures 1 to 3, there is a problem that the cleaning agent drips down in a stripe shape on the vertical surface of the bathtub, and the retention property of the cleaning agent on the vertical surface (ie, the property of the cleaning agent to adhere to the object to be cleaned) is not sufficient. there was.

Here, Patent Literature 5 discloses a detergent having increased viscosity in order to improve adhesion and retention of the detergent on a vertical surface. However, in the technique disclosed in Patent Literature 5, the diffusivity of the cleaning agent (that is, the property that the cleaning agent spreads uniformly and non-uniformly from the area where the cleaning agent was blown to its surroundings) was insufficient.

On the other hand, in order to achieve both adhesion retention and diffusivity, Patent Document 6 discloses a cleaning agent in which a specific solvent, a specific surfactant, and a specific thickener are combined. Further, Patent Literature 7 discloses a cleaning agent having a controlled contact angle to the surface of an object to be cleaned. However, in all of these, the object of cleaning is a toilet bowl, and the cleaning power against metal salts of fatty acids, sebum and protein adhering to bathtubs and the like has not been studied.

Japanese Unexamined Patent Publication No. 2000-109891 Japanese Unexamined Patent Publication No. Hei 11-217600 Japanese Unexamined Patent Publication No. 2005-185352 Japanese Patent Laid-Open No. 7-34091 Japanese Unexamined Patent Publication No. 1-221498 Japanese Unexamined Patent Publication No. 2011-225763 Japanese Unexamined Patent Publication No. 2004-210808

The present invention has been made in view of the above circumstances, and aims at a liquid detergent for bathrooms which has more excellent detergency and also has a good rinse property.

Furthermore, in view of the above circumstances, an object of the present invention is a bathroom liquid detergent having excellent cleaning power even on a vertical surface of a bathtub.

Another object of the present invention is a bathroom liquid detergent having excellent low-temperature stability in addition to the excellent detergency and rinsability described above.

As a result of earnestly examining the present inventors, it was discovered that the above-described subject that the following liquid detergents for bathroom were compatible with sufficient detergency and rinsability was solvable.

[1] Component (A): 0.1 to 5.0% by mass of a surfactant containing a non-soap anionic surfactant (a1), Component (B): a glycol-based solvent, and Component (C): an aminocarboxylic acid type chelating agent It contains, and the mass ratio represented by the component (C)/component (A) is 0.6 to 6.0, and the pH at 25°C exceeds 10 and is less than 12. Liquid detergent for bathroom characterized by the above.

Further, the inventors of the present invention found that sufficient detergency on a vertical surface cannot be obtained simply by increasing the viscosity of the detergent to improve adhesion and retention, and excellent detergency can be obtained even on a vertical surface by having both adhesion and retention and diffusivity. .

Then, the present inventors further conducted an earnest examination and discovered that the following liquid detergent for bathrooms could solve the said subject.

[2] In the above [1], the component (A) is a surfactant further containing a nonionic surfactant (a2), and

(D) component: containing a water-soluble polymer,

A liquid detergent for bathroom, characterized in that the kinematic viscosity measured by a tubular viscometer at 25 ° C is 1.5 to 20 mm / s.

[3] The liquid detergent for bathroom according to [2], wherein the component (D) is a polysaccharide.

Moreover, the present inventors discovered that the said subject of improving low-temperature stability was able to be solved by the following liquid detergent for bathrooms in addition to the excellent cleaning power and rinseability.

[4] The component (A) according to the above [1] is a surfactant further containing a nonionic surfactant (a2),

(C) The mass ratio represented by component/(a1) component is 0.6 to 6.0,

The mass ratio represented by component (C)/component (a2) is 0.4 to 2.0, characterized in that the bathroom liquid detergent.

[5] The liquid detergent for bathroom according to [4], wherein the mass ratio represented by component (a2)/component (A) is 0.30 or more.

[6] The liquid detergent for bathroom according to [4] or [5], wherein the mass ratio represented by component (B)/component (C) is 0.01 to 4.0.

(Effects of the Invention)

ADVANTAGE OF THE INVENTION According to this invention, the liquid detergent for bathrooms which has more excellent cleaning power and also has favorable rinse property can be provided.

Further, according to the present invention, it is possible to provide a bathroom liquid detergent having excellent cleaning power even on a vertical surface of a bathtub.

Further, according to the present invention, it is possible to provide a bathroom liquid detergent having excellent low-temperature stability in addition to the excellent detergency and rinseability.

<<First Embodiment>>

EMBODIMENT OF THE INVENTION Below, the 1st Embodiment of the liquid detergent for bathrooms by this invention is described.

The liquid detergent for bathroom of this invention contains the following (A) - (C) components.

<Component (A)>

Component (A) is a surfactant containing a non-soap anionic surfactant (a1), and is used to impart detergency to a liquid bathroom detergent.

In the present invention, the non-soap anionic surfactant (a1) is an anionic surfactant excluding, for example, a saturated or unsaturated fatty acid salt having 8 to 24 carbon atoms (so-called soap).

Component (A) may consist only of component (a1), or may consist of component (a1) and a surfactant other than this.

(a1) As a component, it is linear alkylbenzene sulfonic acid salt (LAS), for example; straight or branched chain alkyl sulfates (AS); sulfuric acid ester type anionic surfactants such as alkyl ether sulfates or alkenyl ether sulfates (AES); α-olefin sulfonic acid salts (AOS); alkanesulfonic acid salts having an alkyl group; sulfonic acid type anionic surfactants such as α-sulfofatty acid ester salt (α-SF); carboxylic acid type anionic surfactants such as alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, and acylamino carboxylates; phosphoric acid ester type anionic surfactants such as alkyl phosphate ester salts, polyoxyalkylene alkyl phosphate ester salts, polyoxyalkylene alkylphenyl phosphate ester salts, and glycerin fatty acid ester monophosphate ester salts; and the like.

Among these, sulfonic acid type, sulfuric acid ester type, and carboxylic acid type anionic surfactants are preferable, and sulfonic acid type anionic surfactants are more preferable.

Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine salts, diethanolamine salts and triethanolamine salts, and ammonium salts. Among these, an alkali metal salt is preferable.

Among the above, as the straight-chain alkylbenzenesulfonic acid salt, those having 8 to 16 carbon atoms of the straight-chain alkyl group are preferable, and those having 10 to 14 carbon atoms are more preferable.

As an alkyl sulfate, a C10-C20 thing is preferable, and a C10-C16 thing is more preferable.

As the alkyl ether sulfate or alkenyl ether sulfate, polyoxyethylene alkyl ether sulfate or polyoxyethylene alkenyl ether having a straight or branched chain alkyl or alkenyl group having 10 to 20 carbon atoms and adding an average of 1 to 10 moles of ethylene oxide. Sulfates are preferred.

As the α-olefin sulfonic acid salt, those having 10 to 20 carbon atoms are preferable, and those having 10 to 16 carbon atoms are more preferable.

As the alkanesulfonic acid salt, a secondary alkanesulfonic acid salt having an alkyl group of 10 to 20 carbon atoms, preferably 14 to 17 carbon atoms is preferable.

As the α-sulfofatty acid ester salt, an α-sulfofatty acid ester salt having 10 to 20 carbon atoms, preferably 10 to 18 carbon atoms is preferable.

As the polyoxyalkylene ether carboxylate, a polyoxyethylene alkyl ether carboxylate having a straight or branched chain alkyl or alkenyl group having 10 to 20 carbon atoms and adding an average of 1 to 10 moles of ethylene oxide or polyoxyethylene al Kenyl ether carboxylic acid salts are preferred.

Among these, α-olefin sulfonic acid salts are particularly preferred because of their excellent detergency against sebum and protein stains.

As for (a1) component, any 1 type may be used independently, and 2 or more types may be combined together and it may be used.

0.1-5.0 mass % is preferable with respect to the gross mass of the liquid detergent for bathroom, and, as for content of the component (a1) in this embodiment, 1.0-3.0 mass % is more preferable. When the content of the component (a1) is less than 0.1% by mass, there is a risk that sufficient detergency may not be obtained. (a1) When content of a component exceeds 5.0 mass %, rinseability will fall.

In this embodiment, 50-100 mass % is preferable with respect to the total mass of (A) component, and, as for content of component (a1) in (A) component, 80-100 mass % is more preferable.

(A) When the content of the component (a1) in the component is within the above range, good detergency is easily obtained.

In the present embodiment, component (A) may contain surfactants (hereinafter, also referred to as optional surfactants (a3)) other than component (a1) and component (a2) described in detail later (nonionic surfactant).

Although it does not specifically limit as arbitrary surfactant (a3), For example, a higher fatty acid salt, a cationic surfactant, an amphoteric surfactant, etc. are mentioned.

In addition, it is preferable that the component (A) does not contain the component (a3) from the viewpoint of obtaining better detergency.

As the higher fatty acid salts, saturated or unsaturated fatty acids having 8 to 24 carbon atoms such as laurate, myristate, and stearate, or mixtures thereof, such as palm oil fatty acid salts, hardened palm oil fatty acid salts, hardened palm oil fatty acid salts, beef tallow Fatty acid salts, hardened beef tallow fatty acid salts, and the like are exemplified. Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine salts, diethanolamine salts and triethanolamine salts, and ammonium salts.

Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, benzalkonium salts, benzethonium salts, pyridinium salts, and imidazolium salts. A halogen ion etc. are mentioned as a counter ion of these salts.

Examples of amphoteric surfactants include alkylcarboxybetaines, alkylsulfobetaines, alkylhydroxysulfobetaines, alkylamide betaines, and imidazolinium betaines.

As for (a3) component, any 1 type may be used independently, and 2 or more types may be used in combination.

Content of (A) component in this embodiment is 0.1-5.0 mass % with respect to the gross mass of the liquid detergent for bathroom, and 1.0-3.0 mass % is more preferable.

(A) If the content of the component is less than 0.1% by mass, sufficient detergency is not obtained.

(A) When content of component exceeds 5.0 mass %, favorable rinse property is not obtained.

<Component (B)>

(B) component is a glycol-type solvent.

As the glycol-based solvent of the present invention, those selected from compounds represented by the following general formula (I) are preferred.

R ¹ -O-(C ₂ H ₄ O) _x -(C ₃ H ₆ O) _y -R ² ...(Ⅰ)

In the above formula (I), R ¹ and R ² are each independently a hydrogen atom, an alkyl or alkenyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group. x is a number representing the average repeating number of oxyethylene groups, and in this embodiment, 0 to 5 are preferable, 1 to 3 are more preferable, and 1 or 2 is still more preferable. y is a number representing the average repeating number of oxypropylene groups, and in this embodiment, 0 to 5 are preferable, and 0 to 2 are more preferable. However, in the general formula (I), x and y do not become 0 at the same time.

As the component (B), for example, ethylene glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, propylene glycol solvents such as propylene glycol, dipropylene glycol, tripropylene glycol and isoprene glycol, ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Ethylene glycol ethers such as propyl ether, diethylene glycol monobutyl ether, diethylene glycol monobenzyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene Propylene glycol ethers such as glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether , dialkyl glycol ether solvents such as propylene glycol methyl ethyl ether and dipropylene glycol methyl ethyl ether.

As component (B), diethylene glycol monobutyl ether, diethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monopropyl ether, and ethylene glycol monohexyl ether are preferable, and diethylene glycol monobutyl ether is particularly preferable. .

(B) component may be used individually by any 1 type, and may be used in combination of 2 or more types.

0.1-5.0 mass % is preferable with respect to the gross mass of the liquid detergent for bathroom, and, as for content of (B) component, 1.0-3.0 mass % is more preferable. (B) It becomes easy to obtain favorable cleaning power as content of a component is more than the said lower limit. (B) It becomes easy to obtain favorable rinse property as content of a component is below the said upper limit.

<Component (C)>

Component (C) is an aminocarboxylic acid type chelating agent.

In the present invention, by using the component (C) under an alkaline condition in which the pH at 25°C exceeds 10 and is less than 12, even if the content of the component (A) is in a suppressed range (0.1 to 5.0% by mass), it adheres to a bathtub or the like. Increases detergency against fatty acid metal salts, sebum and protein contamination.

(C) Components include methylglycine diacetic acid (MGDA), aspartic acid diacetic acid (ASDA), isoserine diacetic acid (ISDA), β-alanine diacetic acid (ADAA), serine diacetic acid (SDA), glutamic acid diacetic acid (GLDA) , iminodisuccinic acid (IDS), hydroxyiminodisuccinic acid (HIDS), ethylenediaminetetraacetic acid (EDTA), N-lauroylethylenediaminetriacetic acid, nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA) ), hydroxyethylenediaminetriacetic acid (HEDTA), triethylenetetraaminehexaacetic acid (TTHA), 1,3-propanediaminetetraacetic acid (PDTA), 1,3-diamino-2-hydroxypropanetetraacetic acid (DPTA) -OH), hydroxyethyleneiminodiacetic acid (HIDA), dihydroxyethylglycine (DHEG), glycoletherdiaminetetraacetic acid (GEDTA), dicarboxymethylglutamic acid (CMGA), (S,S)-ethylenediaminedisuccinic acid (EDDS) or salts thereof.

(C) Component includes ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), dihydroxyethylglycine (DHEG), hydroxyethyleneiminodiacetic acid (HIDA), diethylenetriaminepentaacetic acid (DTPA) ) is preferred, and ethylenediaminetetraacetic acid (EDTA) is particularly preferred.

(C) component may be used individually by any 1 type, and may be used in combination of 2 or more types.

0.2-5.0 mass % is preferable with respect to the gross mass of the liquid detergent for bathroom, and, as for content of (C)component in this embodiment, 1.5-4.0 mass % is more preferable.

(C) Detergency becomes higher as content of component is more than the said lower limit. (C) Rinsing property improves more as content of a component is below the said upper limit.

The mass ratio represented by component (C)/component (A) [the mass ratio of the content of component (C) to the content of component (A), hereinafter also referred to as “C/A ratio”] is 0.6 to 6.0, and is 0.6 to 6.0. 5.0 is preferable and 0.6 to 3.0 are more preferable.

In the present invention, by setting the C/A ratio within the above range, even when the content of the component (A) is in a suppressed range (0.1 to 5.0% by mass), excellent detergency against metal salts of fatty acids, sebum and protein stains adhering to bathtubs and the like is obtained, Also, good rinsing properties are obtained. In particular, when the bathtub is cleaned without scrubbing, the amount of detergent used increases because the liquid detergent for bathroom is applied to the entire surface of the bathtub. By making the C/A ratio within the above range, good rinsability is obtained even when the usage-amount of the cleaning agent is increased.

When the C/A ratio is less than 0.6, sufficient rinsing properties are not obtained. Further, when the C/A ratio exceeds 6.0, sufficient detergency is not obtained.

In this embodiment, the total content of (A) component and (B) component (hereinafter also referred to as "A+B total content") is preferably 0.5 to 8.0 mass% with respect to the total mass of the liquid detergent for bathroom. The detergency becomes higher when the total content of the component (A) and the component (B) is more than the lower limit. Rinsing property becomes higher as the total content of (A) component and (B) component is below the said upper limit.

The mass ratio represented by component (B)/component (C) [the mass ratio of the content of component (B) to the content of component (C), hereinafter also referred to as “B/C ratio”] is preferably 0.01 to 4.0, 0.4 to 3.0 are more preferable. Detergency becomes higher as B/C ratio is the said preferable range.

<Solvent>

The liquid detergent for bathroom of the present invention usually contains water as a solvent for reasons such as ease of preparation of the liquid detergent for bathroom and easy dissolution in water at the time of rinsing.

Although the compounding quantity of the water in bathroom liquid detergent is not specifically limited, 50-99.5 mass % is preferable in bathroom liquid detergent, 70-99 mass % is more preferable, 75-98 mass % is still more preferable.

<Optional ingredients>

The liquid detergent for bathroom of the present invention may contain components that can be used in normal detergents in addition to the above components as needed. Examples of such optional components include bactericides, preservatives, antifungal agents, pigments, antioxidants, thickeners, ultraviolet absorbers, solubilizers (but not including component (B)), flavoring agents, pH adjusters, and the like. .

The pH adjuster is not particularly limited, but a powder selected from inorganic acids such as hydrochloric acid and sulfuric acid, citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid, and organic acids such as p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, and carbonic acid It is preferable to use an alkali agent selected from sodium, potassium carbonate, ammonia and its derivatives, monoethanolamine, diethanolamine, triethanolamine and the like, and a powder agent selected from hydrochloric acid, sulfuric acid and citric acid, sodium hydroxide and potassium hydroxide It is more preferable to use an alkali chemicals.

Any 1 type of pH adjuster may be used independently, and 2 or more types may be combined together and it may be used.

The pH of the liquid detergent for bathroom of this invention at 25 degreeC exceeds 10 and is less than 12, pH 10.1-11.4 are preferable, and pH 10.4-11.4 are more preferable.

Even if the liquid detergent for bathroom of this invention is the range (0.1-5.0 mass %) in which the content of (A) component was suppressed by using the (A)-(C) component in a specific C/A ratio in the said range, a bathtub etc. Good detergency is obtained against adhering metal salts of fatty acids, sebum and protein stains.

In addition, the pH of the liquid detergent for bathroom of this invention is the value measured in 25 degreeC by the method prescribed|regulated by JIS Z8802:2011.

It is preferable that the viscosity in 25 degreeC of the liquid detergent for bathroom of this invention is 1-100 mPa*s, and it is more preferable that it is 1-50 mPa*s.

The adhesiveness of the liquid detergent for bathroom with respect to washing objects, such as a bathtub, improves more that the viscosity in 25 degreeC is more than the said lower limit. When the viscosity at 25°C is equal to or less than the above upper limit, it is easy to discharge the liquid detergent for bathroom from a discharge container such as a spray container, and the handling property becomes good.

The liquid detergent for bathroom of this invention is manufactured by a conventionally well-known manufacturing method. For example, the method of adding the said (A) - (C) component to the water which is a solvent, adding an arbitrary component as needed, and mixing this etc. are mentioned.

As a method of using the liquid bathroom detergent of the present invention, for example, a cleaning tool such as a sponge is impregnated with the liquid bathroom detergent, and objects for washing such as a bathroom wall surface, a bathtub surface, and other bathroom accessory facilities are rubbed and cleaned with a sponge or the like. A method of using "cleaning without rubbing" in which the liquid detergent for bathroom is placed in a discharge container, an appropriate amount of liquid detergent for bathroom is applied from the discharge container to the object to be cleaned, and then rinsed in a shower or the like after a certain period of time has elapsed. etc. can be mentioned.

The liquid bathroom detergent of the present invention has high cleaning power against fatty acid metal salts, sebum and protein contamination adhering to the bathtub, and has excellent rinsing properties even when the amount of the detergent is increased by applying the liquid bathroom detergent to the entire surface of the bathtub. Since it has, it is suitably used in the usage method of "cleaning without rubbing".

Although a spray container, a squeeze container, etc. are mentioned as a discharge container which accommodates the liquid detergent for bathrooms of this invention, A spray container is preferable from the point which is excellent in applicability to a washing object.

Examples of spray containers include aerosol spray containers, trigger spray containers (direct pressure type or pressure pressure type), dispenser spray containers, and the like. These containers may be of a manual type or of a motorized type.

As an aerosol spray container, what is described in Unexamined-Japanese-Patent No. 9-3441, Unexamined-Japanese-Patent No. 9-58765 etc. is mentioned, for example. When filling an aerosol spray container, LPG (liquefied propane gas), DME (dimethyl ether), carbon dioxide gas, nitrogen gas, nitrous oxide gas, etc. can be used as a propellant. These propellants may be used alone or in combination of two or more.

As an example of a trigger spray container, what was described in Unexamined-Japanese-Patent No. 9-268473, Unexamined-Japanese-Patent No. 10-76196 etc. is mentioned, for example.

As an example of a dispenser spray container, what was described in Unexamined-Japanese-Patent No. 9-256272 etc. is mentioned, for example.

As an accumulator type trigger spray container, the thing of Unexamined-Japanese-Patent No. 2013-154276 grade|etc., is mentioned, for example.

Among these, an accumulative pressure type trigger spray container is preferable from the viewpoint that the spray properties and spray patterns are good and good coating properties are obtained.

As described above, the liquid detergent for bathroom of the present invention contains components (A) to (C), the mass ratio of component (C)/component (A) is within a specific range, and the pH at 25°C is Since is within a specific range, the cleaning power is higher and the rinsing property is also excellent.

<<Second Embodiment>>

2nd Embodiment of the liquid detergent for bathrooms by this invention is described below.

Note that, in the following description of the second embodiment, the detailed description of the configuration similar to that of the first embodiment is omitted in some cases.

In the liquid detergent for bathroom of the present embodiment, in the components (A) to (C) shown in the first embodiment, the component (A) is a surfactant further containing a nonionic surfactant (a2), and (D) Component: It is a composition containing a water-soluble polymer and having a kinematic viscosity of 1.5 to 20 mm 2 /s measured with a tubular viscometer at 25°C.

<Component (A)>

In this embodiment, component (A) is a surfactant containing 0.1 to 5.0% by mass of a surfactant containing a non-soap anionic surfactant (a1) and a nonionic surfactant (a2), and is added to a bath liquid detergent for bathroom use. It is used to impart cleaning power on the vertical surface of

In the present embodiment, the nonionic surfactant (a2) is a polyoxyalkylene type nonionic surfactant obtained by adding an alkylene oxide to a higher alcohol, alkylphenol, higher fatty acid or higher amine, polyoxyethylene polyoxypropylene block copolymer, Fatty acid alkanolamides, polyalcohol fatty acid esters or alkylene oxide adducts thereof, fatty acid polyglycerin esters, glycol fatty acid esters, alkyl (or alkenyl) amine oxides, amide amine oxides, alkylene oxide adducts of hydrogenated castor oil, and N-alkyl polyhydroxy fatty acid amides, alkyl glycosides, alkyl polyglycosides, and glyceryl ether.

Among these, a polyoxyalkylene type nonionic surfactant obtained by adding an alkylene oxide to a higher alcohol is preferred.

Examples of the alkylene oxide include ethylene oxide, propylene oxide and butylene oxide, preferably ethylene oxide and propylene oxide, and more preferably ethylene oxide. 3-50 are preferable, as for the average number of added moles of an alkylene oxide, 4-20 are more preferable, and 6-15 are especially preferable.

8-20 are preferable and, as for carbon number of the alkyl group of a higher alcohol, 10-15 are more preferable.

Especially, oxo alcohol ethoxylate, Guerbet alcohol ethoxylate, and polyoxyethylene alkyl ether are preferable.

In oxoalcohol ethoxylate, it is preferable that the number of carbon atoms of an alkyl group is 10-15 and the average number of added moles of ethylene oxide is 6-15. Specifically, Lutensol TO from BASF, LTD. is preferable.

In Guerbet alcohol ethoxylate, it is preferable that the number of carbon atoms of an alkyl group is 10 and the average number of added moles of ethylene oxide is 6 to 15. Specifically, Lutensol XP from BASF, LTD. is preferable.

In polyoxyethylene alkyl ether, it is preferable that the number of carbon atoms of an alkyl group is 12 to 14 and the average number of added moles of ethylene oxide is 6 to 15. Specifically, LMAO-90 from LION CHEMICAL CORPORATION is preferable.

As for (a2) component, any 1 type may be used independently, and 2 or more types may be combined together and it may be used.

The content of the component (a2) is preferably 0.04 to 5.0% by mass, more preferably 0.5 to 5.0% by mass, still more preferably 1.0 to 3.0% by mass with respect to the total mass of the liquid detergent for bathroom. When the content of the component (a2) is within the above range, more excellent detergency can be easily obtained on the vertical surface of the bathtub.

The content of component (a2) in component (A) is preferably 0.1 to 100% by mass, more preferably 30 to 90% by mass, and still more preferably 40 to 85% by mass, based on the total mass of component (A).

When the content of the component (a2) in the component (A) is within the above range, better detergency on the vertical surface of the bathtub can be easily obtained.

In the present embodiment, component (A) includes the non-soap anionic surfactant (hereinafter also referred to as component (a1)) described in the first embodiment as surfactants other than component (a2).

In the present embodiment, the non-soap anionic surfactant (a1) is an anionic surfactant excluding saturated or unsaturated fatty acid salts having 8 to 24 carbon atoms, and can be appropriately selected from components similar to those exemplified in the first embodiment.

Also in this embodiment, component (a1) is used in order to impart detergency to the liquid detergent for bathroom.

In this embodiment, any 1 type of component (a1) may be used independently, and 2 or more types may be used in combination.

0.1-3.0 mass % is preferable with respect to the gross mass of the liquid detergent for bathroom, and, as for content of the component (a1) in this embodiment, 0.5-2.0 mass % is more preferable. When the content of the component (a1) is within the above numerical range, more excellent detergency on the vertical surface of the bathtub can be easily obtained.

In this embodiment, as in the case of the first embodiment, component (A) may contain surfactants other than component (a1) and component (a2) (hereinafter, also referred to as optional surfactant (a3)).

Although it does not specifically limit as arbitrary surfactant (a3), For example, the thing similar to the composition illustrated in 1st embodiment, such as a higher fatty acid salt, a cationic surfactant, and an amphoteric surfactant, is mentioned.

In addition, it is preferable that the component (A) does not contain the component (a3) from the viewpoint of obtaining better detergency.

Also in this embodiment, as in the case of the first embodiment, any one type of component (a3) may be used alone, or two or more types may be used in combination.

0.1-6.0 mass % is preferable with respect to the gross mass of the liquid detergent for bathroom, and, as for content of (A) component in this embodiment, 1.0-3.0 mass % is more preferable.

In this embodiment, when the content of component (A) is within the above numerical range, more excellent detergency on the vertical surface of the bathtub can be easily obtained.

<Component (B)>

Also in this embodiment, component (B) is a glycol-based solvent similarly to the first embodiment.

The glycol-based solvent of the present invention is preferably selected from compounds represented by the following general formula (I) as described in the first embodiment.

R ¹ -O-(C ₂ H ₄ O) _x -(C ₃ H ₆ O) _y -R ² ...(Ⅰ)

In the above formula (I), R ¹ and R ² are each independently a hydrogen atom, an alkyl or alkenyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group. x is a number representing the average repeating number of oxyethylene groups, and in this embodiment, 1 to 5 are preferable, 1 to 3 are more preferable, and 1 or 2 is still more preferable. y is a number representing the average repeating number of oxypropylene groups, and in this embodiment, 1 to 5 are preferable, and 1 to 2 are more preferable. However, in the general formula (I), x and y do not become 0 at the same time.

As the component (B), those satisfying the above conditions can be appropriately selected from among the various compounds exemplified in the first embodiment.

(B) component may be used individually by any 1 type, and may be used in combination of 2 or more types.

Also in this embodiment, 0.1-5.0 mass % is preferable with respect to the gross mass of the liquid detergent for bathroom, and, as for content of (B) component, 1.0-3.0 mass % is more preferable. (B) When content of component is in the said range, more favorable cleaning power will become easy to be obtained.

<Component (C)>

In this embodiment, component (C) is an aminocarboxylic acid type chelating agent.

Also in the present embodiment, by using the component (C), as in the first embodiment, the cleaning power against metal salts of fatty acids, sebum and protein adhering to bathtubs and the like is increased.

Also as component (C), it can be appropriately selected from among the various compounds exemplified in the first embodiment.

(C) component may be used individually by any 1 type, and may be used in combination of 2 or more types.

0.2-8.0 mass % is preferable with respect to the gross mass of the liquid detergent for bathroom, and, as for content of (C)component in this embodiment, 1.5-7.0 mass % is more preferable. (C) When the content of the component is within the above range, more excellent detergency is easily obtained.

In this embodiment, the mass ratio represented by component (C)/component (a1) [the mass ratio of the content of component (C) to the content of component (a1), hereinafter also referred to as “C/a1 ratio”] is 0.1 to 0.1. 5.0 is preferable, 0.4 to 4.0 are more preferable, and 0.6 to 3 are particularly preferable.

In the present embodiment, by setting the C/a1 ratio within the above range, it is easier to obtain better detergency against metal salts of fatty acids, sebum and protein stains adhering to bathtubs and the like.

In the present embodiment, the mass ratio represented by component (C)/component (a2) [the mass ratio of the content of component (C) to the content of component (a2), hereinafter also referred to as “C/a2 ratio”] is 0.6 to 6.0 are preferable, 0.6 to 5.0 are more preferable, and 0.6 to 3.0 are particularly preferable.

In the present embodiment, by setting the C/a2 ratio within the above range, it is easier to obtain more excellent detergency against metal salts of fatty acids, sebum and protein stains adhering to bathtubs and the like.

In the present embodiment, the mass ratio represented by component (B)/component (C) [the mass ratio of the content of component (B) to the content of component (C), hereinafter also referred to as “B/C ratio”] As for the case of 1st Embodiment, 0.01-4.0 are preferable, and 0.4-3.0 are more preferable. When the B/C ratio is within the preferred range, more excellent detergency is easily obtained.

<Component (D)>

In this embodiment, component (D) is a water-soluble polymer. Component (D) is used to impart adhesion retention and diffusivity on the vertical surface of the bathtub.

In addition, the polymer demonstrated in this specification means a thing with a weight average molecular weight of 1000 or more. The weight average molecular weight is a value obtained by converting a value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent based on a calibration curve in PEG (polyethylene glycol). In addition, the water-soluble polymer means that 10 g of the polymer is added to 1000 g of water in a 1 liter beaker at 40 ° C., and dissolved after stirring (200 rpm) for 12 hours with a stirrer (8 mm in thickness, 50 mm in length).

Examples of the component (D) in the present embodiment include polysaccharides typified by xanthan gum, gellan gum, carrageenan, and guar gum; cellulosic polymers such as cationized cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose (CMC); pyrrolidone-based polymers such as polyvinylpyrrolidone and N-alkylpyrrolidone; polyalkylene glycol-based polymers such as polyethylene glycol (PEG), polypropylene glycol, and polyethylene glycol/polypropylene glycol copolymers; and polyvinyl-based polymers such as polyvinyl alcohol (PVA) and polyvinyl acetate.

Among them, polysaccharides are preferred.

In addition, as (D)component, the following are included. For example, as component (D), an alkali-soluble/swellable emulsion (ASE) polymer, a hydrophobically modified alkali-soluble/swellable emulsion (HASE) polymer, an acid-soluble/swellable emulsion polymer, a hydrophobically modified acid-soluble/swellable emulsion polymers, acidic homopolymers, copolymers and salts thereof; basic homopolymers, copolymers and salts thereof; poly(quaternized amine) homopolymers, copolymers, and salts thereof; amphoteric polymer; anionic, cationic and amphoteric polysaccharide homopolymers, copolymers and salts thereof; anionic, cationic and amphoteric polysaccharide derivatives; anionic, cationic and amphoteric polypeptide homopolymers, copolymers and salts thereof; anionic, cationic and amphoteric polypeptide derivatives; chemically modified polypeptide homopolymers, copolymers and salts thereof; nucleic acid homopolymers, copolymers and salts thereof; chemically modified nucleic acids, naturally derived nucleic acids, enzymes, synthetic and naturally derived proteins, gelatin, lignosulfonic acid homopolymers, copolymers and salts thereof; jonene homopolymers, copolymers and salts thereof; anionic, cationic and amphoteric polyester homopolymers, copolymers and salts thereof; anionic, cationic and amphoteric polyurethane homopolymers, copolymers and salts thereof; combinations of the listed homopolymers, copolymers and copolymers of their salts; ionic and nonionic micelles; combinations of stoichiometric and non-stoichiometric interpolymers of the listed homopolymers, copolymers and salts thereof; polymer matrices of the recited homopolymers, copolymers and salts thereof; physical blends of the recited homopolymers, copolymers and salts thereof; listed homopolymers, copolymers and salts thereof, and combinations thereof, having anionic, cationic and amphoteric components grafted thereon.

Moreover, as component (D), xanthan gum, gellan gum, carrageenan, guar gum, CMC, cationized cellulose, PVA, and PEG are especially preferable.

As for (D) component, any 1 type may be used independently, and 2 or more types may be combined.

0.005-0.15 mass % is preferable with respect to the gross mass of the liquid detergent for bathroom, and, as for content of (D) component, 0.01-0.10 mass % is more preferable.

When the content of component (D) is equal to or greater than the above lower limit, adhesion retention on the vertical surface of the bathtub is likely to increase, and better detergency on the vertical surface of the bathtub can be easily obtained. When the content of component (D) is equal to or less than the above upper limit, the diffusivity on the vertical surface of the bathtub is easily increased, and better detergency on the vertical surface of the bathtub is easily obtained.

As a preferable combination of components (A) to (D) in the present embodiment, component (a1) is an α-olefin sulfonate, component (a2) is oxoalcohol ethoxylate, Guerbet alcohol ethoxylate, and polyoxyethylene. It is at least one selected from the group consisting of alkyl ethers, and component (B) is diethylene glycol monobutyl ether, diethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monopropyl ether, and ethylene glycol monohexyl ether. It is at least one kind selected from the group consisting of, and component (C) is ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetetraacetic acid (HEDTA), dihydroxyethylglycine (DHEG), and hydroxyethyleneiminodiacetic acid (HIDA). ) And at least one member selected from the group consisting of diethylenetriamine pentaacetic acid (DTPA), and component (D) consists of xanthan gum, gellan gum, carrageenan, guar gum, CMC, cationized cellulose, PVA and PEG It is preferable that it is at least 1 sort(s) selected from the group.

<Solvent>

Also in the bathroom liquid detergent of the present embodiment, as in the case of the first embodiment, water is usually contained as a solvent for reasons such as easy preparation of the bathroom liquid detergent and easy dissolution in water during rinsing.

It can be set as the same compounding quantity as 1st Embodiment also as a compounding quantity of the water in the liquid detergent for bathroom in this embodiment.

<Optional ingredients>

In the bathroom liquid detergent of the present embodiment, as in the case of the first embodiment, components that can be used for cleaning agents normally can be contained in addition to the above components as needed. As these optional components, the same components as those exemplified in the first embodiment, that is, disinfectants, antiseptics, antifungal agents, pigments, antioxidants, thickeners, ultraviolet absorbers, solubilizers (however, component (B) is not included), A flavoring agent, a pH adjuster, etc. are mentioned.

Although it does not specifically limit as a pH adjuster, It can select suitably from the various compounds exemplified in 1st Embodiment.

Moreover, any 1 type of pH adjuster may be used independently, and 2 or more types may be used in combination.

Moreover, also in the bathroom liquid detergent of this embodiment, it is preferable that pH in 25 degreeC exceeds 10 and is less than 12 similarly to 1st embodiment, pH 10.1-11.4 are more preferable, and pH 10.4-11.4 more preferable

When the liquid detergent for bathroom of the present embodiment has a pH within the above range, it is easier to obtain better detergency against metal salts of fatty acids, sebum and protein stains adhering to bathtubs and the like.

In addition, the pH of the liquid detergent for bathroom of this embodiment is also a value measured on conditions similar to the case of 1st Embodiment.

<Viscosity>

The liquid detergent for bathroom of this embodiment is 1.5-20 mm<2>/s of the kinematic viscosity measured with the tube viscometer in 25 degreeC. Moreover, the viscosity of the liquid detergent for bathroom of this embodiment is more preferably 1.8-15 mm<2>/s.

If the kinematic viscosity of the liquid detergent for bathroom measured with a tubular tube at 25°C is less than the lower limit, adhesion retention on the vertical surface of the bathtub is not obtained, and the detergent drips down in a stripe shape, and sufficient detergency on the vertical surface of the bathtub is not obtained. don't When the kinematic viscosity of the liquid detergent for bathroom measured with a tubular tube at 25°C exceeds the above upper limit, the diffusivity in the vertical surface of the bathtub deteriorates and sufficient cleaning power in the vertical surface of the bathtub is not obtained.

Kinematic viscosity using a tubule can be measured in the order of the viscosity measurement method by a tubular viscometer specified in JIS Z8803 (2011).

The liquid detergent for bathroom of this embodiment is manufactured by a conventionally well-known manufacturing method. For example, the method of adding the said (A) - (D) component to water as a solvent, adding an arbitrary component as needed, and mixing this etc. are mentioned.

The method of using the liquid bathroom detergent of the present embodiment is the same as the method of use described in the first embodiment. A method of using "cleaning without scrubbing" in which a liquid detergent for bathroom of <RTI ID=0.0>is applied to the object to be cleaned and rinsed in a shower or the like after a certain period of time has elapsed.

The liquid bathroom detergent of the present embodiment has high cleaning power against fatty acid metal salts, sebum and protein contamination adhering to the bathtub, and also has excellent cleaning power on the vertical surface of the bathtub when the bathroom liquid detergent is applied to the entire surface of the bathtub. , In particular, it is used suitably for the usage method of "cleaning without rubbing".

Also as a discharge container accommodating the liquid detergent for bathroom of this embodiment, it can select suitably from the various containers illustrated in 1st embodiment. As the discharge container for accommodating the liquid detergent for bathroom of the present embodiment, a spray container is preferable from the viewpoint of excellent applicability to the cleaning object, and the liquid detergent for bathroom is poured into a spray container selected from among the various containers exemplified in the first embodiment. It is desirable to accept

As described above, according to the liquid detergent for bathroom of the present embodiment, components (A) to (D) are contained, and the kinematic viscosity measured with a tubular viscometer at 25° C. is within a specific range, so that it has a detergency even on the vertical surface of the bathtub. great.

[Modification of the second embodiment]

In this embodiment, even when the liquid detergent for bathroom is a composition containing the following (A) to (D) components, for example, the liquid detergent for bathroom having excellent cleaning power even on the vertical surface of the bathtub as described above You can get it.

(A) component: a surfactant containing a nonionic surfactant (a2);

(B) component: a glycol-based solvent;

Component (C): an aminocarboxylic acid type chelating agent;

(D) component: containing a water-soluble polymer,

A liquid detergent for bathrooms having a kinematic viscosity of 1.5 to 20 mm/s as measured by a tubular viscometer at 25°C.

That is, the bathroom liquid detergent of this embodiment does not contain a non-soap type anionic surfactant (a1) as component (A), and the mass ratio represented by component (C)/component (A) is in the range of 0.6 to 6.0. is not satisfied, and the pH at 25 ° C. exceeds 10 and does not satisfy the range of less than 12, by satisfying the composition and kinematic viscosity of the components (A) to (D) above, with respect to the vertical surface of the bathtub It is possible to obtain a liquid detergent for bathrooms having sufficient cleaning power.

<<Third Embodiment>>

3rd Embodiment of the liquid detergent for bathrooms by this invention is described below.

Note that, in the description of the third embodiment below, detailed descriptions of components similar to those of the first and second embodiments may be omitted in some cases.

In the liquid detergent for bathroom of the present embodiment, in the components (A) to (C) shown in the first embodiment, the component (A) is a surfactant further containing a nonionic surfactant (a2), and [(C ) component/(a1) component] is 0.6 to 6.0, and the mass ratio represented by [(C) component/(a2) component] is 0.4 to 2.0.

<Component (A)>

In this embodiment, (A) component is surfactant containing a non-soap type anionic surfactant (a1) and a nonionic surfactant (a2).

[Component (a1)]

In this embodiment, the non-soap type anionic surfactant (a1) is used in order to impart detergency to the bathroom liquid detergent.

In the present embodiment, the non-soap anionic surfactant (a1) is an anionic surfactant excluding saturated or unsaturated fatty acid salts having 8 to 24 carbon atoms, and can be appropriately selected from components similar to those described in the first embodiment.

As for (a1) component, any 1 type may be used independently, and 2 or more types may be combined together and it may be used.

In this embodiment, the content of component (a1) is 0.1 to 5.0% by mass, more preferably 0.5 to 5.0% by mass, and 1.0 to 3.0% by mass, similarly to the case of the first embodiment, relative to the total mass of the liquid detergent for bathroom. % is more preferred. When the content of the component (a1) is less than 0.1% by mass, there is a possibility that sufficient detergency may not be obtained as in the case of the first embodiment. (a1) When content of a component exceeds 5.0 mass %, rinseability will fall.

In the present embodiment, the mass ratio represented by component (a1)/component (A) [the mass ratio of the content of component (a1) to the content of component (A), hereinafter also referred to as “a1/A ratio”] is from 0.10 to 0.10. 0.90 is preferable, 0.20 to 0.80 are more preferable, and 0.30 to 0.80 are still more preferable. When the a1/A ratio is within the above preferred range, more favorable detergency can be easily obtained.

[Component (a2)]

In this embodiment, component (a2) is a nonionic surfactant, and is used in order to impart low-temperature stability to the liquid detergent for bathroom.

In the present embodiment, the component (a2) can be appropriately selected from among the various compounds exemplified in the first embodiment.

In this embodiment, any 1 type of component (a2) may be used independently, and 2 or more types may be used in combination.

The content of the component (a2) is preferably 0.5 to 5.0% by mass, more preferably 0.5 to 4.0% by mass, still more preferably 0.5 to 3.0% by mass, based on the total mass of the liquid detergent for bathroom.

When the content of the component (a2) is equal to or higher than the lower limit, better low-temperature stability is easily obtained. (a2) When the content of the component is below the upper limit, better rinseability is easily obtained.

In the present embodiment, the mass ratio represented by component (a2)/component (A) [the mass ratio of the content of component (a2) to the content of component (A), hereinafter also referred to as “a2/A ratio”] is 0.20 to 0.90 is preferable, 0.30 or more is more preferable, and 0.35 to 0.85 are still more preferable. When the a2/A ratio is within the above preferred range, better low-temperature stability is easily obtained.

In the present embodiment, the mass ratio represented by component (a2)/component (a1) [the mass ratio of the content of component (a2) to the content of component (a1), hereinafter also referred to as “a2/a1 ratio”] is 0.1 to 0.1. 5.0 is preferable, 0.2 to 4.0 are more preferable, and 0.3 to 2.0 are still more preferable. When the a2/a1 ratio is within the above preferred range, more excellent detergency, rinseability and low-temperature stability can be easily obtained.

In this embodiment, as in the case of the first and second embodiments, component (A) contains a surfactant other than component (a1) and component (a2) (hereinafter, also referred to as optional surfactant (a3)). It may be.

Although it does not specifically limit as arbitrary surfactant (a3), For example, the thing similar to the composition illustrated in 1st embodiment, such as a higher fatty acid salt, a cationic surfactant, and an amphoteric surfactant, is mentioned.

In addition, it is preferable that the component (A) does not contain the component (a3) from the viewpoint of obtaining better detergency and low-temperature stability.

Also in the present embodiment, as in the case of the first embodiment and the second embodiment, as for the (a3) component, any one type may be used alone, or two or more types may be used in combination.

<Component (B)>

Also in this embodiment, component (B) is a glycol-based solvent similarly to the first and second embodiments.

As the glycol-based solvent of the present invention, those selected from compounds represented by the following general formula (I) as described in the first embodiment and the second embodiment are also preferred.

R ¹ -O-(C ₂ H ₄ O) _x -(C ₃ H ₆ O) _y -R ² ...(Ⅰ)

In the above formula (I), R ¹ and R ² are each independently a hydrogen atom, an alkyl or alkenyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group. x is a number representing the average repeating number of oxyethylene groups, and in this embodiment, 0 to 5 are preferable, 1 to 3 are more preferable, and 1 or 2 is still more preferable. y is a number representing the average repeating number of oxypropylene groups, and in this embodiment, 1 to 5 are preferable, and 1 to 2 are more preferable. However, in the above general formula (I), x and y do not become 0 at the same time.

As the component (B), those satisfying the above conditions can be appropriately selected from among the various compounds exemplified in the first embodiment.

(B) component may be used individually by any 1 type, and may be used in combination of 2 or more types.

In this embodiment, 0.1-5.0 mass % is preferable with respect to the gross mass of the liquid detergent for bathroom, as for content of (B) component, 0.5-5.0 mass % is more preferable, and 1.0-3.0 mass % is still more preferable. (B) When content of component is more than the said lower limit, more favorable cleaning power will become easy to be obtained. (B) When the content of the component is below the above upper limit, better rinseability is easily obtained.

<Component (C)>

Also in this embodiment, component (C) is an aminocarboxylic acid type chelating agent.

In this embodiment, by using the component (C) under an alkaline condition in which the pH at 25°C is greater than 10 and less than 12, the content of the component (a1) is in a controlled range (0.1 to 5.0% by mass), so that it adheres to a bathtub or the like. Increases detergency against contaminated metal salts of fatty acids, sebum and protein.

Also as component (C), it can be appropriately selected from among the various compounds exemplified in the first embodiment.

(C) component may be used individually by any 1 type, and may be used in combination of 2 or more types.

0.2-6.0 mass % is preferable with respect to the gross mass of the liquid detergent for bathroom, as for content of (C)component in this embodiment, 1.0-5.0 mass % is more preferable, and 1.5-4.0 mass % is still more preferable. . (C) When content of component is more than the said lower limit, more favorable cleaning power will become easy to be obtained. (C) When content of component is below the said upper limit, more favorable rinse property becomes easy to be obtained.

In the present embodiment, the mass ratio represented by component (C)/component (a1) [the mass ratio of the content of component (C) to the content of component (a1), hereinafter also referred to as “C/a1 ratio”] is 0.6 to 6.0. The C/a1 ratio is preferably 0.6 to 5.0, and more preferably 0.6 to 3.0.

In the present embodiment, by setting the C/a1 ratio within the above range, even when the content of the component (a1) is in a suppressed range (0.1 to 5.0% by mass), excellent detergency against metal salts of fatty acids, sebum and protein stains adhering to bathtubs and the like is obtained. , and also good rinseability is obtained. In particular, when the bathtub is cleaned without scrubbing, the amount of detergent used increases because the liquid detergent for bathroom is applied to the entire surface of the bathtub. By making the C/a1 ratio within the above range, good rinseability is obtained even when the usage-amount of the cleaning agent is increased.

In the present embodiment, the mass ratio represented by component (C)/component (a2) [the mass ratio of the content of component (C) to the content of component (a2), hereinafter also referred to as “C/a2 ratio”] is from 0.4 to 0.4. 2.0. The C/a2 ratio is preferably 0.4 to 1.7.

In the present embodiment, by setting the C/a2 ratio within the above range, excellent detergency against fatty acid metal salts, sebum and protein stains adhering to bathtubs and the like is obtained, and good rinseability and low-temperature stability are easily obtained. In particular, when the bathtub is cleaned without scrubbing, the amount of detergent used increases because the liquid detergent for bathroom is applied to the entire surface of the bathtub. By making C/a2 ratio into the said range, even when the usage-amount of a detergent increases, favorable rinseability becomes easy to be obtained. In addition, by setting the C/a2 ratio within the above range, sufficient detergency is obtained and low-temperature stability is also improved.

In the present embodiment, the mass ratio represented by component (B)/component (C) [the mass ratio of the content of component (B) to the content of component (C), hereinafter also referred to as “B/C ratio”] 0.01 to 4.0 are preferable, and 0.4 to 3.0 are more preferable, similarly to the case of 1st Embodiment and 2nd Embodiment. When the B/C ratio is within the above preferred range, more favorable detergency is easily obtained.

As a preferable combination of components (A) to (C) in the present embodiment, component (a1) is an α-olefin sulfonate, component (a2) is oxoalcohol ethoxylate, Guerbet alcohol ethoxylate, and polyoxyethylene. It is at least one selected from the group consisting of alkyl ethers, and component (B) is diethylene glycol monobutyl ether, diethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, propylene glycol monopropyl ether, and ethylene glycol monohexyl ether. It is at least one kind selected from the group consisting of, and component (C) is ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetetraacetic acid (HEDTA), dihydroxyethylglycine (DHEG), and hydroxyethyleneiminodiacetic acid (HIDA). ) and at least one combination selected from the group consisting of diethylenetriamine pentaacetic acid (DTPA).

<Solvent>

Also in the bathroom liquid detergent of the present embodiment, as in the case of the first embodiment and the second embodiment, water is usually used as a solvent for reasons such as ease of preparation of the bathroom liquid detergent and easy dissolution in water during rinsing. contain

It can be set as the same compounding quantity as 1st Embodiment and 2nd Embodiment also as a compounding quantity of the water in the liquid detergent for bathroom in this embodiment.

<Optional ingredients>

In the bathroom liquid detergent of this embodiment, as in the case of the first embodiment and the second embodiment, components that can be used for cleaning agents normally can be contained in addition to the above components as needed. As these optional components, the same components as those exemplified in the first embodiment, that is, disinfectants, antiseptics, antifungal agents, pigments, antioxidants, thickeners, ultraviolet absorbers, solubilizers (however, component (B) is not included), A flavoring agent, a pH adjuster, etc. are mentioned.

Although it does not specifically limit as a pH adjuster, It can select suitably from the various compounds exemplified in 1st Embodiment.

Moreover, any 1 type of pH adjuster may be used independently, and 2 or more types may be used in combination.

Moreover, also in the bathroom liquid detergent of this embodiment, pH in 25 degreeC exceeds 10 and is less than 12 similarly to 1st Embodiment and 2nd Embodiment. As for pH in 25 degreeC, 10.1-11.4 are more preferable, and 10.4-11.4 are still more preferable.

The liquid detergent for bathroom of this embodiment becomes easy to obtain the outstanding detergency, the outstanding rinseability, and the outstanding low-temperature stability when pH is the said range.

In addition, the pH of the liquid detergent for bathroom of this embodiment is also a value measured on conditions similar to the case of 1st Embodiment and 2nd Embodiment.

It is preferable that the viscosity in 25 degreeC of the liquid detergent for bathroom of this embodiment is 1-100 mPa*s, and it is more preferable that it is 1-50 mPa*s.

The adhesiveness of the liquid detergent for bathroom to cleaning objects, such as a bathtub, improves more that the viscosity of the liquid detergent for bathroom in 25 degreeC is more than the said lower limit. If the viscosity of the liquid detergent for bathroom in 25 degreeC is below the said upper limit value, it is easy to discharge a liquid detergent for bathroom from discharge containers, such as a spray container, and handling property becomes favorable.

In addition, the viscosity at 25 degreeC of the liquid detergent in this embodiment shows the value measured using the B-type viscometer (made by TOKIMEC, INC.) by adjusting a sample to 25 degreeC (an example of measurement conditions: rotor No. 1, rotation speed 60 rpm, viscosity measured after 10 rotations).

The liquid detergent for bathroom of this embodiment is manufactured by a conventionally well-known manufacturing method. For example, the method of adding the said (A) - (C) component to the water which is a solvent, adding an arbitrary component as needed, and mixing this etc. are mentioned.

The method of using the liquid bathroom detergent of the present embodiment is the same as the method of use described in the first and second embodiments. or a usage method of "cleaning without scrubbing" in which an appropriate amount of liquid bathroom detergent is applied to the cleaning target from a discharge container and rinsed in a shower or the like after a certain period of time has elapsed.

The liquid bathroom detergent of the present embodiment has a high cleaning power against fatty acid metal salts, sebum and protein contamination adhering to the bathtub, and is excellent in rinsing even when the bathroom liquid detergent is applied to the entire surface of the bathtub and the amount of the detergent is increased. Because it has properties, it is suitably used in the usage method of "cleansing without rubbing". In addition, it has stability that precipitates do not precipitate even under low-temperature storage conditions.

Also as a discharge container accommodating the liquid detergent for bathroom of this embodiment, it can select suitably from the various containers illustrated in 1st embodiment similarly to the case of 2nd embodiment. As the discharge container for accommodating the liquid detergent for bathroom of the present embodiment, a spray container is preferable from the viewpoint of excellent applicability to the cleaning object, and the liquid detergent for bathroom is poured into a spray container selected from among the various containers exemplified in the first embodiment. It is desirable to accept

As described above, according to the liquid detergent for bathroom of the present embodiment, the components (A) to (C) are contained, the content of the component (a1) and the component (a2) is within a specific range, and the component (C) / ( a1) The mass ratio of the component is in a specific range, the mass ratio of (C) component/(a2) component is in a specific range, and the pH at 25°C is in a specific range. Therefore, the cleaning power is higher, the rinseability is also excellent, and the low-temperature stability is also excellent.

[Modification of the third embodiment]

In the present embodiment, even when the liquid detergent for bathroom is a composition containing the following components (A) to (C), in addition to the above excellent cleaning power and rinseability, the liquid detergent for bathroom has excellent low-temperature stability can be obtained.

Component (A): a surfactant containing a non-soap anionic surfactant (a1) and a nonionic surfactant (a2);

(B) component: a glycol-based solvent;

Component (C): containing an aminocarboxylic acid type chelating agent,

(a1) The content of the component is 0.1 to 5.0% by mass,

(C) The mass ratio represented by component/(a1) component is 0.6 to 6.0,

(C) The mass ratio represented by component/(a2) component is 0.4 to 2.0,

Moreover, the liquid detergent for bathroom characterized by the pH at 25 degreeC exceeding 10 and being less than 12.

That is, the bathroom liquid detergent of the present embodiment, as in the first embodiment, even when the mass ratio represented by [component (C) / component (A)] does not satisfy the range of 0.6 to 6.0, the above (A) to ( C) has sufficient detergency and rinseability by satisfying the composition of the component and the mass ratio represented by [component (C) / component (a1)] and the mass ratio represented by [component (C) / component (a2)], Furthermore, it is possible to obtain a liquid detergent for bathroom sufficiently equipped with low-temperature stability.

Example

The present invention will be described in more detail below using Examples, but the present invention is not limited to these Examples. In this Example, "%" represents "mass %" unless otherwise specified.

<<Example 1>>

Each condition, procedure, and result of the first experimental example are described below.

In the 1st experimental example, about the liquid bathroom detergent (liquid bathroom detergent of 1st Embodiment) by Claim 1 of this invention, the bathroom liquid detergent of the Example and the comparative example was produced and evaluated, respectively.

The composition of the bathroom liquid detergent of each Example in a 1st experimental example and a comparative example was shown to following Table 1 - Table 6.

The raw materials used in this experimental example are as follows.

<Component (A)>

[component (a1), non-soap anionic surfactant]

a1-1: AOS, sodium C14-α olefin sulfonate, manufactured by LION CORPORATION, trade name "LIPOLAN LJ441". In addition, "C" of the said "C14" means carbon number, and the same applies below.

a1-2: LAS, long-chain alkyl (C10-16) sodium alkylbenzenesulfonate, manufactured by LION CORPORATION, trade name "LIPON PS-230".

a1-3: AES, polyoxyethylene alkyl (C12-14) ether sulfate [average added mole number of ethylene oxide 2]. New JAPAN CHEMICAL CO., LTD., trade name SINOLIN SPE-1250.

a1-4: MES, C16-18 α sulfofatty acid methyl ester salt, manufactured by LION CORPORATION, trade name “MIZULAN FL-80”.

a1-5: SDS, lauryl sulfate, manufactured by LION CORPORATION, trade name "SANNOL LM-1130".

[component (a2), nonionic surfactant]

a2-1: Alkylamine oxide (AX), manufactured by LION SPECIALTY CHEMICALS CO., LTD., trade name "CADENAX DM12D-W(C)".

a2-2: polyoxyethylene alkyl ether (AE), C ₁₃ H ₂₇ O (CH ₂ CH ₂ O) ₇ H (average ethylene oxide adduct of 7 moles of branched C13 alcohol), manufactured by BASF, LTD., trade name 「Lutensol TO-7」.

a2-3: Alkyl polyglycoside, manufactured by BASF JAPAN, LTD., trade name "Glucopon 215 UP".

a2-4: Polyoxyethylene nonylphenyl ether (average ethylene oxide 8 mol adduct of nonylphenol), manufactured by LION CORPORATION, trade name "LAOL XA-60-50".

a2-5: glyceryl ether (CH ₃ (CH ₂ ) ₅ OCH ₂ CH(OH)CH ₂ OH), synthetic product (n-hexanol and 1-chloro-2,3-epoxypropane in the presence of a Lewis acid catalyst, prepared by condensation by an etherification reaction and ring-opening an epoxy ring by hydrolysis).

[component (a3), optional surfactant]

a3-1: C10-18 fatty acid potassium, manufactured by LION CORPORATION, trade name "coconut fatty acid potassium 30% aqueous solution".

a3-2: Fatty acid amide propyl betaine, manufactured by LION CORPORATION, trade name "ENAGICOL L-30B".

<Component (B)>

B-1: Diethylene glycol monobutyl ether, manufactured by NIPPON NYUKAZAI CO., LTD., trade name "butyldiglycol".

B-2: Diethylene glycol monobenzyl ether, manufactured by NIPPON NYUKAZAI CO., LTD., trade name "phenyldiglycol".

B-3: Ethylene glycol monophenyl ether, manufactured by NIPPON NYUKAZAI CO., LTD., trade name "phenyl glycol".

B-4: Propylene glycol monopropyl ether, manufactured by NIPPON NYUKAZAI CO., LTD., trade name "propyl propylene glycol".

B-5: Ethylene glycol monohexyl ether, manufactured by NIPPON NYUKAZAI CO., LTD., trade name "hexyl glycol".

B-6: Diethylene glycol monoethyl ether, manufactured by THE DOW CHEMICAL COMPANY JAPAN.

B-7: (CH ₃ ) ₂ CH-O-(C ₂ H ₄ O)-(C ₃ H ₆ O)-H, synthetic product (adding 1 mol of propylene oxide and 1 mol of ethylene oxide to i-propanol) manufactured by).

B-8: Dipropylene glycol monomethyl ether, manufactured by NIPPON NYUKAZAI CO., LTD., trade name "methyl propylene diglycol".

B-9: C ₄ H ₉ -O-(C ₂ H ₄ O) ₂ -(C ₃ H ₆ O) ₂ -H, manufactured by SANYO CHEMICAL INDUSTRIES, LTD., NEWPOL 50HB-55.

<Component (C)>

C-1: Ethylenediaminetetraacetic acid disodium (EDTA2Na), AKZO NOBEL N.V. product, brand name "DISSOLVINE NA2".

C-2: Hydroxyethylenediamine triacetic acid, CHELEST CORPORATION, brand name "HEDTA".

C-3: Dihydroxyethyl glycine, CHELEST CORPORATION, brand name "DHEG".

C-4: Hydroxyethylene iminodiacetic acid, CHELEST CORPORATION, brand name "HIDA".

C-5: Diethylenetriamine pentaacetic acid, CHELEST CORPORATION, brand name "DTPA".

<Other ingredients>

pH adjuster: 1N sodium hydroxide, 1N hydrochloric acid (manufactured by KANTO CHEMICAL CO., INC.).

<Examples 1-1 to 1-35, Comparative Examples 1-1 to 1-19>

After adding and mixing the components (A) to (C) to water according to the composition shown in Tables 1 to 6 below, the pH was adjusted to the value in the table with a pH adjuster, and the liquid detergent for bathroom in each case was obtained.

The composition (mixing component, content (mass %)) of the liquid detergent for bathroom of each obtained case is shown to following Table 1 - Table 6. In addition, unless otherwise indicated, mass % represents pure content.

In the table below, when there is a blank ingredient, that ingredient is not blended.

In the following table|surface, content "suitable amount" of a pH adjuster is quantity required when making the pH of the liquid detergent for bathrooms of each case into the value in a following table|surface.

In the following table|surface, content "balance" of water means the balance added so that the compounding quantity (mass %) of the sum total of all compounding components contained in the liquid detergent for bathrooms may become 100 mass %.

<Evaluation method of liquid detergent for bathroom>

About the liquid detergent for bathroom of each case, the cleaning power and rinse property were evaluated by the following method.

The evaluation results are shown in Tables 1 to 6 below.

[Evaluation of detergency]

After fixing a test piece (2 cm × 10 cm) made of glass fiber reinforced plastic (FRP) on the inner wall of a commercially available bathtub in a general household, 3 adult males bathed 3 times each (1 bath 3 times per day). This was repeated for days, in which time only the bath water was replaced, and the bathtub was used without washing) to allow contamination to adhere to the test piece.

After sufficiently drying the soiled test piece, the liquid detergent for bathroom in each case was dripped onto the test piece so that the entire surface was wet, left to stand for 30 seconds, and then rinsed with tap water (15°C). Then, the test pieces were sufficiently dried, and the state of contamination removal on the surfaces of the five test pieces was evaluated by visual observation and finger touch according to the following detergency evaluation criteria. In the following evaluation criteria, (double-circle) and (circle) were set as the pass.

[Evaluation criteria for detergency]

◎: Decontamination was very good [out of 5 test pieces, no contamination was observed with the naked eye in all 5 pieces, and a smooth finger feel was obtained on the entire surface of the test piece in all 5 pieces].

○: Decontamination is good [out of 5 test pieces, at least 1 piece is not visually observed, and a smooth finger feel is obtained on the entire surface of the test piece, and at least 1 out of 5 test pieces feel rough finger touch on the tying test piece].

△: Almost no contamination was removed [out of the 5 test pieces, contamination was observed by the naked eye on all 5 pieces, and rough finger touch was felt on all 5 pieces, but the contamination by the naked eye and rough finger touch were It is reduced compared to before cleaning].

×: Contamination is not removed at all [Out of the 5 test pieces, contamination by the naked eye is observed on all 5 pieces, and rough finger touch is felt on all 5 pieces, and the contamination by the naked eye and rough finger touch are No change from before cleaning].

These evaluation results are shown in the column of cleaning power (30 seconds) in Tables 1 to 6 below.

In addition, in the evaluation of the cleaning power, the cleaning power was evaluated in the same manner as described above by changing the standing time after dropping the liquid bathroom detergent onto the test piece from 30 seconds to 60 seconds and 120 seconds.

These evaluation results are shown in the columns of cleaning power (60 seconds) and cleaning power (120 seconds) in Tables 1 to 6 below, respectively.

[Evaluation of rinseability]

After spraying and adhering 40 g of the liquid bath detergent in each case to the entire surface in the bathtub, rinsing with tap water using a shower (water temperature 15 ° C, flow rate 0.2 L / sec), foam is completely removed from the drain port of the bathtub. The time until washing was measured, and the rinse property of the bathroom liquid detergent was evaluated according to the following evaluation criteria. In the following evaluation criteria, (double-circle) and (circle) were set as the pass.

[Evaluation criteria for rinseability]

◎: Less than 40 seconds

○: 40 seconds or more and less than 50 seconds

△: 50 seconds or more and less than 60 seconds

×: 60 seconds or more

These evaluation results are shown in the column of rinseability (15°C) in Tables 1 to 6 below.

In addition, in the evaluation of the rinse property, the water temperature at the time of rinsing with tap water using a shower was changed from 15 ° C. to 40 ° C., and the rinse property was evaluated in the same manner as above. did.

These evaluation results are shown in the column of rinseability (40°C) in Tables 1 to 6 below.

From the results shown in Tables 1 to 6, it was confirmed that the bathroom liquid detergents of Examples 1-1 to 1-35 to which the present invention was applied had excellent detergency and also had good rinseability.

On the other hand, liquid detergents for bathrooms (Comparative Examples 1-1, 1-2, 1-8) whose C/A ratio does not satisfy the scope of the present invention, which do not contain at least one of the components (A) to (C) The liquid detergent for bathroom (Comparative Examples 1-6, 1-7, 1-10, 1-11, 1-13, 1-16 to 1-19) was not able to obtain sufficient cleaning power. Moreover, the liquid detergent for bathrooms in which content of (A) component exceeds the upper limit of this invention (Comparative Examples 1-8, 1-9, 1-12) was not obtained sufficient rinse property. In addition, liquid detergents for bathrooms (Comparative Examples 1-3 to 1-5, 1-13 to 1-15, and 1-17 to 1-19) whose pH value does not satisfy the range of the present invention did not obtain sufficient cleaning power. or insufficient rinsing property was not obtained.

From the above results, it was confirmed that the liquid detergent for bathroom to which the present invention was applied was excellent in cleaning power and also had good rinsing property.

<<Second Experimental Example>>

Each condition, procedure, and result of the second experimental example are described below.

In the 2nd experimental example, about the liquid bathroom detergent (liquid bathroom detergent of 2nd embodiment) by Claim 2 of this invention, the bathroom liquid detergent of the Example, the comparative example, and the reference example was produced and evaluated, respectively.

The composition of the bathroom liquid detergent of each Example in a 2nd experimental example, a comparative example, and a reference example was shown to following Table 7 - Table 9.

The raw materials used in this experimental example are as follows.

<Component (A)>

[component (a1), non-soap anionic surfactant]

a1-1: AOS, sodium C14-α olefin sulfonate, manufactured by LION CORPORATION, trade name "LIPOLAN LJ441".

a1-2: LAS, long-chain alkyl (C10-16) sodium benzenesulfonate, manufactured by LION CORPORATION, trade name "LIPON PS-230".

[component (a2), nonionic surfactant]

a2-2: Polyoxyethylene alkyl (C13, branched 100%) ether [average number of added moles of ethylene oxide: 7], manufactured by BASF, LTD., trade name "Lutensol TO-7". In addition, "C" of the said "C13" means carbon number of an alkyl group (hydrocarbon group), and the same applies below.

a2-6: Polyoxyethylene mono(2-propylheptyl) ether [average added mole number of ethylene oxide: 8], manufactured by BASF, LTD., trade name "Lutensol XP80".

a2-7: Polyoxyethylene mono(2-propylheptyl) ether [average added mole number of ethylene oxide: 10], manufactured by BASF, LTD., trade name "Lutensol XP100".

a2-8: Polyoxyethylene alkyl (C12-14, linear 100%) ether [average number of added moles of ethylene oxide: 15], manufactured by LION CORPORATION, trade name "LMAO-90".

<Component (B)>

B-1: Diethylene glycol monobutyl ether, manufactured by NIPPON NYUKAZAI CO., LTD., trade name "butyldiglycol".

<Component (C)>

C-1: Ethylenediaminetetraacetic acid disodium (EDTA2Na), AKZO NOBEL N.V. product, brand name "DISSOLVINE NA2".

<Component (D)>

D-1: xanthan gum, manufactured by SANSHO CO., LTD., trade name "KELZAN".

D-2: gellan gum, made by DSP GOKYO FOOD & CHEMICAL CO., LTD., trade name "KELCOGEL".

D-3: Carrageenan, manufactured by SAN-EI GEN F.F.I., INC., trade name "CARRAGEENIN CS-558".

D-4: Guar gum, manufactured by SANSHO CO., LTD., trade name "GRINDSTED GUAR175".

D-5: Carboxymethyl cellulose, manufactured by LION CORPORATION, trade name "LEOGARD GP".

D-6: Cationic cellulose, manufactured by LION CORPORATION, trade name "XE-511K".

D-7: Polyvinyl alcohol, manufactured by KURARAY CO., LTD., trade name "KURARAY POVAL PVA-217".

D-8: Polyethylene glycol, manufactured by LION CORPORATION, trade name "PEG #1000".

<Other ingredients>

pH adjuster: 1N sodium hydroxide, 1N hydrochloric acid (manufactured by KANTO CHEMICAL CO., INC.).

<Examples 2-1 to 2-11, 2-14 to 2-17, 2-19, 2-20, Comparative Examples 2-1 to 2-7, Reference Examples 2-12, 2-13, 2-18 >

After adding and mixing the components (A) to (D) to water according to the composition shown in Tables 7 to 9 below, the pH was adjusted to the value in the table with a pH adjuster, and the liquid detergent for bathroom in each case was obtained.

The composition (mixing component, content (mass %)) of the liquid detergent for bathroom of each obtained case is shown to following Table 7 - Table 9. In addition, unless otherwise indicated, mass % represents pure content.

In the table below, when there is a blank ingredient, that ingredient is not blended.

In the following table|surface, content "suitable amount" of a pH adjuster is quantity required when making the pH of the liquid detergent for bathrooms of each case into the value in a following table|surface.

In the following table|surface, content "balance" of water means the balance added so that the compounding quantity (mass %) of the sum total of all compounding components contained in the liquid detergent for bathrooms may become 100 mass %.

<Viscosity measurement method>

About the liquid detergent for bathroom of each case, the kinematic viscosity at the time of using a tubular viscometer and the viscosity at the time of using a B-type viscometer were measured by the following method.

[Kinematic viscosity measured with a custom tube viscometer]

The sample was adjusted to 25°C, and the kinematic viscosity was measured with a Canon-Pensky viscometer of an automatic kinematic viscosity measuring device (manufactured by TANAKA SCIENTIFIC, LTD.) as a tubular viscometer (based on JISZ8803 (2011: Viscosity Measurement Method Using a Custom Tube Viscometer)).

The measurement results are shown in Tables 7 to 9 below.

<Evaluation method of liquid detergent for bathroom>

About the liquid bathroom detergent of each case, the cleaning power in a vertical surface and the cleaning power in a horizontal surface were evaluated by the following method.

The evaluation results are shown in Tables 7 to 9 below.

[Evaluation of detergency in vertical plane]

After fixing a test piece (10 cm × 10 cm) made of glass fiber reinforced plastic (FRP) on the inner wall of a commercially available bathtub in a general household, three adult males bathe each three times (one bath per day for three times). This was repeated for 10 days, and only the bath water was replaced during that time, and the bathtub was used without washing) to allow stains to adhere to the surface of the test piece at 10 locations.

After sufficiently drying the soil-adhered test piece, the bathroom detergent of each example was applied in a straight line to the top of the test piece, tilted at 90° and left for 1 minute, then rinsed with tap water (15°C). Then, the test piece was sufficiently dried, and the state of removal of dirt on the surface of the test piece was evaluated by visual observation and finger touch according to the following detergency evaluation criteria. In the following evaluation criteria, (double-circle) and (circle) were set as the pass. In addition, as 10 test piece surface locations, 10 locations located at substantially equal intervals on the entire surface of the test piece were selected.

[Evaluation criteria for detergency]

◎: Decontamination is very good [the cleaning agent spreads unevenly over the entire surface of the test piece, no visual contamination was observed at 8 or more out of 10 test piece surfaces, and the entire surface of the test piece was smooth at 8 or more places Finger touch is obtained].

○: Decontamination is good [the detergent is spread over almost the entire surface of the test piece, and contamination by the naked eye is not observed at 5 or more out of 10 places on the surface of the test piece, and a smooth finger feel is obtained over the entire surface of the test piece. , at least 3 out of 10 test piece surfaces felt a rough finger touch on the test piece].

△: Almost no contamination [the detergent is spread on about half of the surface of the test piece, and contamination by the naked eye is observed at 6 or more out of 10 places on the surface of the test piece, and a rough finger touch is felt, but the above-mentioned Contamination by and rough finger feel are reduced compared to before washing].

×: Contamination is not removed at all [the cleaning agent is not uniformly spread on the surface of the test piece, so contamination by the naked eye is observed in all 10 of the 10 test piece surfaces on the test piece surface, and a rough finger touch is felt, Contamination by the naked eye and rough finger feel are unchanged from before washing]

These evaluation results are shown in the column of detergency in the vertical plane of Tables 7 to 9 below.

In addition, the number of places where decontamination was confirmed among 10 test piece surfaces is shown in the columns of decontamination sites in Tables 7 to 9 below.

[Evaluation of cleaning power on a horizontal surface]

After fixing a test piece (2 cm × 10 cm) made of glass fiber reinforced plastic (FRP) on the inner wall of a commercially available bathtub in a general household, three adult males bathe each three times (one bath per day for three times). This was repeated for days, in which time only the bath water was replaced, and the bathtub was used without washing) to allow contamination to adhere to the test piece.

After sufficiently drying the test piece to which this contamination had adhered, this test piece was placed horizontally. After that, the liquid detergent for bathroom in each case was dripped onto this test piece so that the entire surface thereof was wet, and after leaving it to stand for 5 minutes, it was rinsed with tap water (15°C). Then, the test pieces were sufficiently dried, and the state of contamination removal on the surfaces of the five test pieces was evaluated by visual observation and finger touch according to the following detergency evaluation criteria. In the following evaluation criteria, (double-circle) and (circle) were set as the pass.

[Evaluation criteria for detergency]

◎: Decontamination was very good [out of 5 test pieces, no contamination was observed with the naked eye in all 5 pieces, and a smooth finger feel was obtained on the entire surface of the test piece in all 5 pieces].

○: Decontamination is good [out of 5 test pieces, at least 1 piece is not visually observed, and a smooth finger feel is obtained on the entire surface of the test piece, and at least 1 out of 5 test pieces feel rough finger touch on the tying test piece].

△: Almost no contamination was removed [out of the 5 test pieces, contamination was observed by the naked eye on 3 pieces, and rough finger touch was felt on all 3 pieces, but the contamination by the naked eye and rough finger touch were It is reduced compared to before cleaning].

×: Contamination is not removed at all [Out of the 5 test pieces, contamination by the naked eye is observed on all 5 pieces, and rough finger touch is felt on all 5 pieces, and the contamination by the naked eye and rough finger touch are No change from before cleaning].

These evaluation results are shown in the column of cleaning power (5 minutes) on a horizontal surface in Tables 7 to 9 below.

In addition, in the evaluation of the cleaning power on the horizontal surface, the standing time after dropping the liquid detergent for bathroom on the test piece was changed from 5 minutes to 10 minutes, and the cleaning power was evaluated in the same manner as above.

These evaluation results are shown in the column of cleaning power (10 minutes) on a horizontal surface in Tables 7 to 9 below.

From the results shown in Tables 7 to 9, the bathroom liquid detergents of Examples 2-1 to 2-11, 2-14 to 2-17, 2-19, and 2-20 to which the configuration according to claim 2 of the present invention was applied It was confirmed that the cleaning power on the vertical surface was excellent, and the cleaning power on the horizontal surface was also good. The reason for the excellent detergency on the vertical surface is presumed to be that the detergent exhibits detergency on the vertical surface by spreading unevenly without dripping even on the vertical surface because the detergent has excellent adhesion retention and diffusivity.

On the other hand, in the bathroom liquid detergent (Comparative Example 2-1) not containing (D) component, sufficient detergency was not obtained on a vertical surface.

The liquid detergent for bathroom (Comparative Examples 2-2 and 2-3) whose kinematic viscosity does not satisfy the range of the present invention did not obtain sufficient cleaning power on a vertical surface.

(a1) Sufficient cleaning power was not obtained in the vertical surface in the bathroom liquid detergent (Comparative Example 2-4) which does not contain a component.

(D) In the bathroom liquid detergent (Comparative Example 2-5) which does not contain component and whose kinematic viscosity does not satisfy the range of this invention, sufficient cleaning power was not obtained in a vertical surface.

(C) In the bathroom liquid detergent (Comparative Example 2-6) containing no component, sufficient detergency was not obtained on a vertical surface and a horizontal surface.

(B) In the bathroom liquid detergent (Comparative Example 2-7) containing no component, sufficient detergency was not obtained on a vertical surface and a horizontal surface.

In addition, although the bathroom liquid detergents of Reference Examples 2-12, 2-13, and 2-18 do not satisfy a part of the regulations in claim 1 of the present invention, the structural requirements described in claim 2, namely, component (A) It further contains this nonionic surfactant (a2), further contains a water-soluble polymer as component (D), and satisfies the rule that the kinematic viscosity is 1.5 to 20 mm 2 / s. This is a reference example from which it was confirmed that this was excellent and that the detergency on the horizontal surface was also good.

From the above results, it was confirmed that the bathroom liquid detergent to which the configuration according to claim 2 of the present invention was applied had excellent cleaning power even on the vertical surface of the bathtub.

<<Third experimental example>>

Each condition, procedure, and result of the third experimental example are described below.

In the 3rd experimental example, about the liquid bathroom cleaner (liquid bathroom cleaner of the 3rd embodiment) according to claim 4 of the present invention, the bathroom liquid cleaners of Examples, Comparative Examples, and Reference Examples were produced and evaluated.

The composition of the bathroom liquid detergent of each Example in a 3rd experimental example, a comparative example, and a reference example was shown to following Table 10 - Table 16.

The raw materials used in this experimental example are as follows.

<Component (A)>

[component (a1), non-soap anionic surfactant]

a1-1: AOS, sodium C14-α olefin sulfonate, manufactured by LION CORPORATION, trade name "LIPOLAN LJ441". In addition, "C" of the said "C14" means the number of carbon atoms of an alkyl group (hydrocarbon group), and the following is the same.

a1-2: LAS, long-chain alkyl (C10-16) sodium benzenesulfonate, manufactured by LION CORPORATION, trade name "LIPON PS-230".

a1-3: AES, polyoxyethylene alkyl (C12-14, linear 100%) ether sulfate [average added mole number of ethylene oxide 2]. Made by NEW JAPAN CHEMICAL CO., LTD. Brand name "SINOLIN SPE-1250".

a1-4: MES, C16-18 α sulfofatty acid methyl ester salt, manufactured by LION CORPORATION, trade name “MIZULAN FL-80”.

a1-5: SDS, lauryl sulfate, manufactured by LION CORPORATION, trade name "SANNOL LM-1130".

a1-6: AES, polyoxyethylene alkyl (C12-13, 80 mass % linear, 20 mass % branched) ether sulfate [average added mole number of ethylene oxide 2]. SHELL CHEMICALS NEODOL23 A synthetic product obtained by adding an average of 2 moles of ethylene oxide to alcohol by the conventional method and then sulfurizing it.

a1-7: Sodium polyoxyethylene dodecyl ether acetate [average number of added moles of ethylene oxide: 10], manufactured by KAO CORPORATION, trade name "KAOAKYPO RLM-100NV".

a1-8: Dialkyl (C8) sulfosuccinic acid, manufactured by KAO CORPORATION, trade name "PELEX OT-P".

a1-9: n-dodecyldimethylamine oxide, manufactured by KAO CORPORATION, trade name "AMPHITOL 20N".

a1-10: Sodium polyoxyethylene lauryl ether sulfate [average added mole number of ethylene oxide 3], manufactured by KAO CORPORATION, trade name "EMAL 20C".

[component (a2), nonionic surfactant]

a2-2: Polyoxyethylene alkyl (C13, branched 100%) ether [average number of added moles of ethylene oxide: 7], manufactured by BASF, LTD., trade name "Lutensol TO-7".

a2-6: Polyoxyethylene mono(2-propylheptyl) ether [average added mole number of ethylene oxide: 8], manufactured by BASF, LTD., trade name "Lutensol XP80".

a2-8: Polyoxyethylene alkyl (C12-14, linear 100%) ether [average number of added moles of ethylene oxide: 15], manufactured by LION CORPORATION, trade name "LMAO-90".

a2-9: Coconut oil fatty acid diethanolamide, manufactured by KAWAKEN FINE CHEMICALS CO., LTD., trade name "AMISOL CDE".

a2-10: Polyoxyethylene nonylphenyl ether [average added mole number of ethylene oxide 8], manufactured by LION CORPORATION, trade name "LIPONOX NC-80".

a2-11: A compound obtained by adding an average of 2 moles of ethylene oxide to 2-ethyl 1-hexanol, a synthetic product.

a2-12: Compound and synthetic product obtained by adding an average of 2 moles of ethylene oxide to isononyl alcohol.

a2-13: A compound obtained by adding an average of 1 mole of ethylene oxide to 2-ethyl 1-hexanol, a synthetic product.

a2-3: Alkyl (C8-10) polyglycoside, manufactured by BASF JAPAN, LTD., trade name "Glucopon 215 UP".

a2-14: Octyl glucoside, manufactured by AKZO NOBEL N.V., trade name "AG6202".

a2-15: Polyoxyethylene lauryl ether [average added mole number of ethylene oxide 15], manufactured by LION CORPORATION, trade name "LAO-90N".

[component (a3), optional surfactant]

a3-3: Betaine lauryl dimethylaminoacetic acid, manufactured by KAO CORPORATION, trade name "AMPHITOL 20B".

a3-4: Alkyl (C12) dimethylamine oxide, manufactured by LION SPECIALTY CHEMICALS CO., LTD., trade name "CADENAX DM12D-W(C)".

a3-5: Coconut fatty acid potassium, manufactured by LION CORPORATION, trade name "coconut fatty acid potassium 30% aqueous solution".

<Component (B)>

B-1: Diethylene glycol monobutyl ether, manufactured by NIPPON NYUKAZAI CO., LTD., trade name "butyldiglycol".

B-6: Diethylene glycol monoethyl ether, manufactured by THE DOW CHEMICAL COMPANY JAPAN.

B-10: dipropylene glycol dimethyl ether, THE DOW CHEMICAL COMPANY JAPAN, trade name "PROGLIDE DMM".

B-11: dipropylene glycol n-propyl ether, THE DOW CHEMICAL COMPANY JAPAN, trade name "DAWANOL DPnP".

B-12: Ethylene glycol, manufactured by MITSUBISHI CHEMICAL CORPORATION, trade name "ethylene glycol".

<Component (C)>

C-1: Ethylenediaminetetraacetic acid disodium (EDTA2Na), AKZO NOBEL N.V. product, brand name "DISSOLVINE NA2".

<Other ingredients>

pH adjuster: 1N sodium hydroxide, 1N hydrochloric acid (manufactured by KANTO CHEMICAL CO., INC.).

<Examples 3-1 to 3-4, 3-6, 3-9, 3-10, 3-18 to 3-31, 3-33, Comparative Examples 3-1 to 3-27, Reference Example 3-5 , 3-7, 3-8, 3-11~3-17, 3-32>

After adding and mixing the components (A) to (C) to water according to the composition shown in Tables 10 to 16 below, the pH was adjusted to the value in the table with a pH adjuster, and the liquid detergent for bathroom in each case was obtained.

The composition (mixing component, content (mass %)) of the liquid detergent for bathroom of each obtained case is shown to following Table 10 - Table 16. In addition, unless otherwise indicated, mass % represents pure content.

In the following table|surface, content "suitable amount" of a pH adjuster is quantity required when making the pH of the liquid detergent for bathrooms of each case into the value in a following table|surface.

In the table below, when there is a blank ingredient, that ingredient is not blended.

In the following table|surface, content "balance" of water means the balance added so that the compounding quantity (mass %) of the sum total of all compounding components contained in the liquid detergent for bathrooms may become 100 mass %.

<Evaluation method of liquid detergent for bathroom>

About the liquid bathroom detergent of each case, cleaning power, rinseability, and low-temperature stability were evaluated by the following method.

The evaluation results are shown in Tables 10 to 16 below.

[Evaluation of detergency]

After fixing a test piece (20 cm × 20 cm) made of glass fiber reinforced plastic (FRP) on the inner wall of a commercially available bathtub in a general household, three adult males bathe each three times (one bath per day for three times). This was repeated for days, in which time only the bath water was replaced, and the bathtub was used without washing) to allow contamination to adhere to the test piece.

After drying the test piece to which this contamination adhered sufficiently, the liquid bathroom detergent of each example was sprayed on the vertically installed test piece, left to stand for 30 seconds, and then rinsed with tap water (15°C). Then, the test piece was sufficiently dried, and the state of removal of stains on the surface of the test piece was evaluated visually and by finger touch according to the following evaluation criteria for detergency. In the following evaluation criteria, (double-circle) and (circle) were set as the pass. In addition, as 10 test piece surface locations, 10 locations located at substantially equal intervals on the entire surface of the test piece were selected.

[Evaluation criteria for detergency]

◎: Contamination removal was very good [Visual contamination was not observed at 8 or more out of 10 test piece surfaces, and a smooth finger feel was obtained].

○: Decontamination was good [out of 10 places on the surface of the test piece, no contamination was observed at 5 or more places with the naked eye, and a smooth finger feel was obtained].

△: Almost no contamination was removed [out of 10 places on the surface of the test piece, contamination by the naked eye was observed at 6 or more places, and a rough finger touch was felt, but the contamination by the naked eye and the rough finger touch were washed away. reduced than before].

×: Contamination is not removed at all [Out of 10 test piece surfaces, all 10 spots are visually contaminated and feel a rough finger feel, and the visual stain and rough finger feel are different from before washing doesn't exist].

These evaluation results are shown in the column of cleaning power (30 seconds) in Tables 10 to 16 below.

In addition, in the evaluation of the cleaning power, the cleaning power was evaluated in the same manner as described above while changing the standing time after dropping the liquid detergent for bathroom onto the test piece from 30 seconds to 60 seconds and 120 seconds.

These evaluation results are shown in the columns of cleaning power (60 seconds) and cleaning power (120 seconds) in Tables 10 to 16 below, respectively.

[Evaluation of rinseability]

After spraying and adhering 40 g of the liquid bath detergent in each case to the entire surface in the bathtub, rinsing with tap water using a shower (water temperature 15 ° C, flow rate 0.2 L / sec) When foam completely disappears from the drain port of the bathtub The time until was measured, and the rinse property of the liquid detergent for bathroom was evaluated according to the following evaluation criteria. In the following evaluation criteria, (double-circle) and (circle) were set as the pass.

[Evaluation criteria for rinseability]

◎: 40 seconds or less

○: More than 40 seconds and 50 seconds or less

△: More than 50 seconds and 60 seconds or less

×: more than 60 seconds

These evaluation results are shown in the column of rinseability (15°C) in Tables 10 to 16 below.

In addition, in the evaluation of the rinse property, the water temperature at the time of rinsing with tap water using a shower was changed from 15 ° C. to 40 ° C., and the rinse property was evaluated in the same manner as above. did.

These evaluation results are shown in the column of rinseability (40°C) in Tables 10 to 16 below.

[Evaluation of low temperature stability]

After mixing each component, the appearance of the composition left still at -5°C was visually checked after 2 weeks, 4 weeks, and 6 weeks, and low-temperature stability was evaluated according to the following criteria. In this evaluation, ○ was set as pass.

[Evaluation Criteria for Low Temperature Stability]

○: Phase separation or cloudiness did not occur.

x: Phase separation or cloudiness occurred.

These evaluation results are shown in the columns of low-temperature stability (2 weeks), low-temperature stability (4 weeks), and low-temperature stability (6 weeks) in Tables 10 to 16 below, respectively.

At the time of 4 weeks, the thing whose evaluation result was ○ was set as the comprehensive evaluation "○", and the thing whose evaluation result was × at the time of 4 weeks progressed as the comprehensive evaluation "x". These evaluation results are shown in the low-temperature stability (total) column of Tables 10 to 16 below.

From the results shown in Tables 10 to 16, Examples 3-1 to 3-4, 3-6, 3-9, 3-10, 3-18 to 3-31, 3 to which the configuration according to claim 4 of the present invention is applied It was confirmed that the liquid detergent for bathroom of -33 was excellent in cleaning power, good in rinsing property, and also excellent in low-temperature stability.

On the other hand, sufficient detergency was not obtained in the bathroom liquid detergent (Comparative Examples 3-1 and 3-2) in which the C/a1 ratio did not satisfy the range of the present invention.

Sufficient low-temperature stability was not obtained in the liquid detergent for bathrooms (Comparative Examples 3-3 and 3-4) in which the C/a2 ratio did not satisfy the scope of the present invention.

Sufficient cleaning power was not obtained in the liquid bathroom detergents (Comparative Examples 3-5 to 3-7) whose pH value does not satisfy the range of the present invention.

(a1) In the bathroom liquid detergent (Comparative Example 3-8) containing no component, sufficient detergency was not obtained, and sufficient low-temperature stability was not obtained either.

In the bathroom liquid detergent (Comparative Example 3-9) in which the content of the component (a1) does not satisfy the scope of the present invention, sufficient detergency was not obtained, and sufficient rinseability was not obtained either.

(a2) Sufficient low-temperature stability was not obtained in the bathroom liquid detergent (Comparative Example 3-10) which did not contain a component.

(B) In the bathroom liquid detergent containing no component (Comparative Example 3-11), sufficient low-temperature stability was not obtained, and sufficient detergency was not obtained either.

(C) Sufficient cleaning power was not obtained in the bathroom liquid detergent (Comparative Example 3-12) which did not contain component.

Sufficient cleaning power was not obtained in the liquid bathroom detergents (Comparative Examples 3-13 to 3-15) whose pH value does not satisfy the range of the present invention.

Sufficient low-temperature stability was not obtained in the liquid detergent for bathrooms (Comparative Examples 3-16 to 3-21) in which the C/a2 ratio did not satisfy the scope of the present invention.

In the bathroom liquid detergents (Comparative Examples 3-22 to 3-27) whose pH value does not satisfy the range of the present invention, sufficient detergency was not obtained, sufficient rinseability was not obtained, or sufficient low-temperature stability was not obtained.

In addition, although the bathroom liquid detergents of Reference Examples 3-5, 3-7, 3-8, 3-11 to 3-17 and 3-32 do not satisfy a part of the regulations in claim 1 of the present invention, The constitutional requirements described in claim 4, namely, component (A) further includes a nonionic surfactant (a2), and the mass ratio of (C)/(a1) is 0.6 to 6.0, and the mass ratio of (C)/(a2) is Since it satisfies the rule of 0.4 to 2.0, it is a reference example that was confirmed to have excellent detergency, good rinseability, and excellent low-temperature stability as in each example.

From the above results, it was confirmed that the liquid detergent for bathroom to which the present invention was applied had more excellent detergency, excellent rinseability, and excellent low-temperature stability.

Claims (8)

Component (A): 0.1 to 5.0% by mass of a surfactant containing a non-soap anionic surfactant (a1);
Component (B): at least one selected from the group consisting of diethylene glycol monobutyl ether, diethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, and propylene glycol monopropyl ether;
Component (C): containing an aminocarboxylic acid type chelating agent,
The mass ratio represented by the component (C)/component (A) is 0.6 to 6.0, and the pH at 25°C exceeds 10 and is less than 12. Liquid detergent for bathroom, characterized in that: According to claim 1,
A liquid bathroom detergent characterized in that the non-soap anionic surfactant (a1) of the component (A) is an α-olefin sulfonate having 10 to 20 carbon atoms. According to claim 1,
The liquid detergent for bathroom, characterized in that the component (B) is at least one selected from the group consisting of diethylene glycol monobutyl ether, diethylene glycol monobenzyl ether and propylene glycol monopropyl ether. According to any one of claims 1 to 3,
The component (A) is a surfactant further comprising a nonionic surfactant (a2), and
(D) component: contains a water-soluble polymer,
A liquid detergent for bathroom, characterized in that the kinematic viscosity measured by a tubular viscometer at 25 ° C is 1.5 to 20 mm / s. According to claim 4,
The liquid detergent for bathroom, characterized in that the component (D) is a polysaccharide. According to claim 1,
The component (A) is a surfactant further comprising a nonionic surfactant (a2),
(C) The mass ratio represented by component/(a1) component is 0.6 to 6.0,
The mass ratio represented by component (C)/component (a2) is 0.4 to 2.0, characterized in that the bathroom liquid detergent. According to claim 6,
The mass ratio represented by (a2) component/(A) component is 0.30 or more, The bathroom liquid detergent characterized by the above-mentioned. According to claim 6 or 7,
The mass ratio represented by component (B)/component (C) is 0.01 to 4.0, a bathroom liquid detergent characterized by the above.