JP2013199569A - Liquid detergent for bathroom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent for a bathroom that can restrain scum dirt from resticking to the inside of a drain hole, a drain line, etc. by having a reprecipitation restraining effect of scum dirt in a rinsing process and excellent foam breaking properties in addition to excelling in scum dirt cleaning power.SOLUTION: A liquid detergent for a bathroom includes a compound (a) expressed by general formula (1), and a sequestering agent (b). In the formula, x and y are each an integer of 1-7 and x+y=8, PO is oxypropylene, EO is oxyethylene, p is the average number of cycles of PO, q is the average number of cycles of EO, p+q is 1-10, and Mis one of alkali metal, alkali earth metal, ammonium and alkanolamine.

Description

  The present invention relates to a liquid cleaning agent for bathrooms.

  With the recent unitization and systemization of bathrooms, plastics are widely used not only in bathtubs and bathroom walls and floors, but also in drain outlets and drainage channels. However, since the surface of the plastic is hydrophobic, oily dirt such as sebum and scum dirt such as water-insoluble fatty acid calcium in which fatty acid contained in soap and calcium in tap water are bonded to the surface. It's easy to do. Therefore, measures such as hydrophilizing plastic surfaces such as bathtubs, bathroom walls and floors, basins, etc., and devising these shapes are taken in order to suppress such scum contamination. It has become like this. However, since such measures are not often taken on the surfaces of drain outlets and drain paths, there are still many problems of scum contamination adhering to these surfaces.

  On the other hand, as a detergent for cleaning scum dirt, for example, as described in Patent Documents 1 and 2, a composition in which a sequestering agent is combined with a surfactant or a solvent is known. According to this type of detergent, by the action of a sequestering agent, a water-insoluble substance such as fatty acid calcium, which is the main component of scum dirt, is changed to a water-soluble substance such as a fatty acid alkali metal salt, and the surfactant is dispersed. It is thought that the cleaning effect with respect to scum dirt is exhibited by making an agent and a solvent act.

JP 11-335700 A JP 2001-187895 A

However, by using such a detergent, even if the scum dirt adhering to the object to be cleaned such as a wash basin or a bathroom floor can be cleaned well once, a problem easily occurs in the subsequent rinsing process.
That is, when tap water is applied to these objects to be cleaned in the rinsing step and the detergent is diluted, water-soluble substances such as fatty acid alkali metal salts generated by the action of the metal ion sequestering agent are again caused by calcium ions in tap water. It easily returns to water-insoluble substances such as fatty acid calcium and precipitates. In addition, the water-insoluble substance thus precipitated again has a problem that it re-adheres to the inside of the drain outlet or the drainage path as scum dirt.
Thus, the scum dirt reattached to the drain outlet and the drainage path becomes chronic dirt, which not only lowers the drainage efficiency, but also becomes a hotbed of microorganisms and causes odor generation.

Further, such re-adhesion of scum dirt tends to become more prominent when the drainage generated in the rinsing process is foamed.
That is, when the drainage liquid is foamed, water-insoluble substances such as fatty acid calcium precipitated again, dirt removed by a physical force with a brush or a sponge, etc. are easily entangled with the foam and stay in the drain outlet or the drainage path. As a result, scum dirt is likely to be reattached.
Therefore, from the viewpoint of suppressing re-adhesion of scum stains, bathroom detergents are also required to exhibit good foam breaking properties such that bubbles disappear quickly when diluted with tap water in the rinsing step.

  The present invention has been made in view of the above circumstances, and not only has excellent scum dirt detergency, but also has a scum dirt reprecipitation inhibitory effect and excellent foam breakability in the rinsing step, thereby allowing the inside of a drain outlet and drainage. It is an object of the present invention to provide a liquid cleaning agent for bathrooms that can suppress the reattachment of scum dirt to a route or the like.

  As a result of intensive studies, the present inventors have found that the combination of a specific anionic surfactant having a branched alkyl group (compound (a)) and a sequestering agent (b) improves the detergency of scum stains. It has been found that the present invention can provide a liquid cleaning agent for bathrooms that is not only excellent but also has an effect of suppressing reprecipitation of scum dirt in the rinsing process and excellent foam breaking property, thereby suppressing reattachment of scum dirt. Completed. That is, the bathroom liquid cleaning agent of the present invention has a metal ion sequestering agent (b) containing scum dirt as a water-soluble substance, and also includes a compound (a) excellent in the action of taking up scum dirt. Therefore, even if tap water is added in the rinsing process, it is difficult to reprecipitate scum dirt. Furthermore, the liquid detergent for bathrooms of the present invention breaks bubbles quickly when diluted in the rinsing step. For this reason, even if scum dirt re-deposits, it does not get entangled with foam and stays in the drain outlet or the drainage path, and scum dirt re-adhesion can be highly suppressed.

［式（１）中、ｘとｙはそれぞれ１〜７の整数であり、ｘ＋ｙ＝８である。ＰＯはオキシプロピレン基、ＥＯはオキシエチレン基を表す。ｐはＰＯの平均繰返し数、ｑはＥＯの平均繰返し数を表し、ｐ＋ｑは１〜１０である。Ｍ^１はアルカリ金属、アルカリ土類金属、アンモニウムおよびアルカノールアミンのいずれかである。］
（ａ）／（ｂ）で表される質量比は、０．６〜１．７であることが好ましい。
本発明の浴室用液体洗浄剤は、亜鉛（ｃ）をさらに含有することが好ましい。 The liquid detergent for bathrooms of the present invention is characterized by containing a compound (a) represented by the following general formula (1) and a sequestering agent (b).

[In the formula (1), x and y are each an integer of 1 to 7, and x + y = 8. PO represents an oxypropylene group, and EO represents an oxyethylene group. p represents the average number of repetitions of PO, q represents the average number of repetitions of EO, and p + q is 1 to 10. M ¹ is any ^one of alkali metal, alkaline earth metal, ammonium and alkanolamine. ]
The mass ratio represented by (a) / (b) is preferably 0.6 to 1.7.
The bathroom liquid cleaning agent of the present invention preferably further contains zinc (c).

  According to the bathroom liquid cleaning agent of the present invention, not only is it excellent in scum dirt cleaning power, but also has an effect of suppressing scum dirt re-precipitation in the rinsing step and excellent foam breaking property, thereby allowing the inside of a drain outlet and a drain path to be provided. It is possible to suppress the reattachment of scum dirt to the etc.

The bathroom liquid cleaning agent of the present invention (hereinafter sometimes simply referred to as a liquid cleaning agent) contains the compound (a) represented by the general formula (1) and the sequestering agent (b).
Hereinafter, these components may be referred to as component (a) and component (b), respectively.
In addition, the bathroom to be cleaned by the liquid cleaning agent of the present invention includes a bathtub, a wall / floor / ceiling in the bathroom, a bathroom door, a mirror provided in the bathroom, a faucet, a shower, a drain, a drainage path ( Drainage pipes, etc.), etc., which have a hard surface such as plastic, metal, ceramics.

<Compound (a)>
The component (a) is an anionic surfactant represented by the formula (1) having a branched alkyl group. By combining such a component (a) with a component (b) described later, a liquid detergent having excellent scum dirt cleaning power can be obtained. In addition, this liquid cleaning agent has the effect of suppressing the reprecipitation of scum dirt in the rinsing process and the excellent foam breaking property, and therefore, the effect of suppressing the reattachment of the scum dirt to the drain outlet or the drainage path (scum dirt) Reattachment inhibiting effect) is obtained.

［式（１）中、ｘとｙはそれぞれ１〜７の整数であり、ｘ＋ｙ＝８である。ＰＯはオキシプロピレン基、ＥＯはオキシエチレン基を表す。ｐはＰＯの平均繰返し数、ｑはＥＯの平均繰返し数を表し、ｐ＋ｑは１〜１０である。Ｍ^１はアルカリ金属、アルカリ土類金属、アンモニウムおよびアルカノールアミンのいずれかである。］

[In the formula (1), x and y are each an integer of 1 to 7, and x + y = 8. PO represents an oxypropylene group, and EO represents an oxyethylene group. p represents the average number of repetitions of PO, q represents the average number of repetitions of EO, and p + q is 1 to 10. M ¹ is any ^one of alkali metal, alkaline earth metal, ammonium and alkanolamine. ]

In formula (1), x and y are each an integer of 1 to 7, and x + y = 8. Since x + y = 8, the liquid cleaning agent not only has excellent scum dirt detergency, but also has a scum dirt re-precipitation suppression effect and excellent foam breaking property in the rinsing process, and a scum dirt re-adhesion suppression effect. Demonstrate.
_{Examples of} C _x H _{2x + 1} and C _y H _{2y + 1} include a linear alkyl group or a branched alkyl group, respectively, and are excellent in detergency against scum dirt and a scum dirt reattachment suppressing effect. In the form of alkyl. Among them, C _x H _{2x + 1} and C _y H _{2y + 1} are particularly preferably a combination of a propyl group and a pentyl group (one of x and y is 3 and the other is 5).

In the formula (1), PO represents an oxypropylene group, EO represents an oxyethylene group, p represents the average number of repetitions of PO, and q represents the average number of repetitions of EO.
p + q is 1 to 10, preferably 1 to 5, and particularly preferably 3 to 4. When p + q is in the above range, the liquid detergent containing the component (a) not only has excellent scum dirt cleaning power, but also has a scum dirt re-precipitation inhibitory effect and excellent foam breaking property in the rinsing process. , Scum dirt re-adhesion suppression effect is demonstrated.
q is preferably from 1 to 10, and more preferably from 1 to 5. p is preferably from 0 to 9, and more preferably from 0 to 4.

When PO and EO are mixed, the arrangement state of PO and EO is not particularly limited, and may be mixed in a random manner or in a block shape.
Note that p and q indicate the “average” number of repetitions of PO and EO, respectively. That is, the compound represented by the formula (1) is an aggregate of molecules (including molecules having no PO or EO) having different numbers of repetitions of PO and EO. Further, it may be an assembly of molecules having different combinations of C _x H _{2x + 1} and C _y H _{2y + 1} .

In Formula (1), M ¹ is any ^one of an alkali metal, an alkaline earth metal, ammonium, and an alkanolamine, and (C _x H _{2x + 1} ) (C _y H _{2y + 1} ) CH—CH ₂ O— (PO) p _{- (EO) q-SO 3} - with as long as it can form a water-soluble salt.
Examples of the alkali metal include sodium and potassium. Examples of the alkaline earth metal include calcium and magnesium. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine.

(A) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
The component (a) is preferably a sulfate of an alkylene oxide adduct of an alcohol having a branched structure at the β-position obtained by bimolecular condensation by a gerbet reaction.
As the component (a), an alkylene oxide adduct of gerbet alcohol is mixed with, for example, liquid sulfuric anhydride or SO ₃ using a tank type reaction method, a film type reaction method, a tube type gas-liquid mixed phase reaction method, or the like. It can be produced by sulfating by contact with a gas or the like and then neutralizing with an alkali metal compound, an alkaline earth metal compound, ammonium or alkanolamine or the like.

  Specific examples of gerbet alcohol alkylene oxide adducts include BASF's Rutensol XP30 (average addition moles of ethylene oxide 3), Rutensol XP40 (average addition moles of ethylene oxide 4), Rutensol XL40 (average addition of propylene oxide) The number of moles is 1, and the average number of moles of ethylene oxide added is 3) (above, trade name).

The content of the component (a) in the liquid detergent is preferably 1 to 10% by mass, more preferably 3 to 7% by mass.
When the blending amount of component (a) is equal to or greater than the lower limit, the liquid cleaning agent can sufficiently take in scum dirt, and the scum dirt cleaning power is more excellent. Further, even in the rinsing step, the scum dirt is sufficiently retained, and the effect of suppressing the reprecipitation of the scum dirt becomes better. When the amount of the component (a) is not more than the upper limit, when the liquid detergent is diluted with tap water in the rinsing step, the orientation of the component (a) tends to be sparse and the foam breaking tendency tends to be more excellent. There is.

<Metal ion sequestering agent (b)>
As the sequestering agent (b), for example, aminocarboxylic acids, organic carboxylic acids, phosphonic acids, phosphonocarboxylic acids, phosphoric acids, etc., salts of these with basic substances, etc., usually used as sequestering agents Can be adopted. Examples of the salt include salts with alkali metals such as potassium and sodium, and salts with alkanolamines such as monoethanolamine, diethanolamine and triethanolamine. One or more sequestering agents (b) can be used.

As aminocarboxylic acid or its salt, the compound represented by following General formula (2) is mentioned, for example.

In formula (2), M ² , M ³ and M ⁴ may be the same as or different from each other, and are each a hydrogen atom, an alkali metal, an alkaline earth metal, a cationic ammonium group or an alkanolamine. As an alkali metal, sodium and potassium are preferable. As the alkanolamine, monoethanolamine, diethanolamine, and triethanolamine are preferable. The ^{M 2, M 3, M 4} , alkali metals are preferred, sodium being particularly preferred.
A represents a linear or branched alkyl group having 8 to 22 carbon atoms, a sulfo group, an amino group, a hydroxyl group, a hydrogen atom, or COOM ⁵ . As A, CH ₃ , OH, H, and COOM ⁵ are preferable, and CH ₃ and H are more preferable, and CH ₃ is particularly preferable. M ⁵ is any one of a hydrogen atom, an alkali metal, an alkaline earth metal, a cationic ammonium group, and an alkanolamine. As an alkali metal, sodium and potassium are preferable. As the alkanolamine, monoethanolamine, diethanolamine, and triethanolamine are preferable. The ^{M 2, M 3, M 4} , alkali metals are preferred, sodium being particularly preferred.
m and n are each an integer of 0-2. m is preferably 0 or 1. n is preferably 0 or 1. When both m and n are 0, A is CH ₃ .

Examples of aminocarboxylic acids represented by the formula (2) (M ² , M ³ and M ⁴ are all hydrogen atoms) include methylglycine diacetate (m = n = 0, A = CH ₃ ), aspartate diacid. Acetic acid (m = 1, n = 0, A = COOH), isoserine diacetate (m = 0, n = 1, A = OH), β-alanine diacetate (m = 0, n = 1, A = H), glutamic acid And diacetic acid (m = n = 0, A = H).

  Other aminocarboxylic acids include ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, iminodisuccinic acid, diethylenetriaminopentaacetic acid, N-hydroxyethylethylenediamineacetic acid, ethylenediaminetetrapropionic acetic acid, triethylenetetrahexaacetic acid, ethylene glycol diether diamine tetra Examples include acetic acid, hydroxyethyliminodiacetic acid, and cyclohexane-1,2-diaminetetraacetic acid.

  Organic carboxylic acids include acetic acid, adipic acid, monochloroacetic acid, oxalic acid, succinic acid, oxydisuccinic acid, carboxymethyl succinic acid, carboxymethyloxysuccinic acid, etc., and glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxymethyltartaric acid And hydroxycarboxylic acid substances such as citric acid, malic acid and gluconic acid.

  Examples of phosphonic acids include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and its derivatives, 1-hydroxyethane-1,1,2 -Triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminotrimethylenephosphonic acid and the like.

Examples of phosphonocarboxylic acids include 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, and α-methylphosphonosuccinic acid.
Examples of phosphoric acids include orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, hexametaphosphoric acid, condensed phosphoric acid such as phytic acid, and the like.

  Of these, the sequestering agent (b) is preferably an aminocarboxylic acid or a salt thereof. In particular, methylglycine diacetic acid and its salt (especially alkali metal salt), ethylenediaminetetraacetic acid and its salt (especially alkali metal) from the point that the detergency of scum dirt and the effect of suppressing reprecipitation of scum dirt are better. Salt.) Is preferred.

  The content of the component (b) in the liquid detergent is preferably 1 to 10% by mass, and more preferably 3 to 7% by mass. When the blending amount of component (b) is equal to or greater than the lower limit value, it sufficiently acts on fatty acid calcium, which is the main component of scum soil, and can be changed to a water-soluble substance such as sodium fatty acid. The power is better. In addition, the same action continues in the rinsing step, preventing insolubilization of the water-soluble substance, and more effective in suppressing the reprecipitation of scum stains. On the other hand, when the blending amount of component (b) exceeds the upper limit value, divalent metal ions (calcium ions, etc.) that are included in tap water added in the rinsing step and are considered to contribute to foam breaking properties are necessary. It will be captured. Therefore, it is preferable to make the compounding quantity of (b) component below an upper limit from a viewpoint of maintaining a favorable foam breakability.

  The mass ratio (a) / (b) between the component (a) and the component (b) is preferably 0.6 to 1.7, more preferably 0.8 to 1.3. When the ratio of the component (a) to the component (b) is such a ratio, in particular, both the effect of suppressing the reprecipitation of scum dirt and the foam breaking property in the rinsing process are extremely excellent. And since these two characteristics are both excellent, the scum dirt re-adhesion inhibitory effect with respect to the inside of a drain outlet, a drain path, etc. is exhibited highly.

<Zinc (c)>
The liquid detergent may further contain zinc (c) (hereinafter sometimes referred to as component (c)).
The component (c) is a component that suppresses malodors such as drains caused by scum stains, such as zinc sulfate, zinc chloride, zinc gluconate, zinc bromide, zinc nitrate, zinc ammonium chloride, zinc acetate. It is preferable to be blended in a liquid detergent in the form of water-soluble zinc (zinc compound that dissolves 10 g or more in 1 liter of water at 25 ° C.) such as zinc ammonium sulfate, zinc aluminum sulfate, potassium zinc sulfate, and zinc iodide. In particular, zinc sulfate and zinc chloride are preferable from the viewpoint of the malodor control effect.
(C) As a component, 1 or more types can be used. In addition, in the liquid detergent, the component (c) is a counter ion of the anionic surfactant that is the component (a), a cation that constitutes a salt of the sequestering agent that is the component (b), and the like. It may exist and there is no restriction | limiting in particular in the presence form.

  The content of the component (c) in the liquid detergent is preferably 0.01 to 10% by mass, and more preferably 1 to 5% by mass. When the blending amount of the component (c) is equal to or more than the lower limit, the malodor suppressing effect by the component (c) is sufficiently exhibited. Moreover, the storage stability fall of the liquid cleaning agent by the mixing | blending of (c) component is hard to produce that it is below an upper limit.

  In addition, when the component (c) is blended, it is preferable to employ aminocarboxylic acids or salts thereof as the component (b) in order to further exert the malodor control effect. It is preferable to employ aminocarboxylic acids (methylglycine diacetic acid, aspartic acid diacetic acid, isoserine diacetic acid, β-alanine diacetic acid, glutamic acid diacetic acid, etc.) or salts thereof, more preferably methylglycine diacetic acid or Adopt the salt.

<Solvent>
(water)
The liquid cleaning agent of the present invention usually contains water as a solvent from the viewpoint of easy preparation of the liquid cleaning agent and the viewpoint of easy dissolution in water during rinsing.
The amount of water in the liquid detergent is preferably 50 to 95% by mass, more preferably 70 to 95% by mass, and still more preferably 75 to 90% by mass in the liquid detergent.
When the blending amount of water is at least the lower limit value, the liquid detergent is likely to dissolve and flow in water during rinsing, and if it is less than the upper limit value, the cleaning component can be sufficiently contained.

(Organic solvent)
As the solvent, one or more organic solvents other than water may be used. By using the organic solvent, for example, the effect of dissolving the components (a) to (c) well in the liquid cleaning agent and the effect of improving the cleaning power can be obtained.

Examples of the organic solvent include C2-C4 monohydric alcohols, C4-C12 polyhydric alcohols, C4-C10 glyceryl ethers, and C3-C14 glycol ether solvents.
Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, n-propanol, isopropanol, normal butanol, secondary butanol, and tertiary butanol.
Examples of polyhydric alcohols having 4 to 12 carbon atoms and glyceryl ethers having 4 to 10 carbon atoms include isoprene glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,8-octanediol, 1,9- Nonanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, glycerin, hexyl glyceryl ether and the like can be mentioned.
Examples of the glycol ether solvent having 3 to 14 carbon atoms include ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol. Examples thereof include monobutyl ether, phenyl carbitol, phenyl cellosolve, and benzyl carbitol.

Among these, a glycol ether solvent having 3 to 14 carbon atoms is preferable, and diethylene glycol monobutyl ether is particularly preferable from the viewpoint of the effect of dissolving the components (a) to (c) in the liquid detergent and the detergency.
The content of the organic solvent is preferably 1 to 20% by mass, more preferably 5 to 15% by mass in the liquid detergent. When it is at least the lower limit value, the components (a) to (c) are favorably dissolved in the liquid cleaning agent, and the liquid cleaning agent tends not to be turbid. Moreover, the improvement effect of the detergency by adding an organic solvent is easy to be acquired. On the other hand, if it is not more than the upper limit value, the solubility of the components (a) to (c) and the optional components described later can be maintained, and a uniform liquid cleaning agent free from gelation or lumps tends to be obtained.

<Optional component>
The liquid cleaning agent of the present invention may contain a component that can be used for a bathroom cleaning agent as long as the effect of the present invention is not hindered. Examples of such optional components include the following components. One or more optional components can be used as necessary.

(Surfactant)
Examples of the surfactant include surfactants other than the component (a) described above (anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and semipolar surfactants). It is done.
It does not specifically limit as an anionic surfactant, A well-known thing can be used. For example, linear alkylbenzene sulfonate; α-olefin sulfonate; linear or branched alkyl sulfate ester salt; alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt; alkane sulfonate having an alkyl group; α- And sulfo fatty acid ester salts.
Examples of the salt include alkali metal salts such as sodium and potassium, and alkanolamine salts such as monoethanolamine and diethanolamine.

Among these, as the linear alkylbenzene sulfonate, those having 8 to 16 carbon atoms in the linear alkyl group are preferable, and those having 10 to 14 carbon atoms are particularly preferable.
The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms.
As the alkyl sulfate ester salt, those having 10 to 20 carbon atoms are preferable.
The alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms, and an average of 1 to 10 moles of ethylene oxide added thereto (ie, Polyoxyethylene alkyl ether sulfate ester salt or polyoxyethylene alkenyl ether sulfate ester salt) is preferable.
The carbon number of the alkane sulfonate is 10 to 20, preferably 14 to 17, and the secondary alkane sulfonate is particularly preferable.
The α-sulfo fatty acid ester salt is preferably one having 10 to 20 carbon atoms.

  These anionic surfactants can be easily obtained on the market. Moreover, you may synthesize | combine by a well-known method.

  It does not specifically limit as a nonionic surfactant, A well-known thing can be used. Specifically, alkylamine oxide type surfactants include N-lauryl-N, N-dimethylamine oxide, N-myristyl-N, N-dimethylamine oxide, N-palmityl-N, N-dimethylamine oxide. Alkylamine oxide selected from lauroylaminopropyldimethylamine oxide and the like is preferable.

R ¹¹ —O— (R ¹² O) _t —H (R ¹¹ is a linear or branched hydrocarbon group having 10 to 18 carbon atoms, R ¹² is a hydrocarbon group having 1 to 3 carbon atoms, preferably An alkylene group, t is an average number of added moles, and is a number of 1 to 20, preferably 5 to 15.) Polyoxyalkylene addition type nonionic surfactants, alkylglycosides, sorbitan fatty acid esters and the like represented by And polyoxyalkylene (2 to 3 carbon atoms) alkyl (10 to 18 carbon atoms) ether (alkylene oxide average addition mole number 5 to 20) is preferable.

The amphoteric surfactant is not particularly limited, and known ones can be used. Specific examples include amphoteric surfactants such as a carboxylate salt type, a sulfate ester salt type, a sulfonate salt type, and a phosphate ester salt type. Among these, a carboxylic acid type is preferable from the viewpoint of detergency.
Examples of the carboxylate type amphoteric surfactant include lauryl dimethylaminoacetic acid betaine, coconut alkyldimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyl betaine, lauric acid amidopropyl dimethylaminoacetic acid betaine, coconut alkylamidopropyldimethylaminoacetic acid betaine And betaine-type amphoteric surfactants.

It does not specifically limit as a cationic surfactant, A well-known thing can be used. Specifically, didecyldimethylammonium chloride, didecyldimethylammonium methosulfate, distearyldimethylammonium chloride, dioctyldimethylammonium chloride, distearyl dihydroxyethylammonium chloride, di-tallow alkyldimethylammonium chloride, di (stearoyloxyethyl) dimethyl Ammonium chloride, di (oleoyloxyethyl) dimethylammonium chloride, di (palmitoyloxyethyl) dimethylammonium methosulfate, di (stearoyloxyisopropyl) dimethylammonium chloride, di (oleoyloxyisopropyl) dimethylammonium chloride, di (oleoyl) Oxybutyl) dimethylammonium chloride Di (stearoyl oxy ethyl) methyl-hydroxyethyl ammonium methosulfate, tri (stearoyl oxyethyl) methyl methosulfate, and the like. The “beef tallow alkyl” group has 14 to 18 carbon atoms.
Of these, didecyldimethylammonium chloride and stearyltrimethylammonium chloride are preferable.

The pH of the liquid detergent of the present invention is preferably 5 to 10 at 25 ° C., more preferably 7 to 9.
When the pH of the liquid cleaning agent is within the above range, the influence on the material in the bathroom is mild, and the cleaning power against various stains is good, which is preferable.

The liquid cleaning agent demonstrated above contains the compound (a) which is a sulfate ester salt which has a branched structure, and a sequestering agent (b). Therefore, not only is the scum dirt detergency excellent, but it is also possible to suppress the scum dirt from being reattached to the inside of the drain outlet or the drainage path in the rinsing process.
The reason why such an effect is obtained is not necessarily clear, but is estimated as follows.

That is, the compound (a) has a higher dynamic surface tension reducing ability than a general linear or branched anionic surfactant due to a specific structure branched at the β-position. Therefore, when a new interface is formed, a surfactant molecule film is rapidly formed. Therefore, it is considered that the water-insoluble scum dirt is excellent in dissolution and dispersibility, and exhibits excellent detergency combined with the water-solubilizing action of the scum dirt by the component (b). In addition, the component (a) is excellent in dissolution and resolution of scum dirt, and is difficult to re-precipitate scum dirt even when tap water is added in the rinsing process, and highly reattaches scum dirt to the drain outlet and drainage channel. It can be suppressed.
In addition, the component (a) having a bulky hydrophobic group has a structure that is difficult to orientate densely at the interface, and therefore, when tap water is added and diluted in the rinsing step, bubbles are easily broken. Therefore, even if the scum dirt is re-deposited, it is considered that the scum dirt can be more highly suppressed without being entangled with bubbles and kept in the drain outlet or the drainage path.

  Further, by using the component (c), the bad odor suppressing effect of the liquid detergent can be enhanced. The reason why such an effect is obtained by using the component (c) is not clear, but the component (a) and the component (b) suppress the adhesion of scum to the drain outlet and the drainage route, and as a result, the antibacterial effect is obtained. It is considered that an excellent malodor control effect can be obtained by directly acting on the soil component (odor component) in which a small amount of the component (c) zinc is left.

  As described above, according to the liquid cleaning agent of the present invention, scum dirt can be removed, and bathroom cleaning can be completed without being reattached to the inside of the drain outlet or the drainage path. Therefore, it is very effective to use such a liquid cleaning agent on a daily basis in terms of keeping drain outlets, drainage paths, and the like that are rarely washed with a detergent stock solution clean.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

<Preparation of liquid detergent>
According to the composition shown in the table, 1000 g of the liquid cleaning agent of each example and comparative example was prepared by the manufacturing method shown below.
The unit of the blending amount in the table is “mass%”, and all the components indicate the amount in terms of pure content.
In addition, the liquid cleaning agent of each example was prepared by balancing with water so that the total of each component described in the table was 100% by mass.

[Preparation method]
In a 1 L beaker, 70 to 80% of distilled water as a balance component is added, and then the components (a) or (a ′), (b), (c), and optional components are listed in the table. And stirred thoroughly with a magnetic stirrer (F-606N manufactured by Fine).
After mixing by stirring, an appropriate amount of a pH adjusting agent (amount of about 2 g or less with pure sodium hydroxide) was added as necessary so that the pH at 25 ° C. was 8. Then, distilled water was added so that the whole amount might be 100 mass%, and it stirred further, and manufactured the liquid detergent for bathrooms of each case, respectively.
In addition, the “balance” indicating the blending amount of water means the balance added so that the total blending amount (% by mass) of all the blending components contained in the liquid detergent is 100% by mass.

  For pH measurement, the temperature of the liquid cleaning agent is adjusted to 25 ° C., and a glass electrode type pH meter (product name: HM-30G, manufactured by Toa DKK Corporation) is used to immerse the glass electrode directly in the liquid cleaning agent. went. Moreover, the value of pH shown after 1 minute passage was employ | adopted for the value of pH.

  In the table, (a) / (b) means the ratio (mass ratio) of the component content (a) to the component content (b) in the liquid detergent.

[Each component]
Below, the component shown in the table | surface is demonstrated.
((A) component)
(A) -1: Polyoxyethylene mono (2-propylheptyl) ether sulfate Na
290 g of BASF “Rutensol XP30” was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Further, this was obtained by neutralizing with an aqueous sodium hydroxide solution.
(A) -1 corresponds to C _x H _{2x + 1} = propyl group, C _y H _{2y + 1} = pentyl group, x + y = 8, p = 0, q = 3, and M ¹ = sodium in formula (1).

(A) -2: Polyoxyethylene mono (2-propylheptyl) ether sulfate Na
It was prepared in the same manner as (a) -1, except that 334 g of “Rutensol XP40” manufactured by BASF was used instead of “Rutensol XP30” manufactured by BASF.
(A) -2 corresponds to C _x H _{2x + 1} = propyl group, C _y H _{2y + 1} = pentyl group, x + y = 8, p = 0, q = 4, and M ¹ = sodium in formula (1).

(A) -3: Polyoxyethylene polyoxypropylene mono (2-propylheptyl) ether sulfate Na
It was prepared in the same manner as (a) -1, except that 349 g of “Rutensol XL40” manufactured by BASF was used instead of “Rutensol XP30” manufactured by BASF.
(A) -3 corresponds to C _x H _{2x + 1} = propyl group, C _y H _{2y + 1} = pentyl group, x + y = 8, p = 1, q = 3, M ¹ = sodium in formula (1).

((A ′) component which is a comparative product of (a) component)
(A ′)-1: Linear alkylbenzene sulfonate Sodium alkylbenzene sulfonate having an alkyl group having 10 to 14 carbon atoms (manufactured by Teika, neutralized Teika Power L121 with sodium hydroxide)

(A ′)-2: 2-propylheptyl ether sulfate Na
Hexylaldehyde is subjected to gel condensation with alkali (dimerization), and 158 g of 2-propylheptanol obtained in this manner is placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) is added to the reaction temperature. It was dripped slowly, keeping at 40 degreeC. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired alkyl ether sulfuric acid. Further, this was obtained by neutralizing with an aqueous sodium hydroxide solution.
(A ′) _{-2 corresponds to} C _x H _{2x + 1} = propyl group, C _y H _{2y + 1} = pentyl group, x + y = 8, p = 0, q = 0, and M ¹ = sodium in formula (1).

(A ′)-3: Sodium polyoxyethylene (2-butyloctyl) ether sulfate (addition of 3 moles of ethylene oxide on average)
In a 4 L autoclave, 372 g of trade name ISOFOL12 (C _x H _{2x + 1} = butyl group, C _y H _{2y + 1} = hexyl group in formula (1)) and 0.8 g of potassium hydroxide catalyst were charged in a 4 L autoclave. The interior of the autoclave was purged with nitrogen, and the temperature was raised while stirring. Thereafter, 271 g of ethylene oxide was introduced while maintaining a temperature of 180 ° C. and a pressure of 0.3 mPa, to obtain a reaction product having an average added mole number of ethylene oxide of 3. Next, 321 g of the alcohol ethoxylate thus obtained was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Furthermore, this was neutralized with an aqueous sodium hydroxide solution to obtain (a ′)-3.
(A ′)-3 corresponds to C _x H _{2x + 1} = butyl group, C _y H _{2y + 1} = hexyl group, x + y = 10, p = 0, q = 3, and M ¹ = sodium in formula (1).

(A ′)-4: Polyoxyethylene (2-butyloctyl) ether sulfate sodium salt (average addition of 12 moles of ethylene oxide)
In a 4 L autoclave, 372 g of trade name ISOFOL12 (C _x H _{2x + 1} = butyl group, C _y H _{2y + 1} = hexyl group in formula (1)) manufactured by Sasol Corporation and 0.8 g of potassium hydroxide catalyst were charged. The autoclave was purged with nitrogen, and the temperature was raised while stirring. Thereafter, 1084 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure of 0.3 mPa, to obtain a reaction product having an average addition mole number of ethylene oxide of 12. Next, 728 g of the alcohol ethoxylate thus obtained was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Furthermore, this was neutralized with an aqueous sodium hydroxide solution to obtain (a ′)-4.
(A ′) _{-4 corresponds to} C _x H _{2x + 1} = butyl group, C _y H _{2y + 1} = hexyl group, x + y = 10, p = 0, q = 12, and M ¹ = sodium in formula (1).

(A ′)-5: Sulfur oxide as an EO average 3 mol addition product to a branched alcohol having 13 carbon atoms, 332 g of “Lutensol TO3” manufactured by BASF Corporation was placed in a 500 mL flask equipped with a stirrer and replaced with nitrogen. 81 g of (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Further, this was neutralized with an aqueous sodium hydroxide solution to obtain (a ′)-5.

(A ′)-6: Sulfur oxide of EO average 5 mol addition product of linear lauryl alcohol In a 4 L autoclave, 372 g of trade name Conol 1275 manufactured by Shin Nippon Chemical Co., Ltd. and 0.8 g of potassium hydroxide catalyst The inside of the autoclave was purged with nitrogen, and the temperature was raised while stirring. Thereafter, 453 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure of 0.3 mPa, to obtain a reaction product having an average added mole number of ethylene oxide of 5 mol. Next, 413 g of the alcohol ethoxylate thus obtained was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Furthermore, this was neutralized with an aqueous sodium hydroxide solution to obtain (a ′)-6.
Note that (a ′)-6 does not have a branched structure.

(A ′)-7: Sulfur oxide of EO average 2 mol addition product of linear lauryl alcohol In a 4 L autoclave, 372 g of trade name Conol 1275 manufactured by Shin Nippon Chemical Co., Ltd. and 0.8 g of potassium hydroxide catalyst The inside of the autoclave was purged with nitrogen, and the temperature was raised while stirring. Thereafter, 181 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 0.3 mPa, to obtain a reaction product having an average added mole number of ethylene oxide of 2 mol. Next, 274 g of the alcohol ethoxylate thus obtained was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Furthermore, this was neutralized with an aqueous sodium hydroxide solution to obtain (a ′)-7.
(A ′)-7 does not have a branched structure.

(A ′)-8: Sulfur oxide of EO average 15 mol addition product of linear lauryl alcohol In a 4 L autoclave, 372 g of trade name Conol 1275 manufactured by Shin Nippon Chemical Co., Ltd. and 0.8 g of potassium hydroxide catalyst The inside of the autoclave was purged with nitrogen, and the temperature was raised while stirring. Thereafter, 1359 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure of 0.3 mPa, to obtain a reaction product having an average addition mole number of ethylene oxide of 15. Next, 866 g of the alcohol ethoxylate thus obtained was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Furthermore, this was neutralized with an aqueous sodium hydroxide solution to obtain (a ′)-8.
Note that (a ′)-8 does not have a branched structure.

(A ′)-9: Sulfur oxide of EO average 3 mol addition product of linear myristyl alcohol 412 g of Kao Corporation, trade name Calcoal 4098 and 0.8 g of potassium hydroxide catalyst were charged in a 4 L autoclave. The interior of the autoclave was purged with nitrogen, and the temperature was raised while stirring. Thereafter, 271 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 0.3 mPa, to obtain a reaction product having an average addition mole number of ethylene oxide of 3. Next, 342 g of the alcohol ethoxylate thus obtained was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Further, this was neutralized with an aqueous sodium hydroxide solution to obtain (a ′)-9.
Note that (a ′)-9 does not have a branched structure.

(A ′)-10: Sulfur oxide of an EO average 3 mol addition product of synthetic alcohol having C12,13 carbon atoms In a 4 L autoclave, 400 g of trade name Safol 23 manufactured by Sasol Co., Ltd. and 0 of potassium hydroxide catalyst .8 g was charged, the inside of the autoclave was purged with nitrogen, and the temperature was raised while stirring. Thereafter, 271 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 0.3 mPa, to obtain a reaction product having an average addition mole number of ethylene oxide of 3. Next, 334 g of the alcohol ethoxylate thus obtained was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Further, this was neutralized with an aqueous sodium hydroxide solution to obtain (a ′)-10.

((B) component)
(B) -1: Trisodium methylglycine diacetate (manufactured by BASF, Trilon M)
(B) -2: Disodium ethylenediaminetetraacetate (manufactured by BASF, Trilon BD)
(B) -3: 2,2′-Iminodisuccinic acid tetrasodium (manufactured by LANXESS, Baypure CX100)
(B) -4: Trisodium citrate dihydrate (manufactured by Fuso Chemical Industries, purified sodium citrate)

(Component (c))
(C) -1: Zinc sulfate (manufactured by Kanto Chemical, special grade)
(C) -2: Zinc chloride (manufactured by Kanto Chemical, special grade)

As the optional component diethylene glycol monobutyl ether, “butyl diglycol” manufactured by Nippon Emulsifier was used.
As the pH adjuster, sodium hydroxide (manufactured by Kanto Chemical Co., Ltd., reagent special grade) or sulfuric acid (manufactured by Kanto Chemical Co., Ltd., reagent special grade) was used. Moreover, the sodium hydroxide aqueous solution used when manufacturing the component (a) and the component (a ′) was obtained by dissolving sodium hydroxide (manufactured by Kanto Chemical Co., Ltd., reagent grade) in water.

<Evaluation and confirmation test of liquid detergent>
Each liquid cleaning agent in each example was evaluated by the following evaluation methods, and the results were also shown in the table.

[Scum dirt cleaning power evaluation]
10ml liquid detergent on the surface of a polypropylene washbasin (Iris Oyama, Ofurotime series, white) with soap residue (scum stain) that cannot be easily removed by rubbing with a sponge for 6 months. Was rubbed 10 times with a urethane sponge (Scotch Bright, bath shine antibacterial sponge, 75 × 160 × 47 mm), and the removal state of dirt was visually evaluated. The evaluation criteria were as follows, and 3 or more points were accepted.
5 points: Dirt was completely removed.
4.5 points: Dirt was almost completely removed.
4 points: Most of the dirt was removed.
3.5 points: Dirt was considerably removed.
3 points: Dirt was removed to some extent.
2 points: Not very dirty.
1 point: Dirt is hardly removed.

[Evaluation of foam breaking property]
Evaluation was performed as follows. Three or more points were accepted.
(1) 100-fold dilution test 1 mL of liquid detergent is placed in a 500 mL rigid polyvinyl chloride container (AS ONE, clear wide-mouth bottle), and then tap water (4.6 ° C.) at room temperature (25 ° C.) for foaming. 10 DH) was added, the lid was closed, and the mixture was well stirred to foam the liquid detergent (corresponding to the foaming process during washing). Next, 100 mL of tap water was added for dilution, the lid was closed, and the mixture was mixed about 5 times (corresponding to the dilution process at the time of rinsing), and allowed to stand for 1 minute. The state of the foam after standing for 1 minute was visually observed, and when all the bubbles were broken, it was set as “5 points”. When bubbles remained, the following test (2) was performed on the liquid detergent.
(2) 300-fold dilution test Except that the amount of tap water added for dilution was changed to 300 mL instead of 100 mL, the state of bubbles after standing for 1 minute was visually observed in the same manner as (1) above. When all the bubbles were broken, “4 points” was set. When bubbles remained, the following test (3) was performed on the liquid detergent.
(3) 500-fold dilution test Except that the amount of tap water added for dilution was changed to 500 mL instead of 100 mL, the state of bubbles after standing for 1 minute was visually observed in the same manner as (1) above. When all the bubbles were broken, “3 points” was set. When bubbles remained, the following test (4) was performed on the liquid detergent.
(4) 1000-fold dilution test The amount of detergent is 0.5 mL instead of 1 mL, the amount of tap water added for foaming is 5 mL instead of 10 mL, and the amount of tap water added for dilution is 100 mL. In the same manner as (1) except that the volume was changed to 500 mL, the state of bubbles after standing for 1 minute was visually observed. When all bubbles were broken, “2 points” was set. When bubbles remained, the following test (5) was performed on the liquid detergent.
(5) 2000-fold dilution test The amount of detergent is 0.25 mL instead of 1 mL, the amount of tap water added for foaming is 2.5 mL instead of 10 mL, and the amount of tap water added for dilution is The state of the foam after standing for 1 minute was visually observed in the same manner as in the above (1) except that 500 mL was used instead of 100 mL. When all bubbles were broken, “1 point” was assigned. When bubbles remained, the liquid cleaning agent was set to “0 point”.

[Evaluation of bad odor control effect at bathroom drain]
0.1 g of slime collected from the bathroom drain outlet at home was put in a 900 mL glass bottle (AS ONE, UM sample bottle), and 1 g of liquid detergent was added so as to come into contact with the slime. The odor intensity in the bottle after 5 minutes was evaluated by 5 men in their 30s and 5 women according to the following evaluation criteria, and the average score was obtained.
An average score of less than 1 point was evaluated as “、 １”, 1 point or more and less than 3 points as “◯”, and 3 points or more as “x”, and the evaluation was made in three stages.
In addition, the odor intensity | strength (blank test) in a bottle when not adding a liquid detergent is 5 points | pieces.
5 points: Strong odor that cannot be tolerated.
4 points: Strong odor.
3 points: Obvious odor.
2 points: Odor enough to tell what odor is.
1 point: An odor that can be finally detected.
0 point: odorless.
-: Not evaluated.

[Reattachment test]
Using the bathroom equipment as shown below, a confirmation test was conducted on the reattachment of scum dirt.
The bathroom flooring (INAX, FA-1609P (4) -W) is provided with a gantry (INAX, FR-1609 (11) -M) and a drain trap (INAX, TP-39-L). A transparent vinyl chloride pipe (SEKISUI, Eslon clear pipe φ50) was connected to make a bathroom for testing.
Use a bathroom basin made of polypropylene (Iris Oyama, Offrotime Series, White) that has been used in the bathroom for 6 months on the bathroom floor of the above equipment and has soap residue (scum stain) that cannot be easily removed by rubbing with a sponge. Then, rub with a urethane sponge (Scotch Bright, bath shine antibacterial sponge, 75 x 160 x 47 mm) containing 10 ml of liquid detergent until it is clean, and then liquid with tap water (4.6 ° DH) at room temperature (25 ° C) Rinse all cleaning agents.
This operation was repeated three times, and the scum dirt reattached into the drain trap (drain port) of the bathroom facility and the vinyl chloride pipe (drain channel) was visually evaluated according to the following evaluation criteria. “◎” and “○” are acceptable.
(Double-circle): Scum dirt has not adhered again.
○: Scum dirt is hardly reattached.
X: Scum stain is clearly reattached.

  From the results shown in the table, according to the liquid cleaning agent of each example, not only “scum dirt cleaning power” is excellent, but also “foam breaking” is excellent, and scum dirt is reattached to the drain outlet or the drainage route. It was confirmed that it was difficult to do.

Claims (3)

The liquid cleaning agent for bathrooms containing the compound (a) represented by following General formula (1), and a sequestering agent (b).

[In the formula (1), x and y are each an integer of 1 to 7, and x + y = 8. PO represents an oxypropylene group, and EO represents an oxyethylene group. p represents the average number of repetitions of PO, q represents the average number of repetitions of EO, and p + q is 1 to 10. M ¹ is any ^one of alkali metal, alkaline earth metal, ammonium and alkanolamine. ]   The bathroom liquid cleaning agent according to claim 1, wherein the mass ratio represented by (a) / (b) is 0.6 to 1.7.   The liquid cleaning agent for bathrooms according to claim 1 or 2, further comprising zinc (c).