JP6118670B2 - Liquid cleaner for wiping - Google Patents

Description

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

Due to the recent increase in hygiene and cleanliness awareness, many products have been sold that are aimed at controlling bacteria and odors. In addition, the awareness of shortening the housework time and improving efficiency has increased, and an increasing number of consumers have used toilet paper, tissue paper, kitchen paper, etc. as wipes when they noticed dirt.
In terms of hygiene technology, approaches to bacteria by using cationic surfactants are common, but when used in combination with anionic surfactants, it has been difficult to fully exert the effect.

As a cleaning agent for wiping and cleaning that does not require wiping twice, for example, Patent Document 1 contains an amphoteric surfactant alkylbetaine, at least one of ethanol and isopropanol, water, and an additive such as a disinfectant. An aqueous detergent composition is disclosed.
Patent Document 2 discloses a disinfectant cleaning composition for toilets containing a surfactant and polyhexamethylene guanidine hydrochloride having a specific structure as a cationic fungicide.

JP 09-53091 A JP 2012-162635 A

However, in the case of the cleaning compositions described in Patent Documents 1 and 2, although there are temporary sterilization effects and bactericidal effects, it is difficult to suppress the growth of bacteria and the generation of odors.
In addition, cleaning agents that do not require wiping twice are required not only to have cleaning power but also to be sticky to the object to be cleaned after wiping and cleaning, and to leave no wiping marks. Yes.
There are various techniques that can solve any of these problems and requirements, but no cleaning agent that satisfies all of these has been proposed.

  The present invention has been made in view of the above circumstances, and is a liquid cleaning agent for wiping that has excellent detergency, can suppress the growth of bacteria and odors, has no stickiness or sliminess, and is less likely to leave wiping marks. The purpose is to provide.

The present invention has the following aspects.
[1] 0.1 to 5% by mass of a surfactant (A) containing at least an anionic surfactant (A1) and at least one selected from copper, manganese, nickel, cobalt, iron and zinc (B) And at least one chelating agent (C) selected from a compound represented by the following general formula (c1) and a compound represented by the following general formula (c2), and a biguanide polymer (D) Liquid cleaning agent for wiping off.

In the formula (c1), X ^{11 to} X ¹⁴ each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, or a cationic ammonium, R ¹¹ represents a hydrogen atom or a hydroxy group, and n1 is 0 or 1 Represents an integer.

In formula (c2), A represents an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxy group, or a hydrogen atom, and X ^{21 to} X ²³ each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, or Represents cationic ammonium, and n2 represents an integer of 0 to 5.

  The liquid detergent for wiping of the present invention is excellent in detergency, can suppress the growth of bacteria and the generation of odors, has no stickiness or sliminess, and hardly leaves a wiping mark.

The liquid cleaning agent for wiping of the present invention is at least selected from surfactant (A) (hereinafter sometimes referred to as “component (A)”) and copper, manganese, nickel, cobalt, iron and zinc. 1 type (B) (hereinafter also referred to as “component (B)”), chelating agent (C) (hereinafter also referred to as “component (C)”), biguanide polymer (D) (Hereinafter also referred to as “component (D)”).
Hereinafter, each component will be described.

<(A) component>
The component (A) is a surfactant. As the liquid cleaning agent for wiping contains the component (A), it is possible to remove dirt and odor components adhering to the object to be cleaned (object to be cleaned) before wiping and cleaning, and to improve deodorizing and deodorizing effects. Can be planned. This is because, in the liquid detergent for wiping, the (A) component forms an association with the (D) component, and this association takes in the complex formed by the (B) and (C) components. Thus, it is considered that the adsorbing power of the liquid detergent for wiping on the article to be washed after wiping and washing improves the antibacterial and deodorizing effects.

The component (A) includes at least an anionic surfactant (A1) (hereinafter sometimes referred to as “component (A1)”).
As the component (A1), a conventionally known anionic surfactant can be used. For example, alkyl sulfate, alcohol ethoxy sulfate, alkylbenzene sulfonic acid, α-sulfo fatty acid, α-olefin sulfonic acid, alkyl sulfonate, alkyl taurate, soap, Examples thereof include alkyl ethoxycarboxylates, acyl alaninates, alkyl phosphates, dialkyl sulfosuccinic acids, alkane sulfonic acids, alkyl iminodiacetic acids, and salts thereof. Examples of the salt include alkali metal salts such as sodium and potassium, amine salts and ammonium salts. Among these, alkane sulfonates and dialkyl sulfosuccinates are preferable from the viewpoint of excellent removal of dirt and odor components and high deodorizing and deodorizing effects. In addition, alcohol ethoxy sulfate is preferable from the viewpoint that wiping traces hardly remain.
These (A1) components may be used individually by 1 type, and may use 2 or more types together.

As the alkane sulfonate, a secondary alkane sulfonate (hereinafter sometimes referred to as “SAS”) is preferable.
SAS is a surfactant, also called “paraffin sulfonate”, and is usually provided in the form of a mixture of secondary alkyl sulfonates having 10 to 21 carbon atoms per molecule. In the present invention, the mixture preferably contains 80% by mass or more, and more preferably 90% by mass or more of the secondary alkyl sulfonate having 13 to 18 carbon atoms per molecule. Note that this mixture may contain a small amount of a primary alkyl sulfonate, disulfonate, or polysulfonate.
As SAS, the compound represented by the following general formula (a1) is preferable.

In the formula (a1), p + q = 10 to 14, and M ⁺ is a counter ion.
That is, the compound represented by the formula (a1) is a secondary alkyl sulfonate having 13 to 17 carbon atoms (however, the carbon number in M in the formula (a1) is not included).
When p + q is 10 or more, the detergency, particularly the detergency against oil stains, is further improved. On the other hand, when p + q is 14 or less, the solubility of the compound itself represented by the formula (a1) is improved, so that precipitation during storage is suppressed.

  Examples of M as a counter ion include alkali metals, alkaline earth metals, ammonium, and alkanolamines. 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. Among these, alkali metals are preferable, and sodium is particularly preferable.

  Commercially available products can be used as the SAS. For example, “HOSTAPUR SAS30A” and “HOSTAPUR SAS60” manufactured by Clariant Japan Co., Ltd. (both have a content of sodium alkyl secondary sulfonate having 13 to 17 carbon atoms of 90% by mass). Above); “MERSOL80” manufactured by Bayer (the content of sodium secondary alkyl sulfonate having an average of 15 carbon atoms and 13 to 17 carbon atoms of 80% by mass or more); “MARRON PS65” and “MARON PS60” manufactured by SASOL ”,“ MALLON PS60W ”(all of which contain a sodium alkyl secondary sulfonate having 13 to 17 carbon atoms in an amount of 90% by mass or more).

  Examples of the dialkyl sulfosuccinate include dialkyl (6 to 18 carbon atoms) sulfosuccinic acid ester salts (for example, sodium di-2-ethylhexyl sulfosuccinate), (poly) oxyethylene (average number of repetitions = 1 to 50) dialkyl (carbon number) 8-24) sulfosuccinic acid ester salts (for example, di-polyoxyethylene (average number of repetitions = 2 to 20) sodium lauryl sulfosuccinate, etc.).

  As the alcohol ethoxy sulfate, for example, any one of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1), Examples include alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added with an average of 0.5 to 10 mol.

  In addition to the component (A1), the component (A) is an amphoteric surfactant (A2) (hereinafter also referred to as “(A2) component”), a nonionic surfactant (A3) (hereinafter referred to as “( A3) component ”) and semipolar surfactant (A4) (hereinafter also referred to as“ (A4) component ”). Furthermore, (A) component can contain the surfactant used for a normal cleaning agent besides (A1)-(A4) component.

When the liquid detergent for wiping contains the component (A2), the detergency for dry urine is improved. In addition, the object to be cleaned after wiping and cleaning is not sticky or sticky, and wiping marks are less likely to remain.
As the component (A2), a conventionally known amphoteric surfactant can be used, and it is selected from a compound represented by the following general formula (a2-1) and a compound represented by the following general formula (a2-2). At least one is preferred.

In formula (a2-1), R ³¹ represents an alkyl group or alkenyl group having 8 to 20 carbon atoms, R ³² represents an alkylene group having 1 to 5 carbon atoms, and R ³³ and R ³⁴ are each independently, represents a hydrogen atom or an alkyl group having 1 to 3 carbon ^{atoms, R 35} represents an alkylene group having 1 to 5 carbon atoms.

In formula (a2-1), the alkyl group and alkenyl group of R ³¹ may be linear or branched. R ³¹ is preferably a linear or branched alkyl group or alkenyl group having 10 to 16 carbon atoms, and more preferably a linear alkyl group.
The alkylene group for R ³² may be linear or branched. R ³² is preferably a linear or branched alkylene group having 1 to 3 carbon atoms, and more preferably a linear alkylene group. The alkylene group for R ³² may be unsubstituted or a part of the hydrogen atoms may be substituted with a substituent, but is preferably unsubstituted. Examples of the substituent include alkyl groups such as methyl group and ethyl group, and hydroxy groups.
The alkyl group of R ³³ and R ³⁴ may be linear or branched. R ³³ and R ³⁴ are preferably each independently a linear or branched alkyl group having 1 to 3 carbon atoms. R ³³ and R ³⁴ may be the same or different. In particular, it is preferable that both R ³³ and R ³⁴ are linear alkyl groups having 1 to 3 carbon atoms.
The alkylene group for R ³⁵ may be linear or branched. R ³⁵ is preferably a linear or branched alkylene group having 1 to 3 carbon atoms, and more preferably a linear alkylene group. The alkylene group for R ³⁵ may be unsubstituted or a part of the hydrogen atoms may be substituted with the above-described substituents, but those that are unsubstituted are preferred.

Specific examples of the compound represented by the formula (a2-1) include lauric acid amidopropyl betaine, octylamidopropyl-N, N-dimethylacetic acid betaine, laurylamidopropyl-N, N-dimethylacetic acid betaine, stearyl-N. , N-dimethylacetic acid betaine, stearyl-N, N-dimethyl-2-hydroxypropyl betaine, and the like. Among these, lauric acid amidopropyl betaine is particularly preferable.
As the compound represented by the formula (a2-1), a commercially available product can be used. For example, as lauric acid amidopropyl betaine, “Enazicol L-30B” manufactured by Lion Corporation; coconut oil fatty acid amidopropyl betaine, "CAB-30" manufactured by Yushi Kogyo Co., Ltd .; "TEGO BETAIN CK-OK" manufactured by Degussa as palm oil fatty acid amidopropyl betaine; "Amho" manufactured by Miyoshi Oil Co., Ltd. as palm kernel fatty acid amidopropyl betaine Rex PB-1 ".

In formula (a2-2), R ⁴¹ represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, and R ⁴² and R ⁴³ each independently represents an alkyl group or alkenyl group having 1 to 4 carbon atoms. , R ⁴⁴ represents an alkylene group having 1 to 6 carbon atoms or a hydroxyalkylene group.

In formula (a2-2), the alkyl group and alkenyl group of R ⁴¹ may be linear or branched. R ⁴¹ is preferably a linear or branched alkyl group or alkenyl group having 10 to 16 carbon atoms, and more preferably a linear alkyl group.
The alkyl group and alkenyl group of R ⁴² and R ⁴³ may be linear or branched. R ⁴² and R ⁴³ are each independently preferably a linear or branched alkyl group or alkenyl group having 1 to 3 carbon atoms, and more preferably a linear alkyl group. R ⁴² and R ⁴³ may be the same or different. In particular, R ⁴² and R ⁴³ are preferably both linear alkyl groups having 1 to 3 carbon atoms.
The alkylene group and hydroxyalkylene of R ⁴⁴ may be linear or branched. R ⁴⁴ is preferably a linear or branched alkylene group having 1 to 3 carbon atoms or a hydroxyalkylene group, and more preferably a linear alkylene group.

Specific examples of the compound represented by the formula (a2-2) include coconut oil alkyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, palmityldimethylaminoacetic acid betaine, and stearyldimethylaminoacetic acid betaine. Among these, lauryldimethylaminoacetic acid betaine is particularly preferable.
A commercially available product can be used as the compound represented by the formula (a2-2). For example, as lauryldimethylaminoacetic acid betaine, “Levon LD-36” manufactured by Sanyo Chemical Industries, Ltd., manufactured by Toho Chemical Industries, Ltd. “Obazoline LB-SF”; examples of stearyldimethylaminoacetic acid betaine include “Amphitol 86B” manufactured by Kao Corporation.

  As the component (A2), lauric acid amidopropyl betaine and lauryldimethylaminoacetic acid betaine are particularly preferable.

  As the component (A3), a conventionally known nonionic surfactant can be used. For example, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, alkyl polyglucoside, fatty acid polyglycerol ester , Fatty acid sucrose ester, fatty acid alkanolamide and the like. Among these, alkylpolyglucoside is preferable.

As the component (A4), a conventionally known semipolar surfactant can be used.
Here, the “semipolar surfactant” is a surfactant having a semipolar bond (a bond having a property intermediate between a nonpolar bond and a polar bond), and a solution in which the semipolar surfactant is dissolved. Or it becomes cationic, anionic, or bipolar depending on the pH of the dispersion.
Examples of the component (A4) include alkylamine oxides such as dodecyldimethylamine oxide, myristyldimethylamine oxide, and coconut alkyldimethylamine oxide; amide amine oxides such as coconut oil fatty acid amidepropylamine oxide and lauric acid amidepropylamine oxide. .

  The content of the component (A) in 100% by mass of the liquid detergent for wiping is 0.1 to 5% by mass, preferably 0.3 to 3% by mass, and 0.7 to 2.2% by mass. More preferred. When the content of the component (A) is less than the lower limit, sufficient detergency cannot be obtained. On the other hand, when the content of the component (A) is more than the above upper limit value, it becomes difficult to suppress stickiness and sliminess during wiping and cleaning, and wiping marks are likely to remain.

  Moreover, 10 mass% or more is preferable, as for content of (A1) component in (A) component 100 mass%, 20-80 mass% is more preferable, and 40-60 mass% is further more preferable. If the content of the component (A1) is less than the lower limit, the detergency may be insufficient. On the other hand, if the content of the component (A1) is more than the above upper limit value, the wiping trace may be easily left. Moreover, there exists a possibility that antibacterial power may become inadequate.

<(B) component>
The component (B) is at least one selected from copper, manganese, nickel, cobalt, iron, and zinc. Since the liquid cleaning agent for wiping contains the component (B), it exhibits excellent deodorizing and deodorizing effects. This is presumably because the component (B) forms a complex with the component (C) in the liquid detergent for wiping, and this complex suppresses the growth of microorganisms or adsorbs odors.

  (B) As a component, manganese, copper, or zinc is preferable, copper or zinc is more preferable, and zinc is further more preferable. By using these components (B), the deodorizing and deodorizing effects can be further enhanced.

  (B) A component may be mix | blended as various metal compounds, and may be mix | blended as a complex with (C) component mentioned later. However, it is preferable to blend the component (B) as a metal compound from the viewpoint of aesthetics of the liquid detergent for wiping, production efficiency, and the like.

  Any metal compound may be used as long as it dissolves in water. Examples of salts forming the metal compound include nitrates, sulfates, chlorides, perchloric acid peroxides, ammonium chlorides, cyanides, and other inorganic salts and acetates. , Organic salts such as gluconate, tartrate, glycine salt and the like.

The manganese compound is not particularly limited as long as it releases manganese ions in water, and examples thereof include manganese nitrate, manganese sulfate, manganese chloride, manganese acetate, manganese perchlorate, and manganese acetylacetonate. Among these, manganese sulfate and manganese chloride are preferable in terms of handleability, cost, raw material supply property, and the like.
The copper compound is not particularly limited as long as it releases copper ions in water. For example, copper nitrate, copper sulfide, copper sulfate, copper chloride, copper acetate, copper cyanide, copper ammonium chloride, copper gluconate, Examples include copper tartrate and copper perchlorate. Among these, copper sulfate, copper chloride, and copper gluconate are preferable and copper sulfate is more preferable in terms of handleability, cost, raw material supply property, and the like.
The zinc compound is not particularly limited as long as it releases zinc ions in water. For example, zinc nitrate, zinc sulfide, zinc sulfate, zinc chloride, zinc acetate, zinc cyanide, ammonium zinc chloride, zinc gluconate, Examples include zinc tartrate and zinc perchlorate. Among these, zinc sulfate, zinc chloride, and gluconate are preferable, and zinc sulfate is more preferable in terms of handling property, cost, raw material supply property, and the like.

  Content of (B) component in 100 mass% of liquid cleaning agents for wiping off can be determined in consideration of the kind of (B) component, for example, 0.1-5 mass% is preferable. If the content of component (B) is less than the above lower limit, the deodorizing / deodorizing effect may be insufficient. On the other hand, if the content of the component (B) is more than the above upper limit value, the wiping trace may be easily left.

For example, when using manganese as the component (B), the content of manganese in 100% by mass of the liquid detergent for wiping is preferably 0.001 to 0.5% by mass, and 0.01 to 0.3% by mass Is more preferable, and 0.02-0.15 mass% is further more preferable. It is because there exists a possibility that the deodorizing effect may become inadequate that content of manganese is less than the said lower limit, and the further improvement of a deodorizing effect may not be aimed at even if it exceeds the said upper limit.
Or when using copper as (B) component, 0.001-0.5 mass% is preferable, and, as for content of copper in 100 mass% of liquid detergents for wiping, 0.01-0.3 mass% Is more preferable, and 0.02-0.15 mass% is further more preferable. It is because there exists a possibility that a deodorizing effect may become inadequate that content of copper is less than the said lower limit, and the further improvement of a deodorizing effect may not be aimed at even if it exceeds the said upper limit.
Further, for example, when zinc is used as the component (B), the content of zinc in 100% by mass of the liquid detergent for wiping is preferably 0.002 to 2% by mass, more preferably 0.02 to 1% by mass. Preferably, 0.05 to 0.5% by mass is more preferable. It is because there exists a possibility that the deodorizing effect may become inadequate that content of zinc is less than the said lower limit, and the further improvement of a deodorizing effect may not be aimed at even if it exceeds the said upper limit.

  (B) When mix | blending a component as a complex with (C) component, a complex can be manufactured with the manufacturing method of the complex as described in international publication 09/078459, for example.

<(C) component>
The component (C) is at least one chelating agent selected from a compound represented by the following general formula (c1) and a compound represented by the following general formula (c2). These chelating agents are aminocarboxylic acid type sequestering agents that form a complex with the component (B). Since the liquid cleaning agent for wiping contains the component (C), an excellent deodorizing and deodorizing effect is exhibited.

In the formula (c1), X ^{11 to} X ¹⁴ each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, or a cationic ammonium, R ¹¹ represents a hydrogen atom or a hydroxy group, and n1 is 0 or 1 Represents an integer.

In formula (c1), examples of the alkali metal in X ^{11 to} X ¹⁴ include sodium and potassium. Examples of the alkaline earth metal include calcium and magnesium. In addition, when at least one of X ^{11 to} X ¹⁴ is an alkaline earth metal, it corresponds to 1/2 atom. For ^example, if ^{X 11} is calcium, -COOX ¹¹ is ^"- 1/2 (Ca) ^- COO".
Examples of the cationic ammonium include alkanolamines such as monoethanolamine and diethanolamine, and examples include those in which 1 to 3 hydrogen atoms of ammonium are substituted with alkanol groups. As for carbon number of an alkanol group, 1-3 are preferable.
Among ^them, X 11 ^{to X 14} are the alkali metal is preferable.
X ^{11 to} X ¹⁴ in the formula (c1) may be the same or different from each other.

R ¹¹ in formula (c1) may be either a hydrogen atom or a hydroxy group.
N1 in the formula (c1) is preferably 1.

  Examples of the compound represented by the formula (c1) include iminodisuccinic acid, 3-hydroxy-2,2'-iminodisuccinic acid, and salts thereof. Examples of the salt include alkali metal salts such as sodium salt and potassium salt, and alkanolamine salts such as monoethanolamine salt and diethanolamine salt. Among these, sodium salt or potassium salt is more preferable.

In formula (c2), A represents an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxy group, or a hydrogen atom, and X ^{21 to} X ²³ each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, or Represents cationic ammonium, and n2 represents an integer of 0 to 5.

In formula (c2), the alkali metal, alkaline earth metal, and cationic ammonium in X ^{21 to} X ²³ are the same as the alkali metal, alkaline earth metal, and cationic ammonium in X ^{11 to} X ¹⁴ , respectively. Is mentioned. X ^{21 to} X ²³ are preferably alkali metals.
X ^{21 to} X ²³ in the formula (c2) may be the same or different from each other.

The alkyl group in A of formula (c2) may be linear or branched. 1-30 are preferable and, as for carbon number of an alkyl group, 1-18 are more preferable. In the alkyl group, a part of the hydrogen atoms may be substituted with a substituent. Examples of the substituent include a sulfo group (—SO ₃ H), an amino group (—NH ₂ ), a hydroxy group, and a nitro group (—NO ₂ ).
A may be any of an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxy group, and a hydrogen atom, and is preferably a hydrogen atom.
N2 in the formula (c2) is preferably an integer of 0 to 2, and more preferably 1.

  Examples of the compound represented by the formula (c2) include nitrilotriacetic acid, methylglycine diacetic acid, dicarboxymethyl glutamic acid, L-aspartic acid-N, N-diacetic acid, serine diacetic acid, hydroxyethyliminodiacetic acid, or their Examples include salts. Among these, nitrilotriacetic acid, methyl glycine diacetic acid, dicarboxymethyl glutamic acid, L-aspartic acid-N, N-diacetic acid or a salt thereof is preferable, and methyl glycine diacetic acid or a salt thereof is more preferable. Examples of the salt include alkali metal salts such as sodium salt and potassium salt, and alkanolamine salts such as monoethanolamine salt and diethanolamine salt. Among these, sodium salt or potassium salt is preferable.

These (C) components may be used individually by 1 type, and may use 2 or more types together.
Although content of (C) component in 100 mass% of liquid cleaning agents for wiping off is not specifically limited, 0.1-5 mass% is preferable, 0.2-2 mass% is more preferable, 0.2- 0.5 mass% is further more preferable. If content of (C) component is in the said range, a deodorizing and deodorizing effect can be improved more.

  Further, the molar ratio of the metal ion in the component (B) to the component (C) (hereinafter sometimes referred to as “(B) / (C) molar ratio”) is preferably 0.3 to 5, preferably 4-3 are more preferable, 0.5-2 are still more preferable, and 1 is especially preferable. When the (B) / (C) molar ratio is within the above range, the deodorizing / deodorizing effect and antibacterial activity can be further enhanced.

<(D) component>
The component (D) is a biguanide polymer.
By using the component (D) and the component (A) in combination, the antibacterial power and the deodorizing / deodorizing effect are enhanced. The reason for exhibiting excellent antibacterial activity and excellent deodorizing / deodorizing effect by using the component (A) and the component (D) in combination is not clear, but is presumed as follows.
In the liquid detergent for wiping, the component (A) and the component (D) form an aggregate (hereinafter also referred to as “AD aggregate”). This AD aggregate is more easily adsorbed to the object to be cleaned than the component (D) alone. For this reason, an antibacterial effect is exhibited by the (D) component adhering to a to-be-washed object as an AD aggregate.
In addition, in high humidity conditions where bacteria are likely to grow, microorganisms metabolize dirt that could not be removed by washing to produce malodorous components. (D) component adhering to to-be-washed | cleaned material is considered that it contributes also to a deodorizing effect by suppressing increase in bacteria by the microbe growth inhibitory effect.
Furthermore, the AD aggregate takes in the complex formed by the component (B) and the component (C), and an excellent deodorizing / deodorizing effect is exhibited by a synergistic effect with the complex.

  As the component (D), for example, a biguanide compound such as a polyalkylene biguanide compound represented by the following general formula (d1) is preferable.

In formula (d1), n5 represents the average number of repeating units represented by [(CH ₂ ) ₃ —NH—C (NH) —NH—C (NH) —NH— (CH ₂ ) ₃ ] It is the number of ~ 40, Preferably it is 2-14, More preferably, it is 11-13, More preferably, it is 12. If n5 is not less than the above lower limit, the component (D) forms an association with the component (A) incorporating the complex formed by the component (B) and the component (C), and It becomes easy to be adsorbed. For this reason, the deodorizing and deodorizing effect can be further enhanced in addition to the fungus growth suppressing effect.
If the average of n5 is below the said upper limit, the solubility of the component (D) in water will be good, and the liquid stability over time of the liquid detergent for wiping can be improved.

  In the formula (d1), HY represents an organic acid or an inorganic acid, preferably hydrochloric acid, gluconic acid, or acetic acid, and more preferably hydrochloric acid.

  In formula (d1), m5 may be the same as or different from n5. Since HY partially binds to the nitrogen atom of the biguanide group to form a salt, n5 and m5 may be different.

As the component (D), a commercially available product can be used. Polyhexamethylene in which n5 of the formula (d1) is 12, HY is HCl, and an aqueous dispersion (pH 4.5) having a pure content of 20% by mass. Biguanide hydrochloride (manufactured by Arch Chemicals Japan, “Proxel IB (registered trademark)”) and the like.
These (D) components may be used individually by 1 type, and may use 2 or more types together.

  The content of the component (D) in 100% by mass of the liquid cleaning agent for wiping is preferably 0.002 to 1% by mass, more preferably 0.005 to 0.1% by mass, and 0.008 to 0.02. More preferred is mass%. When the content of the component (D) is less than the lower limit, antibacterial activity may be insufficient. On the other hand, when the content of the component (D) is more than the above upper limit value, the cleaning power may be insufficient and a wiping mark may remain.

  Moreover, 1-500 are preferable and, as for mass ratio (henceforth "(A1) / (D) mass ratio") represented by (A1) component / (D) component, 10-200 is more. Preferably, 50 to 125 is more preferable. If the mass ratio (A1) / (D) is within the above range, the complex of the component (B) and the component (C) is adsorbed to the object to be washed and remains through the AD aggregate. Therefore, the deodorizing and deodorizing effect can be further enhanced. In addition, the balance between the cleaning power and the antibacterial power is improved.

<Optional component>
The liquid cleaning agent for wiping contains a solvent in addition to the components (A) to (D). Moreover, you may contain the normal additive used for the cleaning agent for wiping cleaning.
Examples of the solvent include water and water-soluble solvents.
The water-soluble solvent is not particularly limited as long as it is mixed with water at an arbitrary ratio and transparently mixed. For example, primary alcohols having 2 to 3 carbon atoms such as ethanol and isopropanol; ethylene glycol, propylene glycol, dipropylene Examples thereof include glycols having 2 to 6 carbon atoms such as glycol; polyhydric alcohols having 3 to 8 carbon atoms such as glycerin and diethylene glycol monobutyl ether. Among these, ethanol is preferable from the viewpoint of the influence of the liquid detergent for wiping on the aroma, the difficulty of tearing the toilet paper, and the price.
These solvents may be used alone or in combination of two or more.

  When ethanol is used as the water-soluble solvent, the content of ethanol in 100% by mass of the liquid detergent for wiping is preferably 15% by mass or more, more preferably 15 to 25% by mass, and further preferably 18 to 22% by mass. . If the content of ethanol is less than the above lower limit value, when wiping and cleaning is performed using a wiping tool that is easy to tear, such as toilet paper, the wiping tool may be torn, and even if the upper limit value is exceeded, the tear suppression effect This is because there is a possibility that the further improvement cannot be achieved.

  Examples of additives include fragrances, pigments, viscosity modifiers, pH adjusters, thickeners, surface modifiers, antioxidants, ultraviolet absorbers, solubilizers, chelating agents (excluding the component (C)) .), Polymer compounds, preservatives, antibacterial agents, natural products extracts, dispersants and the like.

<Manufacturing method>
It does not restrict | limit especially as a manufacturing method of the liquid detergent for wiping off, For example, it manufactures by mixing a (A)-(D) component, a solvent, and an additive as needed. At this time, it is preferable to adjust the pH of the liquid detergent for wiping with a pH adjuster or the like so that the pH of the liquid detergent for wiping becomes pH 3 to 11.
Examples of the acid used for lowering the pH include inorganic acids such as hydrochloric acid and sulfuric acid; and carboxylic acids such as acetic acid and citric acid. On the other hand, examples of the alkali used for raising the pH include alkali metal salts such as sodium hydroxide and potassium hydroxide; alkanolamines such as triethanolamine. Among these, citric acid is preferable as the acid and potassium hydroxide is preferable as the alkali in that the wiping marks are less likely to remain.

<Washing method>
As a method for cleaning an object to be cleaned using the liquid cleaning agent for wiping of the present invention, for example, a liquid cleaning agent for wiping is accommodated in a trigger sprayer and discharged from the trigger sprayer in a foam form to be covered. The method of washing | cleaning a to-be-washed object by wiping off the apply | coated site | part with a wiping tool after apply | coating to washing | cleaning thing and leaving it as it is right after that or suitably is mentioned. Alternatively, a liquid cleaning agent for wiping may be applied to the wiping tool to wipe off dirt or the like adhering to the object to be cleaned.
The wiping liquid cleaning agent of the present invention is different from a laundry cleaning agent for textiles such as clothing.

The object to be washed is not particularly limited as long as it can be applied by discharging a liquid detergent for wiping from a trigger sprayer. For example, clothes, bath towels, handkerchiefs, tablecloths, placemats, curtains, etc. , Textile products such as sofas and carpets; and hard surfaces such as kitchenware, bathrooms, toilets, living floors, walls and furniture. Among them, the liquid cleaning agent for wiping of the present invention is particularly suitable for cleaning a place or an object that is difficult to wash away with water.
Examples of the wiping tool include cloth products; paper products such as toilet paper, tissue paper, and kitchen paper. In particular, if the liquid detergent for wiping contains ethanol, paper products such as toilet paper are difficult to tear during wiping.

The trigger sprayer is not particularly limited, and generally includes those used in a detergent product (a trigger sprayer containing a detergent composition).
Specifically, any liquid cleaning agent that can be wiped off in a mist form may be used. Moreover, the thing which is provided with a foam formation function and can switch between these which can be discharged in a mist form or a foam form may be used. Moreover, the thing which can switch between the wide pattern which discharges the liquid cleaning agent for wiping in a wide range, and the narrow pattern discharged in a narrow range may be used.

<Effect>
According to the liquid cleaning agent for wiping of the present invention described above, due to the interaction of the components (A) to (D), the cleaning power is excellent, and the growth of bacteria and the generation of odor can be suppressed.
The reason why the liquid detergent for wiping of the present invention is excellent in antibacterial activity and deodorizing / deodorizing effect is not clear, but is presumed as follows.
In the liquid detergent for wiping, the component (B) and the component (C) form a complex (hereinafter also referred to as “metal complex”). Since this metal complex has lower water solubility than the component (B) and the component (C), the metal complex is easily incorporated into the AD aggregate. The metal complex taken into the AD aggregate is easily and firmly adsorbed to the object to be washed and remains as compared with the metal complex alone.
In the vicinity of the component (B) of the metal complex adsorbed on the object to be washed, the ligand (C) and the water coordinated with the component (B) are easily replaced with other substances. It is thought that it has become. For this reason, in the metal complex adsorbed on the object to be washed, the positively charged odor is substituted with the component (B) and combined with the (C) component in the metal complex, and the negatively charged odor is water. Or it is thought that it substitutes with (C) component and couple | bonds with (B) component in a metal complex. Thus, it is estimated that a metal complex captures an odor component well.
And it is thought that various odors, such as a fatty acid type, an amine type, and a thiol type, can be deodorized.
Furthermore, the effect that the odor component is captured by the metal complex is continuously exhibited. Therefore, the growth of bacteria and the generation of odor can be suppressed for a long time.

Moreover, since the liquid cleaning agent for wiping of the present invention has a component (A) content of 5% by mass or less, there is no stickiness or sliminess after wiping and cleaning, and wiping marks are difficult to remain.
In particular, if the liquid detergent for wiping contains the component (A2), the effect of suppressing stickiness and stickiness is enhanced, and the wiping marks are less likely to remain.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description. In addition, the compounding quantity of the component used in each example is a pure conversion value unless there is particular notice.

"Raw material"
As the component (A), the following compounds were used.
-(A1-1): Secondary alkane sulfonate sodium (SAS) (manufactured by Clariant Japan KK, “HOSTAPUR SAS60”, average molecular weight 328)
-(A1-2): Sodium polyoxyethylene alkyl ether sulfate ester (AES) (manufactured by Lion Corporation, “Sannol TD-3130”)
・ (A2-1): Amidopropyl betaine laurate (LPB) (manufactured by Lion Corporation, “Enagicol L-30B”)
(A2-2): lauryldimethylaminoacetic acid betaine (LDB) (manufactured by Sanyo Chemical Industries, Ltd., “Levon LD-36”)
(A3-1): alkyl polyglucoside (APG) having 12 to 16 carbon atoms (manufactured by Cognis, “PLANTACARE 1200up”)
-(A3-2): C8-10 alkyl polyglucoside (APG) (BASF Japan, "GLUCOPON 215up")
(A4-1): Dodecyldimethylamine oxide (AX) (manufactured by Lion Akzo, “Aromox DM12D-W (C)”)

As the component (B), the following compounds were used.
-(B-1): Zinc sulfate heptahydrate (manufactured by Kanto Chemical Co., Inc.)

As the component (C) and the substitute for the component (C) (component (C ′)), the following compounds were used.
(C-1): Trisodium methylglycine diacetate (MGDA) (manufactured by BASF)
-(C'-1): Ethylenediaminetetraacetic acid (EDTA) (manufactured by Kanto Chemical Co., Inc.)

The following compounds were used as the component (D) and an alternative to the component (D) (component (D ′)).
(D-1): Polyhexamethylene biguanide hydrochloride (manufactured by Arch Chemicals Japan, “Proxel IB”)
(D'-1): Didecyldimethylammonium salt (manufactured by Lion Akzo Co., Ltd., "Arcade 210-50")

"Example 1"
<Preparation of liquid detergent for wiping>
Each component was mixed with the composition shown in Table 1, and adjusted using a pH adjuster (potassium hydroxide, citric acid) so that the pH of the mixture was 7, to obtain a liquid detergent for wiping.
The following evaluation was performed about the obtained liquid detergent for wiping off. The results are shown in Table 1.
In addition, the unit of the compounding quantity in Table 1 is mass%, and shows the pure amount conversion amount. The balance amount of water is water whose blending amount is adjusted so that the total amount (total amount) of the liquid detergent for wiping, which is the final product, is 100% by mass.

<Evaluation of antibacterial activity>
In accordance with JIS Z 2801, an antibacterial test was conducted as follows.
First, 100 μL of a liquid cleaning agent for wiping was applied on a 5 cm × 5 cm polypropylene plate (PP plate). A 23 cm × 18 cm tissue paper was cut into eight equal parts, and the liquid detergent for wiping on the PP plate was wiped with a wiping tool in which one of the tissue papers was folded in four. The PP plate after wiping was used as a test piece.
Escherichia coli and Staphylococcus aureus cultured according to JIS L 1902 are suspended in a 1/500 NB liquid medium, and the concentration is adjusted so that the number of bacteria becomes 2.5 to 10 × 10 ⁵ cells / mL. Was used as a bacterial solution.
Apply 0.4 mL of bacterial solution on a test piece placed in a sterilized petri dish, and attach a 4 cm × 4 cm reinforced polyethylene film (manufactured by Organo Corp., “Stomacker Film 400”) to a temperature of 35 ± 1 ° C. The cells were cultured for 24 hours under conditions of a humidity of 90% or higher. The number of viable bacteria was determined by counting the number of colonies after culture.
For PP plates (untreated PP plates) that were not wiped with a liquid detergent for wiping, the number of viable bacteria was measured by performing the same operation as the test piece. Calculated from (i), antibacterial activity was evaluated according to the following evaluation criteria.
Antibacterial activity value = log (viable count of untreated PP plate) −log (viable count of test piece) (i)

(Evaluation criteria)
◎◎◎: Antibacterial activity value is 4 or more.
A: The antibacterial activity value is 3 or more and less than 4.
A: The antibacterial activity value is 2 or more and less than 3.
○: The antibacterial activity value is 1 or more and less than 2.
X: Antibacterial activity value is less than 1.

<Evaluation of cleaning power>
<< Detergency against urine dirt >>
100 mL of urine collected from 3 adult men was mixed and used as mixed urine.
50 μL of mixed urine was dropped on a slide glass and left to dry at room temperature. After applying 100 μL of a liquid detergent for wiping on the mixed urine after drying, use a wiping tool in which toilet paper (manufactured by Nippon Paper Crecia Co., Ltd., “Kleenex (single)” 11.5 cm × 30 cm) is folded in eight. Wiped off. The remaining degree of urine stain after wiping was visually confirmed, the remaining roughness was confirmed by tactile sensation, and the detergency against urine stain was evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: All urine stains were removed with a single wipe.
◎: All urine stains were removed by one-time wiping.
○: All urine stains were removed after 1.5 reciprocations.
X: It took 2 roundtrips or more to remove all urine stains.

<< Detergency against oil stains >>
After applying 0.3 mL of a liquid detergent for wiping on a 10 cm square wooden table surface uniformly coated with 30 mg of red colored triolein in an environment of 25 ° C. and 65% RH (relative humidity) It was wiped with 1 g of tissue paper folded in four. The remaining condition of the oil stain (triolein) after wiping was visually confirmed, the remaining texture was confirmed by tactile sensation, and the detergency against the oil stain was evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: All oil stains were removed with a single wipe.
A: All the oil stains were removed by one-time wiping.
○: All oil stains were removed by 1.5 reciprocations.
X: It took 2 roundtrips or more to remove all the oil stains.

<Evaluation of deodorizing power>
<< Deodorizing power against urine odor >>
100 mL of urine collected from 3 adult men was mixed and used as mixed urine.
First, 100 μL of a liquid cleaning agent for wiping was applied on a 5 cm × 5 cm polypropylene plate (PP plate). A 23 cm × 18 cm tissue paper was cut into eight equal parts, and the liquid detergent for wiping on the PP plate was wiped with a wiping tool in which one of the tissue papers was folded in four.
50 μL of mixed urine was dropped onto the PP plate after wiping and left to dry at room temperature, and then put in a 450 mL glass bottle and capped. In this state, the sample was allowed to stand for 1 hour while being heated to 40 ° C., then returned to room temperature, and the odor in the glass bottle was subjected to sensory evaluation by 10 professional panelists based on the following 6-step odor intensity display method.
(6-level odor intensity display method)
5 points: Strong odor that cannot be tolerated.
4 points: Strong odor.
3 points: Obvious odor.
2 points: Odor enough to tell what smell is.
1 point: An odor that can be finally detected.
0 point: odorless.

The average score of sensory evaluation by 10 professional panelists was determined, and the effect of suppressing urine odor was evaluated according to the following evaluation criteria.
(Evaluation criteria)
◎◎◎: Average score is less than 1 point.
A: The average score is 1 or more and less than 1.5.
A: The average score is 1.5 points or more and less than 2 points.
○: The average score is 2 or more and less than 3 points.
X: The average score is 3 or more.

<< Deodorizing power against spoilage odor of ingredients >>
50 g of cabbage shredded and 50 g of ground sardine were mixed to prepare a mixed food.
First, 100 μL of a liquid cleaning agent for wiping was applied on a 5 cm × 5 cm polypropylene plate (PP plate). A 23 cm × 18 cm tissue paper was cut into eight equal parts, and the liquid detergent for wiping on the PP plate was wiped with a wiping tool in which one of the tissue papers was folded in four.
3 mg of the mixed food material was placed on the PP plate after wiping and left to dry at room temperature, and then placed in a 450 mL glass bottle and capped. In this state, the sample was allowed to stand for 1 hour while being heated to 40 ° C., then returned to room temperature, and the odor in the glass bottle was subjected to sensory evaluation by 10 professional panelists based on the following 6-step odor intensity display method.
(6-level odor intensity display method)
5 points: Strong odor that cannot be tolerated.
4 points: Strong odor.
3 points: Obvious odor.
2 points: Odor enough to tell what smell is.
1 point: An odor that can be finally detected.
0 point: odorless.

The average score of sensory evaluation by 10 professional panelists was obtained, and the effect of suppressing the rot odor of food was evaluated according to the following evaluation criteria.
(Evaluation criteria)
◎◎◎: Average score is less than 1 point.
A: The average score is 1 or more and less than 1.5.
A: The average score is 1.5 points or more and less than 2 points.
○: The average score is 2 or more and less than 3 points.
X: The average score is 3 or more.

<< Deodorizing power against bad odor derived from fatty acids >>
First, 100 μL of a liquid cleaning agent for wiping was applied on a 5 cm × 5 cm polypropylene plate (PP plate). A 23 cm × 18 cm tissue paper was cut into eight equal parts, and the liquid detergent for wiping on the PP plate was wiped with a wiping tool in which one of the tissue papers was folded in four.
3 mg of triolein was placed on the PP plate after wiping and left to dry at room temperature, and then put in a 450 mL glass bottle and capped. In this state, the sample was allowed to stand for 1 hour while being heated to 40 ° C., then returned to room temperature, and the odor in the glass bottle was subjected to sensory evaluation by 10 professional panelists based on the following 6-step odor intensity display method.
(6-level odor intensity display method)
5 points: Strong odor that cannot be tolerated.
4 points: Strong odor.
3 points: Obvious odor.
2 points: Odor enough to tell what smell is.
1 point: An odor that can be finally detected.
0 point: odorless.

The average point of sensory evaluation by 10 professional panelists was determined, and the effect of suppressing malodor derived from fatty acids was evaluated according to the following evaluation criteria.
(Evaluation criteria)
◎◎◎: Average score is less than 1 point.
A: The average score is 1 point or more and less than 2 points.
A: The average score is 2 or more and less than 3 points.
A: The average score is 3 or more and less than 4 points.
X: The average score is 4 or more.

<Evaluation of remaining wipes>
On the line (center line) connecting the vicinity of the midpoints of each of a pair of opposing sides of the four sides on the surface of a 20 cm × 20 cm mirror placed on a horizontal plane, and A liquid cleaning agent 0.1 mL for wiping was dropped at a position 2 cm away from one side.
Next, a 23 cm × 18 cm tissue paper is cut into eight equal parts, one of which is folded into four, and a liquid detergent for wiping on a mirror is applied to one side of the set of sides. The mirror surface was wiped once by reciprocating on the center line between a position 2 cm away from the center and a position 2 cm away from the other side of the set of sides.
Then, it left still for 5 minutes and dried, and the state of the wiping trace remaining in the mirror surface was visually determined. The same operation was performed 5 times in total, and the remaining wiping trace was evaluated according to the following evaluation criteria.
A: No wiping marks remained at all five times.
(Double-circle): The wiping trace did not remain at all 4 times. If you look closely once, there was a slight wiping mark remaining.
◯: No wiping marks remained at 3 out of 5 times. If you look closely twice, there was a slight wiping mark remaining.
(Triangle | delta): The wiping trace did not remain at all 1-2 times out of 5 times. If you look closely 3-4 times, there was a slight wiping mark remaining.
X: It was in the state which understood that the wiping trace remained all five times.

<Evaluation of stickiness and sliminess>
100 μL of a liquid detergent for wiping was applied on a 5 cm × 5 cm polypropylene plate (PP plate). A 23 cm × 18 cm tissue paper was cut into eight equal parts, and one of the four was folded in four, and the liquid detergent for wiping on the PP plate was reciprocated once and wiped off. The PP plate immediately after wiping was touched with a hand, and the stickiness and luster were evaluated according to the following evaluation criteria.
(Evaluation criteria)
◎◎: There is no stickiness or sliminess.
A: There is almost no stickiness or sliminess.
○: There is a little stickiness / sliminess.
X: There are stickiness and sliminess.

"Examples 2-32 and Comparative Examples 1-8"
Except having changed the compounding quantity of each component as shown in Tables 1-4, the liquid cleaning agent for wiping of each example was prepared like Example 1, and various evaluation was performed. The results are shown in Tables 1-4.
In Example 32, ethanol (manufactured by Junsei Chemical Co., Ltd., reagent grade 1, pure content 95% by mass) was used as an optional component.

  As is apparent from Tables 1 to 3, the liquid detergent for wiping obtained in each example was excellent in antibacterial activity and was able to suppress the growth of bacteria. Moreover, it was excellent in cleaning power against urine stains and oil stains. Moreover, it was also excellent in deodorizing power against urine odor, food rot odor and fatty acid-derived odor. Furthermore, there was no stickiness or sliminess after wiping, and wiping traces were difficult to remain.

On the other hand, the liquid cleaning agent for wiping of Comparative Example 1 in which the content of the component (A) is 0.03% by mass was inferior in cleaning power.
The liquid cleaning agent for wiping of Comparative Example 2 in which the content of the component (A) is 6% by mass was likely to be sticky, sticky, or leave wiping marks.
The liquid detergent for wiping of Comparative Example 3 containing no component (A1) was inferior in deodorizing power.
The liquid detergent for wiping of Comparative Examples 4 and 5 that does not contain the component (B) or the component (C) was inferior in deodorizing power.
The liquid detergent for wiping of Comparative Example 6 using EDTA instead of the component (C) was inferior in deodorizing power.
(D) The liquid detergent for wiping of the comparative example 7 which does not contain a component was inferior in antibacterial power.
The liquid detergent for wiping of Comparative Example 8 using didecyldimethylammonium salt instead of the component (D) was inferior in cleaning power.

Claims (4)

0.1 to 5% by mass of a surfactant (A) containing at least 10 to 80% by mass of an anionic surfactant (A1) based on the total mass of the surfactant;
0.002 to 2% by mass of at least one (B) selected from copper, manganese, nickel, cobalt, iron and zinc;
At least one chelating agent (C) selected from a compound represented by the following general formula (c1) and a compound represented by the following general formula (c2);
A liquid detergent for wiping, comprising a biguanide polymer (D).

(In the formula (c1), X ^{11 to} X ¹⁴ each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, or a cationic ammonium, R ¹¹ represents a hydrogen atom or a hydroxy group, and n1 represents 0 or Represents an integer of 1)

(In the formula (c2), A represents an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxy group or a hydrogen atom, and X ^{21 to} X ²³ each independently represents a hydrogen atom, an alkali metal, or an alkaline earth metal. Alternatively, it represents cationic ammonium, and n2 represents an integer of 0 to 5.) The liquid cleaning agent for wiping according to claim 1, comprising a biguanide polymer (D) in an amount of 0.002 to 1 mass%. The liquid cleaning agent for wiping according to claim 1 or 2, wherein the mass ratio represented by (A1) / (D) is 1 to 500. The liquid detergent for wiping as described in any one of Claims 1-3 whose molar ratio represented by the metal ion in (B) / (C) is 0.3-5.