JP2018039881A - Cleaning composition - Google Patents

Abstract

Disclosed is a cleaning composition that can suppress tearing of toilet paper, has improved cleaning power, and does not easily leave wiping marks. An average particle size of 0.01 μm, comprising a cross-linked product formed of one or more gelling agents selected from agar, gellan gum, carrageenan, pectin and sodium alginate and a cross-linking agent. In the cleaning composition containing the microgel particle group (A) of less than 1,000 μm or more, the surfactant (B), and the water-soluble solvent (C), the (B) with respect to the total mass of the cleaning composition. The mass of a component is 0.1-5 mass%, and the mass of the said (C) component with respect to the total mass of a cleaning composition is 15-75 mass%. [Selection figure] None

Description

  The present invention relates to a cleaning composition.

Toilet paper is often used to clean the toilet seat and the area around the toilet. If you apply a liquid cleaning agent to the toilet paper and wipe it off, the toilet paper will break easily.
Patent Document 1 reports that tearing of toilet paper can be suppressed by blending a liquid detergent with a water-soluble solvent at a high concentration. When this liquid cleaning agent is used on a non-horizontal surface, it drips, so the residence time of the cleaning agent with respect to dirt is shortened. For this reason, there is a problem that the cleaning power inherent to the cleaning agent is not sufficiently exhibited.
Therefore, Patent Document 2 reports a detergent composition having a viscosity increased by blending a polymer in order to increase the viscosity of the solution.

JP 2011-225762 A Japanese Patent Application Laid-Open No. 07-157796

However, when the polymer compound is simply blended and thickened, the retention property with respect to the object to be cleaned increases, so that the components of the cleaning composition easily remain on the surface to be cleaned. For this reason, it was necessary to rinse with water twice or thoroughly with water, which was complicated.
Then, this invention aims at the cleaning composition which can suppress the tear of a toilet paper, improves a cleaning power, and does not leave a wiping trace easily.

The present invention has the following aspects.
[1] An average particle size of 0.01 μm or more, comprising a crosslinked product formed from one or more gelling agents selected from agar, gellan gum, carrageenan, pectin and sodium alginate and a crosslinking agent In the cleaning composition containing the microgel particle group (A) of less than 1,000 μm, the surfactant (B), and the water-soluble solvent (C), the component (B) with respect to the total mass of the cleaning composition Is a detergent composition in which the mass of the component (C) is 15 to 75 mass% with respect to the total mass of the detergent composition.
[2] The cleaning composition according to [1], wherein a mass of the gelling agent is 0.005 to 1% by mass with respect to a total mass of the cleaning composition.
[3] The cleaning composition according to [1] or [2], wherein the mass of the component (A) and the mass of the component (C) satisfy the relationship of the following formula (1).
[Mass of component (A)] / [Mass of component (C)] = 0.12 to 4 (1)

（上記（ｂ１１）式中、ｐ＋ｑ＝１０〜１４である。Ｍは、アルカリ金属、アルカリ土類金属、アンモニア、アルカノールアミンのいずれかを示し、ｓは、Ｍの価数を表す。）

（上記（ｂ１２）式中、Ｒ^１及びＲ^２は、それぞれ独立に、炭素数６〜１８のアルキル基又は炭素数６〜１８のアルケニル基である。Ｍ^ａは、水素、アルカリ金属、アルカリ土類金属、アンモニア、アルカノールアミンのいずれかを示し、ｔはＭ^ａの価数を表す。）

（上記（ｂ２１）式中、Ｒ^１１は、炭素数８〜２０のアルキル基又は炭素数８〜２０のアルケニル基を示す。Ｒ^１２は、炭素数１〜５のアルキレン基を示す。Ｒ^１３及びＲ^１４は、それぞれ独立に、水素又は炭素数１〜３のアルキル基を示す。Ｒ^１５は、炭素数１〜５のアルキレン基を示す。）

（上記（ｂ２２）式中、Ｒ^２１は、炭素数８〜１８の直鎖もしくは分岐鎖のアルキル基又は炭素数８〜１８の直鎖もしくは分岐鎖のアルケニル基を示す。Ｒ^２２及びＲ^２３は、それぞれ独立に、炭素数１〜４の直鎖もしくは分岐鎖のアルキル基又は炭素数２〜４の直鎖もしくは分岐鎖のアルケニル基を示す。Ｒ^２４は、炭素数１〜６の直鎖もしくは分岐鎖のアルキレン基又は炭素数１〜６の直鎖もしくは分岐鎖のヒドロキシアルキレン基を示す。） [4] The component (B) includes at least one surfactant selected from a secondary alkanesulfonate represented by the following formula (b11) and a compound represented by the following formula (b12); The cleaning according to any one of [1] to [3], comprising a compound represented by the formula (b21) and at least one amphoteric surfactant selected from compounds represented by the following formula (b22) An agent composition may be used.

(In the formula (b11), p + q = 10 to 14. M represents any one of alkali metal, alkaline earth metal, ammonia, and alkanolamine, and s represents the valence of M.)

(In the formula (b12), R ¹ and R ² are each independently an alkyl group having 6 to 18 carbon atoms or an alkenyl group having 6 to 18 carbon atoms. M ^a is hydrogen, alkali metal, alkaline earth. metalloid, ammonia, indicates one of the alkanolamines, t represents the valence of M ^a.)

(In the formula (b21), R ¹¹ represents an alkyl group having 8 to 20 carbon atoms or an alkenyl group having 8 to 20 carbon atoms. R ¹² represents an alkylene group having 1 to 5 carbon atoms. R ¹³ and R ¹⁴ independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and R ¹⁵ represents an alkylene group having 1 to 5 carbon atoms.)

(In the formula (b22), R ²¹ represents a linear or branched alkyl group having 8 to 18 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms. R ²² and R ²³ are Each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched alkenyl group having 2 to 4 carbon atoms, and R ²⁴ represents a linear or branched chain alkenyl group having 1 to 6 carbon atoms; A branched alkylene group or a linear or branched hydroxyalkylene group having 1 to 6 carbon atoms is shown.)

  According to the cleaning composition of the present invention, it is possible to suppress the tearing of toilet paper, the cleaning power is improved, and it is difficult to leave a wiping trace.

(Cleaning composition)
The cleaning composition of this invention contains (A) component, (B) component, and (C) component.
Although the viscosity of the cleaning composition in the present invention is not particularly limited, for example, 2 to 100 mPa · s is preferable. If the viscosity is equal to or higher than the above lower limit value, it easily stays in the cleaning target when applied to the cleaning target. If the viscosity is equal to or lower than the upper limit value, the cleaning composition is easily poured out and easily wiped off.
The viscosity of the cleaning composition is a value (measurement conditions: rotor No. 2, rotation speed 60 rpm, viscosity after 60 rotations) measured at 25 ° C. with a B-type viscometer (manufactured by TOKIMEC).

<(A) component>
The component (A) contains a crosslinked product formed from one or more gelling agents selected from agar, gellan gum, carrageenan, pectin and sodium alginate and a crosslinking agent, and the average particle size is 0. A group of microgel particles having a diameter of 0.01 μm or more and less than 1,000 μm.
By blending the component (A), it is possible to obtain a cleaning composition that imparts thixotropy to the cleaning composition, improves the retention in a non-horizontal plane and the cleaning power, and does not leave wiping marks. The thixotropic property is a property exhibited by an intermediate substance between a plastic solid such as a gel and a non-Newtonian liquid such as a sol, and refers to a property that the viscosity changes with time.

  In the present invention, the component (A) has an average particle size of 0.01 μm or more and less than 1,000 μm, preferably 0.05 to 700 μm, more preferably 0.1 to 500 μm. When the average particle diameter of the component (A) is 1,000 μm or more, the retention in the non-horizontal plane is lowered, and as a result, the cleaning power may be lowered. On the other hand, if it is less than 0.01 μm, the wiping trace may remain easily.

  Here, the average particle size measurement of the component (A) is performed by manual flow cell measurement using a laser diffraction scattering type particle size distribution measuring device LA-920 (particle size measurement range: 0.02 to 2,000 μm) manufactured by Horiba, Ltd. Measure by method. The measurement temperature is 25 ° C., the circulation pump speed scale of the flow cell is 2, and the relative refractive index is set to 112A000I.

  In the present invention, the gelling agent means one having a property of being gelled by a crosslinking agent described later. The gelling agent of the present invention is selected from agar, gellan gum, carrageenan, pectin and sodium alginate. Examples of gellan gum include deacylated gellan gum and native gellan gum. Agar and deacylated gellan gum are preferred. These gelling agents can be used alone or in combination of two or more.

  Moreover, as a compounding quantity in the cleaning composition of a gelatinizer, 0.005-1 mass% is preferable with respect to the total mass of a cleaning composition, More preferably, 0.05-0.5 mass%, More preferably, it is 0.1-0.3 mass%. If the blending amount is less than 0.005% by mass, the retention and detergency on the non-horizontal surface may be small, and if it exceeds 1% by mass, the wiping traces may remain easily.

Examples of the crosslinking agent that forms a gel (crosslinked body) by crosslinking the gelling agent include acidic substances and metal salts as pH adjusting agents. Examples of the acidic substance include organic acids such as citric acid, lactic acid, malic acid, acetic acid, phosphoric acid, adipic acid, tartaric acid, and fruit juices. The metal salt is preferably a salt having a divalent cation, such as a soluble calcium salt or magnesium salt, which can exist as a cation in the aqueous solution.
Specific examples include food materials such as calcium glutamate, calcium lactate, calcium chloride, calcium citrate, calcium gluconate, calcium hydroxide, magnesium chloride, magnesium sulfate, milk casein, bittern, seawater and the like.

If the cross-linking agent is an acidic substance, it is preferable to add the cross-linking agent to the solution of the gelling agent in a range where the pH of the solution obtained by dissolving the gelling agent in an aqueous solvent is 3-7. If the cross-linking agent is a metal salt, the amount of addition varies depending on the concentration of the gelling agent, but the metal is present as a cation in an amount of 0.1 × 10 ^{−3 to 1} mol / kg with respect to the total mass of the cleaning composition. It is preferable to blend as described above. The cation concentration of the metal is more preferably 0.05 × 10 ^{−3 to} 0.5 mol / kg, further preferably 0.1 × 10 ^{−3 to} 0.1 mol / kg, particularly preferably 0.1 ×. 10 ^{−3 to} 0.05 mol / kg. Although depending on the gelling agent concentration, when the blending amount is within this range, a good detergent composition in which the polymer compound does not salt out can be obtained.

The cleaning composition containing the component (A) of the present invention can be obtained, for example, by the following two methods. First, a gelling agent is heated and dissolved in an aqueous solvent to obtain a solution, a crosslinking agent is added to the solution, and then a shearing force is applied with a device that applies a shearing force while cooling to remove component (A). It is a method of preparation. The remaining component is mixed and stirred with the component (A) to obtain a cleaning composition.
Second, after dissolving the gelling agent in an aqueous solvent by heating, apply a shearing force with a device that applies a shearing force while cooling, and add a crosslinking agent while applying a shearing force when the liquid temperature is 40 ° C or lower. (A) component. Similarly to the first method, the remaining component can be mixed and stirred with the component (A) to obtain a cleaning composition.

The blending amount of the gelling agent is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, and still more preferably 0.05 to 2% by mass with respect to the total mass of the component (A). is there. When the blending amount is less than 0.01% by mass, it is difficult to obtain the component (A), and when it exceeds 5% by mass, the viscosity of the component (A) becomes too high, and the handleability may deteriorate.
More specifically, the gelling agent is 0.1 to 2% by mass and the crosslinking agent is 0.006 to 0.6% by mass with respect to the total mass of the component (A).
The gelling agent is preferably heated and dissolved by dissolving the gelling agent in an aqueous solvent at a temperature equal to or higher than the melting point. For example, the temperature of the gelling agent solution is 85 to 90 ° C.
The component (A) is prepared by the above two methods, and can be sheared and crushed while being gelled to obtain a micro gel aggregate having fluidity and yield value. Any method may be used for cooling, such as cooling in a blending tank jacket, a method of introducing a cooling coil, cooling by external circulation, and the like.

  The cooling rate in the preparation of the component (A) is preferably 0.05 ° C./min or more, more preferably 0.1 ° C./min or more. When the cooling rate is less than 0.05 ° C./min, it takes too much time for cooling, and the production efficiency may deteriorate. The upper limit of the cooling rate is not particularly limited, and even if the cooling rate is large, there is no influence on the quality of the resulting cleaning composition as long as cooling is performed while applying a shearing force. In particular, in the temperature range of 55 to 20 ° C., cooling is performed at a cooling rate of 0.1 to 30 ° C./min, preferably 0.1 to 10 ° C./min, more preferably 0.1 to 5 ° C./min. preferable. The crosslinking agent may be added before cooling or after cooling is stopped, but is preferably added before reaching 40 ° C.

In the present invention, the degree of shearing and crushing during gelation can be appropriately adjusted according to the required average particle diameter of the component (A). When a smoother appearance is required, it is sufficiently crushed by high-speed stirring to form a fine particle size component (A). On the other hand, a dispersoid with a large specific gravity difference from the solution or a large occupied volume Is added, it is preferable to weaken the degree of crushing by light agitation to obtain the component (A) having a slightly larger particle size.
The shearing force is not particularly limited, but a stronger shearing force is preferable to a weaker shearing force for the purpose of normal uniform mixing. Specifically, the lower limit of the shear force is preferably 2 m / s or more, and more preferably 3 m / s or more. The upper limit of the shear force is preferably 30 m / s or less, and more preferably 25 m / s or less. If the shearing force during gelation is less than 2 m / s, the whole may gel without forming the component (A), and if it is too large, an effect commensurate with it cannot be obtained.

  (A) The apparatus which gives the shearing force at the time of preparing a component will not be specifically limited if a shearing force can be given. Specific examples of the apparatus for applying a shearing force include general emulsifiers such as a homogenizer, a disper blade, a paddle blade, a mechanical stirrer, a CLEARMIX, a milder, and an ultramixer. As a device for applying a shearing force, it is more preferable to use these in combination, or to use a oyster blade or an anchor blade in combination to promote the entire flow of the solution.

In the present invention, the shearing force is represented by the peripheral speed Ut at the tip of the stirring blade.
The peripheral speed Ut at the tip of the stirring blade can be calculated by the following mathematical formula (2).
Ut = π × n × d (2)
(Where n is the blade rotation speed [rps] and d is the blade diameter [m].)

  (A) As for the compounding quantity of a component, 10-80 mass% is preferable with respect to the total mass of a cleaning composition, More preferably, it is 10-65 mass%, More preferably, it is 10-55 mass%. When the blending amount is 10% by mass or more, sufficient retention and detergency on a non-horizontal surface can be obtained, and when the blending amount is 80% by mass or less, wiping traces are less likely to remain.

<(B) component>
Component (B) is a surfactant. (B) By mix | blending a component, the cleaning composition excellent in the detergency can be obtained.
As the component (B), an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant, which are usually used for cleaning agents, can be used.
From the viewpoint of detergency and remaining wiping traces, anionic surfactants and amphoteric surfactants are preferred.

Examples of the anionic surfactant include sulfo fatty acid alkyl ester salts, higher fatty acid salts, linear alkylbenzene sulfonates, α-olefin sulfonates, linear or branched alkyl sulfate salts, and alkyl ether sulfate esters. Examples thereof include salts or alkenyl ether sulfates, alkane sulfonates having an alkyl group, dialkyl sulfo fatty acid salts, α-sulfo fatty acid salts and esters thereof.
Examples of these salt forms include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, alkanolamine salts such as monoethanolamine and diethanolamine, and the like. Secondary alkane sulfonate (b11) and dialkylsulfosuccinate (b12) are preferred from the viewpoints of detergency and remaining wiping marks.

  (B) The compounding quantity of a component is 0.1-5 mass% with respect to the gross mass of a cleaning composition, Preferably it is 0.5-1.5 mass%. When the blending amount is less than 0.1% by mass, the detergency is insufficient, and when the blending amount exceeds 5% by mass, it causes a remaining wiping trace.

((B11) component)
The component (b11) is a secondary alkane sulfonate. The component (b11) is a surfactant also called paraffin sulfonate, and is usually provided in the form of a mixture having 10 to 21 carbon atoms. The content of the component (b11) having 13 to 18 carbon atoms is preferably 80% by mass or more, preferably 90% by mass or more, and may be 100% by mass with respect to the total mass of the mixture.
The component (b11) may be supplied as a mixture containing a small amount of primary alkane sulfonate, disulfonate, polysulfonate, and the like.

  Suitable examples of the component (b11) include compounds represented by the following formula (b11).

(B11) In the formula, p + q = 10-14. That is, the compound represented by the formula (b11) is a secondary alkanesulfonate having 13 to 17 carbon atoms (however, the carbon number in “M” in the formula (b11) is not included). If p + q is 10 or more, the detergency against oil stains is increased. If p + q is 14 or less, the solubility of the component (b11) in the cleaning composition is improved, and the precipitation of the component (b11) during storage at low temperatures is difficult to occur.
(B11) In the formula, M is a counter ion. Examples of M as the counter ion include alkali metals, alkaline earth metals, ammonia, alkanolamines and the like. Examples of the alkali metal include sodium, potassium, lithium and the like. Examples of the alkaline earth metal include calcium and magnesium. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine. Especially, as M, an alkali metal is preferable and sodium and potassium are more preferable.
(B11) In formula, s represents the valence of M. For example, if M is calcium, s is 2.

  As a commercially available product suitable as the component (b11), HOSTAPUR SAS30 (trade name, manufactured by Clariant Japan Co., Ltd., containing 90% by mass or more of sodium secondary alkanesulfonate having 13 to 17 carbon atoms), HOSTAPUR SAS60 (trade name) Manufactured by Clariant Japan Co., Ltd., containing 90% by mass or more of secondary alkane sulfonate having 13 to 17 carbon atoms, MERSOL80 (trade name, manufactured by Bayer, Inc., average carbon number 15 (secondary having 13 to 17 carbon atoms) 80% by mass or more of sodium alkane sulfonate), PS65, PS60, PS60W of the MARLON series (trade name, manufactured by SASOL Corporation. 90 mass of secondary alkane sulfonate having 10 to 18 carbon atoms (13 to 17 carbon atoms) %)))) And the like.

((B12) component)
The component (b12) is a compound represented by the following formula (b12) and is a dialkylsulfosuccinic acid ester or a salt thereof.

(B12) In the formula, R ¹ and R ² are each independently an alkyl group having 6 to 18 carbon atoms or an alkenyl group having 6 to 18 carbon atoms.
The number of carbon atoms of R ¹ and ^{R 2,} 8-14 is preferred. If it is at least the above lower limit, the detergency against oil stains is further increased, and if it is not more than the above upper limit, the solubility of the component (b12) in the detergent composition becomes good, and ( b12) Precipitation of components is difficult to occur.
R ¹ and R ² may be linear or branched, with a branched chain being preferred.
R ¹ and R ² are preferably alkyl groups.
M ^a is a counter ion and is any one of hydrogen, an alkali metal, an alkaline earth metal, ammonia, and an alkanolamine. Examples of the alkali metal include sodium, potassium, lithium and the like. Examples of the alkaline earth metal include calcium and magnesium. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine. Among them, the M ^a, alkali metals are preferred, sodium, potassium and more preferably.
t represents the valence of M ^a . For example, t is 2 if M ^a is calcium.

  Examples of the component (b12) include di-2-ethylhexyl sulfosuccinic acid ester salt, di-tridecyl sulfosuccinic acid ester salt, and dilauryl sulfosuccinic acid ester salt. These (b12) components may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the amphoteric surfactant include sulfobetaine and carbobetaine having a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, and an amide having a linear or branched alkyl group having 8 to 24 carbon atoms. Examples include sulfobetaine and amidocarbobetaine.
Especially, the following (b21) component and (b22) component are preferable from a viewpoint of detergency, wiping trace remaining property, and foamability.

((B21) component)
The component (b21) is a compound represented by the following formula (b21).

(B21) In the formula, R ¹¹ is an alkyl group having 8 to 20 carbon atoms or an alkenyl group having 8 to 20 carbon atoms.
The number of carbon atoms in R ¹¹ is preferably 9-15. If it is in the said range, the solubility of (b21) component in a cleaning composition will become favorable, and it will be hard to produce precipitation at the time of a preservation | save.
R ¹¹ may be a straight chain or a branched chain, and among them, a straight chain is preferable.
R ¹¹ is preferably an alkyl group.

R ¹² is an alkylene group having 1 to 5 carbon atoms.
The number of carbon atoms in R ¹² is preferably 2-3. If it is in the said range, the liquid stability in low temperature will become favorable.
R ¹² may be a straight chain or a branched chain, and among them, a straight chain is preferable.

R ¹³ and R ¹⁴ are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms.
When R ¹³ or R ¹⁴ is an alkyl group, the alkyl group preferably has 1 to 2 carbon atoms. If it is in the said range, precipitation of the (b21) component at low temperature will not arise easily.
When R ¹³ or R ¹⁴ is an alkyl group, this alkyl group may be a straight chain or a branched chain, and among them, a straight chain is preferable.
R ¹⁵ is an alkylene group having 1 to 5 carbon atoms. The number of carbon atoms of R ¹⁵ is 1 to 3 are preferred. If it is in the said range, precipitation of the (b21) component at low temperature will not arise easily.
R ¹⁵ may be a straight chain or a branched chain, and among them, a straight chain is preferable.

  Examples of the component (b21) include octylamidopropyl-N, N-dimethylacetic acid betaine (amidopropyloctane octoate), lauramidopropyl-N, N-dimethylacetic acid betaine (amidopropylbetaine laurate), and stearyl-N. N-dimethylacetic acid betaine (amidopropyl betaine stearate), stearyl-N, N-dimethyl-2-hydroxypropyl betaine, coconut oil fatty acid amidopropyl betaine, and the like. Especially, as a (b21) component, lauric acid amide propyl betaine is preferable.

  The component (b21) is commercially available. As lauric acid amidopropyl betaine, for example, “Enagicol L-30B” manufactured by Lion Co., Ltd. can be mentioned. As coconut oil fatty acid amidopropyl betaine, for example, “CAB-30” manufactured by Otsuka Oil & Fat Co., Ltd., Degussa "TEGO BETAIN CK-OK" manufactured by the company is mentioned. Examples of the palm kernel oil fatty acid amidopropyl betaine include “Amholex PB-1” manufactured by Miyoshi Oil & Fat Co., Ltd.

((B22) component)
The component (b22) is a compound represented by the following formula (b22).

(B22) In the formula, R ²¹ is a linear or branched alkyl group having 8 to 18 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms.
The number of carbon atoms in R ²¹ is preferably 10 to 16. If it is in the said range, since the solubility of (b22) component in a cleaning composition will become favorable, precipitation at the time of a preservation | save will not arise easily.
R ²¹ may be a straight chain or a branched chain, and among them, a straight chain is preferable.
R ²¹ is preferably an alkyl group.

R ²² and R ²³ are each independently a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched alkenyl group having 2 to 4 carbon atoms.
The number of carbon atoms of R ²² and ^{R 23,} 1-2 is preferred. If it is in the said range, since the solubility of (b22) component in a cleaning composition will become favorable, precipitation at the time of a preservation | save will not arise easily.
R ²² and R ²³ may be a straight chain or a branched chain, and among them, a straight chain is preferable.
R ²² and R ²³ are preferably an alkyl group.

R ²⁴ is a linear or branched alkylene group having 1 to 6 carbon atoms or a linear or branched hydroxyalkylene group having 1 to 6 carbon atoms.
The number of carbon atoms of R ²⁴ is 1 to 3 are preferred. If it is in the said range, since the solubility of (b22) component in a cleaning composition will become favorable, precipitation at the time of a preservation | save will not arise easily.
R ²⁴ may be a straight chain or a branched chain, and among them, a straight chain is preferable.
R ²⁴ is preferably an alkylene group.

Examples of the component (b22) include coconut oil alkyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, palmityldimethylaminoacetic acid betaine, and stearyldimethylaminoacetic acid betaine. Especially, as a (b22) component, lauryl dimethylamino acetic acid betaine is preferable. These (b22) components may be used individually by 1 type, and may be used in combination of 2 or more type.
The component (b22) is commercially available. Examples of lauryldimethylaminoacetic acid betaine include “Levon LD-36” manufactured by Sanyo Chemical Industries, Ltd. and “Obazoline LB-SF” manufactured by Toho Chemical Industries, Ltd. Examples of stearyldimethylaminoacetic acid betaine include “Amphitol 86B” manufactured by Kao Corporation.

  The nonionic surfactant is not particularly limited, and examples thereof include alcohol ethoxylates represented by the following formula (b31).

_{^{R 31 - (OE) n -OH}} ··· (b31)

(B31) In the formula, R ³¹ is a branched alkyl group. The number of carbon atoms of R ³¹ is from 8 to 18, 12 to 15 is preferred. If it is in the said range, precipitation of the (b31) component at low temperature is hard to produce.
The average number of side chains of R ³¹ (hereinafter sometimes referred to as average branch number) is 0.2 to 2, and preferably 0.4 to 1.5. If it is in the said range, precipitation of the (b31) component at low temperature is hard to produce.

The number (number of branches) of the side chain of R ³¹ is defined as the number obtained by subtracting 1 from the number of methyl groups in the component (b31). The average branch number is a statistical average value of the number of side chains in the component (b31). The average number of methyl groups in the component (b31) is easily measured by ¹ H-NMR spectroscopy. The average branch number in this specification is calculated by the following formula (3). That is, the average number of branches was determined by dividing the signal region corresponding to the methyl proton (CH ₃ group) in the ¹ H-NMR spectrum by 3, and this value and the signal of the methylene proton of the CH ₂ —OH group divided by _2. This is a value obtained by comparing the area.

Average branch number = {(integral value of signal region corresponding to methyl proton of CH ₃ group / 3) − (integral value of signal region corresponding to methylene proton of CH ₂ —OH group / 2)} / (CH ₂ − Integral value of signal region corresponding to methylene proton of OH group / 2) (3)

^{In 1} H-NMR spectroscopy, the measurement target (component (b31)) is dissolved in heavy water or deuterated chloroform, and the sample concentration is set to 30% by mass. This is measured by ¹ H-NMR (JNM-LA300 FT NMR SYSTEM manufactured by JEOL).

In the formula (b31), OE represents an oxyethylene group, and n is a number representing the average number of repeating oxyethylene groups (that is, the average number of moles of ethylene oxide added).
n is preferably from 2 to 7, and more preferably from 2 to 4. If it is in the said range, precipitation of the (b31) component at low temperature is hard to produce.

<(C) component>
Component (C) is a water-soluble solvent. (C) By mix | blending a component, the cleaning composition which improves a detergency and a wiping trace does not remain can be obtained. In addition, it is possible to obtain a cleaning composition that suppresses tearing of toilet paper.
The water-soluble solvent refers to a solvent that is mixed with water at an arbitrary ratio and mixed transparently. Although it will not specifically limit if it is a water-soluble solvent; C2-C3 primary alcohols, such as ethanol and isopropanol; C2-C6 glycols, such as ethylene glycol, propylene glycol, dipropylene glycol; and glycerin, diethylene glycol Examples thereof include polyhydric alcohols having 3 to 8 carbon atoms such as monobutyl ether. Among these, ethanol is particularly preferable from the viewpoint of cleaning power and suppression of toilet paper breakage.
As the type of ethanol, any of synthetic ethanol, fermented ethanol, denatured ethanol, and industrial ethanol may be used.

(C) As for the compounding quantity of a component, 15-75 mass% is preferable with respect to the total mass of a cleaning composition, 15-25 mass% is more preferable, 18-22 mass% is further more preferable.
If the blending amount of the component (C) is 15% by mass or more with respect to the total mass of the cleaning composition, the effect of suppressing the tearing of the toilet paper can be enhanced. You can increase your power.

It is preferable that the mass of the component (A) and the mass of the component (C) satisfy the relationship of the following formula (1).
[Mass of component (A)] / [Mass of component (C)] = 0.12 to 4 (1)
In the formula (1), the mass ratio of the component (A) and the component (C) is more preferably 0.6 to 2.5. When the said mass ratio is less than 0.12, the retention in a non-horizontal plane will fall and a cleaning power may fall. On the other hand, if the mass ratio exceeds 4, the detergency may decrease due to a decrease in the amount of the water-soluble solvent.

Examples of combinations of the components (A) to (C) of the present invention include, for example, a microgel particle group containing deacylated gellan gum and calcium chloride as the component (A), and a secondary sodium alkanesulfonate (B) as the component (B). SAS) and (C) component include a detergent composition containing ethanol.
In addition, for example, (A) component contains deacylated gellan gum, pectin, tricalcium phosphate and magnesium sulfate, (B) component contains lauric acid amidopropyl betaine (LPB), and (C) component contains ethanol. Cleaning agent composition.

<Optional component>
The cleaning composition may contain optional components other than the components (A) to (C) as long as the effects of the present invention are not impaired.
For example, a chelating agent is mentioned, and it contributes to the detergency to dry urine, especially the inorganic component in it. As the chelating agent, ethylenediaminetetraacetic acid (EDTA) or a salt thereof is preferable.
The salt is preferably an alkali metal salt such as sodium salt or potassium salt, ammonium salt, monoethanolamine salt, diethanolamine salt or triethanolamine salt, more preferably sodium salt, potassium salt, monoethanolamine salt or triethanolamine salt. .
EDTA or a salt thereof is commercially available. For example, Akzo Nobel “Dissolvin Z”, “Dissolvin NA”, Kirest “Chirest 3A”, “Chirest 2K”, “Chirest 2B” and the like can be used.

The cleaning composition of the present invention can further contain components that are usually included in the cleaning composition. Examples of such components include preservatives, flavoring agents, plant extracts, pH adjusters and the like.
The cleaning composition of this invention can be manufactured by mixing the said component according to a conventional method.
The cleaning composition of the present invention is used, for example, for cleaning toilet bowls. Specifically, the stock solution can be applied directly or thinly from the storage container and applied to the toilet bowl or its surrounding floor or wall, or filled and sprayed in a spray container, left for a predetermined time if necessary, and then wiped with toilet paper. Can be used.

As for pH of the cleaning composition of this invention, 5-8 are preferable. Examples of the pH adjuster include sulfuric acid and sodium hydroxide.
The pH of the cleaning composition of the present invention is a value measured according to JIS Z8802. Specifically, the liquid detergent composition is adjusted to 25 ° C., and a display value after immersion for 3 minutes using a glass electrode type hydrogen ion concentration indicator (for example, HM-25R, manufactured by Toa DKK Co., Ltd.).

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.
The raw materials used in this example are as shown in <Used raw materials> below.

<Raw materials>
<< (A) component: Microgel particle group >>
[Gelling agent]
Deacylated gellan gum KELCOGEL AFT (manufactured by Sanki Co., Ltd.).
Agar Reagent Agar (Wako Pure Chemical) special grade.
Kappa Carrageenan Reagent κ-Carrageenan (Tokyo Kasei)
Sodium alginate Reagent sodium alginate (Kanto Chemical) deer grade 1.
Pectin reagent (Kanto Chemical).
Native gellan gum KELCOGEL CG-HA (manufactured by Sanki Co., Ltd.).
Comparative product: Xanthan gum Kelzan T (Kelco).
[Crosslinking agent]
Magnesium sulfate reagent Magnesium sulfate heptahydrate (Kanto Chemical) special grade.
Malic acid reagent DL-malic acid (Wako Pure Chemical) special grade.
Calcium chloride reagent Calcium chloride (Wako Pure Chemical) special grade.
Tricalcium phosphate Reagent Tricalcium phosphate (Kanto Chemical) Food additive.
Calcium lactate reagent DL-calcium lactate pentahydrate (Wako Pure Chemicals) first grade.
Citric acid Citric acid (Fuso Chemical).
Calcium gluconate Reagent Calcium gluconate monohydrate (Wako Pure Chemicals) special grade.

Tables 1 and 2 show the composition and average particle diameter of the microgel particle group (component (A)). The preparation method is as follows.
(1) A gelling agent is mixed with purified water, heated and dissolved at 85 to 90 ° C., a crosslinking agent is added, and then forced cooling (cooling rate 0.5 ° C./min), TK Robotics (PRIMIX Corporation) (A) Component was prepared by applying a shearing force (blade tip speed 13 m / s) with a stirrer: homomixer MARK II 2.5 type). The remaining component was mixed and stirred with the component (A) to obtain a cleaning composition.
(2) A gelling agent is mixed with purified water, heated and dissolved at 85 to 90 ° C., and then forcedly cooled (cooling rate: 0.3 ° C./min), TK Robotics (manufactured by PRIMIX Co., Ltd., stirring section: homoxar MARKII) 2.5 type), applying a shearing force (10 m / s), and adding a cross-linking agent while giving a shearing force (blade tip speed 10 m / s) when the liquid temperature is 40 ° C. or less, Prepared. The remaining component was mixed and stirred with the component (A) to obtain a cleaning composition.
As shown in Table 1 and Table 2, the microgel particle group (component (A)) 1-10 is prepared by the preparation method (1), and the microgel particle group (component (A)) 11 is prepared by the preparation method (2 ).

≪ (B) component: surfactant≫
(B11) Component: Secondary sodium alkanesulfonate (SAS, average molecular weight 328), “HOSTAPUR SAS60” (trade name) manufactured by Clariant Japan Co., Ltd.
(B11) A mixture of p + q = 10 to 14 in the formula, corresponding to the component (b11) in which M is sodium and s is 1.
(B11) Component: LAS sodium linear alkylbenzenesulfonate (LAS, linear alkyl group having 10 to 15 carbon atoms) "Taika Power L121" (trade name) manufactured by Teika Co., Ltd. was neutralized with sodium hydroxide and used. .
(B12) Component: Sodium dialkylsulfosuccinate “Ripal 870P” (trade name) manufactured by Lion Specialty Chemicals Co., Ltd.
(B12) In the formula, R1 and R2 are 2-ethylhexyl, Ma is sodium, and t is 1.
(B21) Component: “Enagicol L-30B” (trade name) manufactured by Lion Specialty Chemicals Co., Ltd.
(B22) Component: Lauryldimethylaminoacetic acid betaine “Levon LD-36” (trade name) manufactured by Sanyo Chemical Industries, Ltd.
Used after neutralization with KOH.
(B31) Component: Alcohol ethoxylate “Rutensol AO3” (trade name) manufactured by BASF Japan Ltd.
Rutensol AO3 manufactured by BASF (mixture of 13 and 15 carbon atoms, average branching number 0.8, average repeating number of oxyethylene groups is 3).

≪ (C) component: water-soluble solvent≫
Ethanol reagent Ethanol (Kanto Chemical) 99.5V / V%.
Propanol Reagent 1-Propanol (Wako Pure Chemical) special grade.
Isopropanol Reagent 2-Propanol (Kanto Chemical) special grade.
Butyl carbitol Butyl diglycol (Japanese emulsifier).

≪Optional ingredient≫
Ethylenediaminetetraacetic acid disodium: “Kyrest 2B” (trade name) manufactured by Kyrest Inc. In addition, in the following table | surfaces, it described as EDTA.

[Examples 1 to 29, Comparative Examples 1 to 7]
According to the composition of Tables 3 to 9, the obtained cleaning composition was evaluated by the following evaluation method, and the urine stain cleaning power on the non-horizontal surface, the oil stain cleaning power on the non-horizontal surface, the difficulty of tearing the toilet paper, the remaining wiping trace, and the retention Sex was evaluated. The results are also shown in Tables 3 to 9.
In addition, the unit of content in a table | surface is "mass%", and (A) component is content as a microgel particle group. The other components indicate pure equivalent amounts. “Balance” means that water is blended so that the total blending amount (mass%) of all blending components contained in the composition of each example is 100 mass%.

(Evaluation method)
As the toilet paper, “Kleenex (single)” 11.5 cm × 30 cm manufactured by Nippon Paper Crecia Co., Ltd. was used. For spraying, a sprayer of a wiper cleaner for Look Mame Pika toilet made by Lion was used.

[Cleaning ability of urine stains on non-horizontal surfaces]
200 μL of real urine for 3 adult men was dropped onto a 20 cm × 20 cm tile at a height of 18 cm, and left to dry at room temperature to create a dirty tile. Tilt the dirt tile at 80 °, spray the cleaning composition onto the dirt depositing part with a specified sprayer for 1 push, and after 3 minutes, wipe it off with toilet paper that has been folded into 8 folds. Detergency was evaluated visually.
◎ and ○ are considered good.
A: All fell.
○: Almost fell.
(Triangle | delta): Remaining to the extent that it understands at a glance.
X: Almost remaining / roughness remains.

[Oil stain cleaning power in non-horizontal plane]
In an environment of 25 ° C. and 65% RH (relative humidity), apply 5 mg of red colored triolein to a 19 cm portion from the bottom of a 20 cm × 20 cm tile, incline to 80 °, and clean with a prescribed sprayer. The composition was sprayed for 1 push, wiped with 1 g of tissue paper folded in 8 after 3 minutes, and the remaining degree of dirt was visually observed and the remaining roughness was evaluated by touch.
◎ and ○ are considered good.
A: All fell.
○: Almost fell.
(Triangle | delta): Remaining to the extent that it understands at a glance.
X: Almost remaining / roughness remains.

[Difficult to tear toilet paper]
The cleaning liquid was sprayed onto a 20 cm × 20 cm tile with a predetermined sprayer, and the entire cushion floor was wiped evenly while impregnating the cleaning liquid into eight folded toilet paper. The degree of tearing of the toilet paper after wiping was visually evaluated.
◎ and ○ are considered good.
A: Not torn.
○: Although only a part was torn, I was hardly interested.
Δ: Clearly torn.
X: Tattered.

[Wipe trace remaining]
A 20 cm × 20 cm tile was sprayed with 1 push of the cleaning liquid with a predetermined sprayer, wiped with a toilet paper folded eight times in a circle, and the remaining condition of the wiping marks was visually evaluated.
◎ and ○ are considered good.
A: No wiping marks remain.
○: Slightly thin linear wiping marks remain, but do not bother.
Δ: There are linear wiping marks and foam residue.
X: A wiping mark remains on the entire surface.

[Residence]
A 20 cm × 20 cm tile was tilted at 80 degrees, and the cleaning liquid was sprayed by one push with a predetermined sprayer at a position of 18 cm in height, and the time for the cleaning liquid to sag to the lowest point of the tile was measured.
◎ and ○ are considered good.
A: The cleaning liquid stays on the tile for 3 minutes or more.
○: The cleaning liquid stays on the tile for 1 minute or longer.
Δ: The cleaning liquid stays on the tile for 30 seconds or more.
X: The cleaning liquid stays on the tile for less than 30 seconds.

As shown in Table 2 to Table 5, Examples 1 to 29 to which the present invention was applied were “◎” or “◯” in all evaluation items, and were good.
On the other hand, in Comparative Examples 1 and 2 using a comparative product instead of the microgel particle group, the remaining wiping trace was “Δ”.
In Comparative Example 3 in which the surfactant content was less than the lower limit, the cleaning power in the non-horizontal plane was “x”, and in Comparative Example 4 in which the upper limit was exceeded, the remaining wiping trace was “x”.
In Comparative Example 5 in which the content of the water-soluble solvent was less than the lower limit, the toilet paper was difficult to break, and in Comparative Example 6 that exceeded the upper limit, the detergency and retention in the non-horizontal plane were “△”. .
In Comparative Example 7 containing no microgel particle group, the detergency and retention in the non-horizontal plane were “x”.

  From these results, it was found that according to the cleaning composition of the present invention, tearing of the toilet paper can be suppressed, the cleaning power is improved, and it is difficult to leave a wiping mark.

Claims (3)

It contains a crosslinked product formed from one or two or more gelling agents selected from agar, gellan gum, carrageenan, pectin and sodium alginate and a crosslinking agent, and has an average particle size of 0.01 μm or more and 1,000 μm In the detergent composition containing less than microgel particle group (A), surfactant (B), and water-soluble solvent (C),
The mass of the component (B) relative to the total mass of the cleaning composition is 0.1 to 5% by mass,
The mass of the said (C) component with respect to the gross mass of a cleaning composition is a cleaning composition which is 15-75 mass%. The mass of the gelling agent is 0.005 to 1% by mass with respect to the total mass of the cleaning composition.
The cleaning composition according to claim 1. The mass of the component (A) and the mass of the component (C) satisfy the relationship of the following formula (1).
The cleaning composition according to claim 1 or 2.
[Mass of component (A)] / [Mass of component (C)] = 0.12 to 4 (1)