JP6126956B2 - Cleaning composition for clothing - Google Patents

Description

  The present invention relates to a cleaning composition for clothing.

  Consumers are becoming more aware of water conservation, and the number of consumers who wash clothes using the remaining hot water of bath water is increasing. When remaining bath water is used for washing, in addition to germs adhering to the washing tub of the washing machine and bacteria present in the clothes worn, germs present in the remaining bath water are washed. May become present in the wash water using the current cleaning composition. In addition, consumers' awareness of hygiene has increased, and there is a need for a laundry detergent that suppresses the dry odor of clothes after washing and the generation of off-flavors when the laundry is stored for a long period of time. The fresh odor of clothing and the strange odor when washing is stored for a long time may be caused by bacteria attached to the clothing. Against this background, laundry detergent providers have developed a technology that has an effect of suppressing the growth of bacteria adhering to clothing by incorporating a bactericidal component or an antibacterial component. For example, Patent Document 1 discloses a liquid detergent composition containing a quaternary ammonium salt having one hydrocarbon group having 6 to 22 carbon atoms.

  On the other hand, Patent Document 2 describes that a specific quaternary ammonium salt having a hydroxide ion as a counter ion can realize good stability of a bleach activator used in an oxygen bleach. (Patent Document 2). Patent Document 2 describes that the liquid bleach composition may contain a surfactant such as an anionic surfactant.

  Patent Document 3 discloses a non-aqueous detergent composition comprising an anionic species, a bleaching agent and a neutralization system for the anionic species, and optionally a metal catalyst, wherein the neutralization system is a specific quaternary quaternary. Non-aqueous detergent compositions are described that comprise ammonium cations.

JP 2011-246585 A JP 2007-208595 A Special table hei 10-502104

  The liquid detergent composition described in Patent Document 1 is excellent in the effect of suppressing the growth of bacteria attached to clothing, but for example, when using remaining hot water in bath water, there is a concern that an increase in bacteria is a concern. Considering the increase in the aspect, further improvement in bactericidal properties is desired. In addition, bacteria present on clothing are known to metabolize sebum soil present on clothing, and there is still a demand for a technique for further improving the cleaning properties of sebum soil on clothing.

  The present invention provides a cleaning composition for clothing that has good detergency and is excellent in bactericidal properties even under cleaning conditions in which the number of bacteria contained in the cleaning liquid is large.

The present invention contains the following components (A) and (B), the content of component (A) is 2% by mass or more and 50% by mass or less, and the molar ratio of component (A) / component (B) The present invention relates to a cleaning composition for clothing, wherein is 1 or more and 50 or less.
(A) Component: Anionic surfactant (B) having a group selected from a sulfonic acid group, a sulfate ester group, and a salt thereof Component: A quaternary ammonium compound represented by the following general formula (1)

[Wherein R ¹ , R ² and R ³ are each independently a hydrocarbon group having 3 to 8 carbon atoms, R ⁴ is a hydrocarbon group having 2 to 8 carbon atoms, R The total carbon number of ¹ , R ² , R ³ and R ⁴ is 16 or more and 32 or less, and X ⁻ is an anion. ]

  ADVANTAGE OF THE INVENTION According to this invention, the washing | cleaning composition for clothes which has the favorable detergency and was excellent in bactericidal property also in the washing | cleaning conditions with many bacteria contained in a washing | cleaning liquid is provided.

<(A) component>
The component (A) is an anionic surfactant having a group selected from a sulfonic acid group, a sulfate ester group, and a salt thereof.

  Examples of anionic surfactants having a group selected from sulfonic acid groups and salts thereof include alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts, and α-sulfo fatty acid salts. Examples include anionic surfactants selected from ester salts. The anionic surfactant having a group selected from sulfonic acid groups and salts thereof has 10 or more carbon atoms, 12 or more carbon atoms, 18 or less carbon atoms, 16 or less carbon atoms, and further 14 or less carbon atoms from the viewpoint of developing high cleaning performance. An alkylbenzene sulfonate having an aliphatic alkyl group, preferably a linear alkyl group, and further a linear primary alkyl group is preferred.

  As an anionic surfactant having a group selected from a sulfate ester group and a salt thereof, an aliphatic alkyl having 10 or more carbon atoms, 12 or more carbon atoms, 18 or less carbon atoms, and 16 or less carbon atoms from the viewpoint of developing high cleaning performance. Group, preferably linear alkyl group, alkyl sulfate ester salt having linear primary alkyl group, aliphatic alkyl group having 10 or more, further 12 or more, and 18 or less, and further 16 or less, preferably linear A polyoxyalkylene alkyl ether sulfate salt having an alkyl group, a linear primary alkyl group, and an average addition mole number of alkylene oxide of 1 or more, 1.5 or more, and 10 or less, further 5 or less. Can be mentioned.

  (A) As a counter ion used as the salt of a component, an alkali metal ion, an alkaline earth metal ion, an ammonium ion, and an alkanol ammonium ion are mentioned, However, An alkali metal ion is preferable. Therefore, the salt of the component (A) is preferably an alkali metal salt.

  In the cleaning composition for clothing of the present invention, the component (A) has an alkylbenzene sulfonate having an aliphatic alkyl group having 10 to 18 carbon atoms and an aliphatic alkyl group having 10 to 18 carbon atoms. 1 or more types chosen from the sulfate ester salt and the polyoxyalkylene alkyl ether sulfate ester salt which has a C10-C18 aliphatic alkyl group, and the average addition mole number of alkylene oxide is 1-10. The anionic surfactant is preferably used. From the viewpoint of obtaining good sebum dirt cleaning power, the component (A) is preferably an anionic surfactant having a group selected from a sulfonic acid group and a salt thereof, and the component (A) has 10 or more carbon atoms, It is more preferably an alkylbenzene sulfonate having an aliphatic alkyl group of 12 or more and 18 or less, further 16 or less, and further 14 or less, preferably a linear alkyl group, and further a linear primary alkyl group.

  The garment cleaning composition of the present invention can contain an anionic surfactant other than the component (A), but the proportion of the component (A) in the total anionic surfactant is 60 in terms of bactericidal effect. It is preferably at least mass%, more preferably at least 70 mass%, and even more preferably at least 80 mass%. The total amount of the anionic surfactant, that is, 100% by mass may be the component (A).

  Examples of the anionic surfactant other than the component (A) include fatty acid salts having an aliphatic hydrocarbon group having 10 to 18 carbon atoms. Examples of the counter ion to be a salt include alkali metal ions, alkaline earth metal ions, ammonium ions, and alkanol ammonium ions, with alkali metal ions being preferred. The salt of the fatty acid is preferably an alkali metal salt.

<(B) component>
The component (B) is a quaternary ammonium compound represented by the following general formula (1).

[Wherein R ¹ , R ² and R ³ are each independently a hydrocarbon group having 3 to 8 carbon atoms, R ⁴ is a hydrocarbon group having 2 to 8 carbon atoms, R The total carbon number of ¹ , R ² , R ³ and R ⁴ is 16 or more and 32 or less, and X ⁻ is an anion. ]

In the general formula (1), R ¹ , R ² and R ³ are each independently a hydrocarbon group having 3 to 8 carbon atoms. In terms of suppressing the formation of a complex of the component (B) and the component (A), R ¹ , R ² and R ³ each independently preferably have 4 or more carbon atoms and 5 or more carbon atoms. More preferred. In terms of solubility in water, the number of carbon atoms is preferably 7 or less, and more preferably 6 or less. R ¹ , R ² and R ³ in the general formula (1) are preferably each independently a hydrocarbon group having 4 to 8 carbon atoms. Examples of the hydrocarbon group for R ¹ , R ² and R ³ include an alkyl group and an alkenyl group, and an alkyl group is preferred. The alkyl group is preferably a linear alkyl group.

In the general formula (1), R ⁴ is a hydrocarbon group having 2 to 8 carbon atoms. In terms of suppressing the formation of a complex of the component (B) and the component (A), the carbon number of R ⁴ is preferably 3 or more, and more preferably 4 or more. In terms of solubility in water, the number of carbon atoms is preferably 7 or less, and more preferably 6 or less. Examples of the hydrocarbon group for R ¹ , R ² and R ³ include an alkyl group and an alkenyl group, and an alkyl group is preferable. The alkyl group is preferably a linear alkyl group.

In the general formula (1), the total number of carbon atoms of R ¹ , R ² , R ³ and R ⁴ is 16 or more and 32 or less. In terms of enhancing the antibacterial effect, the total number of carbon atoms of R ¹ , R ² , R ³ and R ⁴ is preferably 18 or more, more preferably 19 or more, and still more preferably 20 or more. Further, in terms of solubility in water, the total number of carbon atoms of R ¹ , R ² , R ³ and R ⁴ is preferably 30 or less, more preferably 28 or less, and even more preferably 26 or less.

In the general formula (1), X ⁻ is an anion, and halide ions such as bromide ion (Br ⁻ ) and chloride ion (Cl ⁻ ) are preferable from the viewpoint of easy production of the component (A).

As a preferred component (B), R ¹ , R ² and R ³ in the general formula (1) are each independently a hydrocarbon group having 4 or more and 8 or less carbon atoms, and R ⁴ is 3 or more carbon atoms, A quaternary ammonium compound having 8 or less hydrocarbon groups may be mentioned.

Further, as a preferred component (B), R ¹ , R ² and R ^{3 in} the general formula (1) are each independently a hydrocarbon group having 5 to 8 carbon atoms, and R ⁴ is ⁴ carbon atoms. As mentioned above, it is a quaternary ammonium compound which is a hydrocarbon group having 8 or less hydrocarbon groups and the total number of carbon atoms of R ¹ , R ² , R ³ and R ⁴ being 19 or more and 30 or less.

Further, as a preferred component (B), R ¹ , R ² , R ³ and R ^{4 in} the general formula (1) are each independently a hydrocarbon group having 4 to 6 carbon atoms, and further an alkyl group. A quaternary ammonium compound in which X ⁻ is a halide ion, and R ¹ , R ² , R ³ and R ^{4 in} the general formula (1) are a hydrocarbon group having 6 carbon atoms and further an alkyl group , X ^- is a quaternary ammonium compound is a halide ion.

  Specific examples of the component (B) are tetrabutylammonium salt, tetrapentylammonium salt, tetrahexylammonium salt, tetraoctylammonium salt, benzyltripropylammonium salt, benzyltributylammonium salt, benzyltripentylammonium salt, benzyltrihexylammonium. Salts, benzyltrioctylammonium salt, tetrabenzylammonium salt, tributylphenylammonium salt, triheptylphenylammonium salt, trihexylphenylammonium salt and trioctylphenylammonium salt. Examples of the salt include one or more salts selected from bromide salts and chloride salts.

  The component (B) is preferably at least one compound selected from tetrahexylammonium chloride and tetrahexylammonium bromide from the viewpoint of compatibility between bactericidal properties and detergency.

  The garment detergent composition of the present invention exhibits excellent bactericidal properties and detergency despite the combined use of different ionic compounds (A) and (B). Although the reason is not necessarily clear, the present inventors presume as follows. A quaternary ammonium compound that does not correspond to the component (B) of the present invention, for example, a quaternary ammonium salt having one hydrocarbon group having 8 to 22 carbon atoms described in Patent Document 1, has a hydrophobic group and a hydrophilic property. The basic cationic groups are next to each other. On the other hand, the anionic surfactant of the component (A) also has an anionic group that is a hydrophobic group and a hydrophilic group adjacent to each other. When these are used in combination, the quaternary ammonium salt and the anionic surfactant form a composite crystal in water by hydrophobic interaction between hydrophobic groups and strong electrostatic interaction between hydrophilic groups. It is estimated that the quaternary ammonium salt is less likely to come into contact with bacteria. On the other hand, the component (B) of the present invention has a hydrophobic group with a close chain length so as to surround the quaternary ammonium group, so that it is difficult to form a crystal with the component (A). It is thought that the quaternary ammonium salt is more accessible to bacteria in water.

  In addition, since the component (B) of the present invention is less likely to form crystals with the component (A), the component (A) effectively acts on dirt as a cleaning component, so that the detergency can be improved. Conceivable.

From this point of view, the component (B) has good solubility in water, the cationic charge is appropriately shielded by a hydrophobic group, and the hydrophobic interaction with the component (A) Since it is presumed that the weaker one is preferable, the hydrocarbon groups of R ¹ , R ² , R ³ and R ^{4 in} the general formula (1) have a carbon number close to each other. It is thought that it is more advantageous due to the effect.

<Cleaning composition for clothing>
In the garment cleaning composition of the present invention, the content of the component (A) is 2% by mass or more and 50% by mass or less. The content of the component (A) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and still more preferably 20% by mass or more in the composition from the viewpoint of detergency. . In addition, the content of the component (A) is preferably 45% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less in the composition from the viewpoint of economy.

In the garment cleaning composition of the present invention, the molar ratio of component (A) / component (B) is 1 or more and 50 or less.
From the viewpoint of the bactericidal effect against Moraxella bacteria and the effect of improving the fresh odor of textile products in the room, the molar ratio of component (A) / component (B) is preferably more than 1, more preferably 1.5 or more. It is preferably 5 or more, more preferably 8 or more, and still more preferably 10 or more.
Further, from the viewpoint of bactericidal properties and detergency against sebum dirt, the molar ratio of component (A) / component (B) is preferably 1.5 or more, more preferably 2 or more, further preferably 5 or more, and 8 or more. Even more preferred is 10 or more.
Further, from the viewpoint of detergency against sebum dirt, the molar ratio of the component (A) / (B) is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.

  In addition, when (A) component and / or (B) component contain a some compound, the whole average mole number is calculated | required from the number-of-moles of a some compound, and the average number-of-moles is (A) component and / or Alternatively, the molar ratio of the component (A) to the component (B) is determined as the number of moles of the component (B).

  It is preferable that the detergent composition for clothes of this invention contains water from the point which improves the dispersibility to the water used for washing | cleaning. The content of water is preferably 10% by mass or more, more preferably 40% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less in the composition. The form is preferably a liquid composition.

  When the detergent composition for clothing of the present invention is a liquid composition containing water, the pH at 20 ° C. is preferably 6 or more, and preferably 7 or more in terms of obtaining excellent cleaning performance. Is more preferably 10 or less and more preferably 9.5 or less. The pH is measured by the method described in JIS K3362: 2008.

  Components that can be contained in the cleaning composition for clothing of the present invention include chelating agents such as ethylenediaminetetraacetic acid and salts thereof, recontamination preventives and dispersants such as polyacrylic acid, enzymes such as protease, fluorescence Examples include dyes, antioxidants such as butylhydroxytoluene, pigments, fragrances, antibacterial preservatives, and antifoaming agents such as silicone.

  The garment cleaning composition of the present invention is used for washing garments as a liquid composition containing the composition and water. Examples of the cleaning method using the garment cleaning composition of the present invention include a cleaning method including a step of bringing the garment into contact with a liquid composition containing the component (A), the component (B) and water. The temperature of the liquid composition brought into contact with the clothing is preferably 0 ° C. or higher and 40 ° C. or lower in terms of bactericidal effect. If the detergent composition for clothes of the present invention is used, a sufficient bactericidal effect can be obtained even at a relatively low temperature. In the point which is easy to realize the bactericidal effect by this invention, 35 degrees C or less is preferable and the temperature of the liquid composition contacted with clothing is more preferable 30 degrees C or less. 5 degreeC or more is preferable and 10 degreeC or more is more preferable at the point of detergency.

  The contact time between the liquid composition and the garment is preferably 2 minutes or more, more preferably 5 minutes or more, still more preferably 10 minutes or more, and more preferably 15 minutes or more in terms of obtaining a higher cleaning effect and sterilization effect. Is even more preferable. 60 minutes or less is preferable from the viewpoint of the efficiency of the cleaning method, 30 or less is more preferable, and 20 minutes or less is more preferable.

  The garment cleaning composition of the present invention is excellent in bactericidal properties against various microorganisms, and in particular, can effectively sterilize Moraxella bacteria.

  Although the cleaning composition of the present invention is for clothing, the clothing can include various products including clothes such as clothes, underwear, socks, and cloths such as towels, sheets, and pillow covers.

The components used in Examples and Comparative Examples are shown below.
<(A) component>
(A-1): Sodium laurylbenzenesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.)
<(B) component>
(B-1): Tetrahexyl ammonium bromide (manufactured by Kanto Chemical Co., Inc.)
(B-2): Tetrabutylammonium bromide (manufactured by Kanto Chemical Co., Inc.)
<(B ′) Component: Comparative Compound of Component (B)>
(B′-1): Tetradecyltrimethylammonium chloride (manufactured by Wako Pure Chemical Industries, Ltd.)
(B'-2): Tetramethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Example 1]
In the composition of Example 1-1 in Table 1, 90% by mass of ion-exchanged water at 30 ° C. necessary for the finished mass to be 50 g was put in a 100 mL glass beaker. A Teflon (registered trademark) stirrer having a diameter of 1.5 cm was added, and then 2 g of component (a-1) was added over 5 minutes while stirring at 50 r / min with a magnetic stirrer. Next, 2.5 g of component (b-1) was added over 5 minutes. Further, after stirring for 10 minutes, ion-exchanged water at 30 ° C. was added so that the finished mass was 50 g, and the mixture was further stirred for 3 minutes to obtain a cleaning composition for clothing described in Example 1-1. Other compositions in Table 1 were prepared similarly.

  Bactericidal properties (bactericidal activity value) were evaluated by the following method using the obtained detergent composition for clothing. The results are shown in Table 1. In Table 1, in some comparative examples, the (A) / (B) molar ratio was determined with the component (A ′) as the component (A) and the component (B ′) as the component (B). .

(1) Test method of bactericidal effect Hardness water prepared by adding the following concentrated hardness adjusting water to ion-exchanged water (0 ° DH) to adjust the hardness to 4 ° DH was prepared. Using this hardness water, a test liquid (1) was obtained by diluting the garment cleaning composition in Table 1 so that its concentration was 333 mg / kg. To 10 mL of this diluted solution, 0.1 mL of a bacterial solution (initial number of bacteria 1.0 × 10 ⁹ CFU / mL) was added, and 10 minutes at 150 r / min under a temperature condition of 25 ° C. with a test tube mixer. Stir. After contacting the test solution (1) with the bacteria for 15 minutes, 500 μL is collected with a micropipette and suspended in 4500 μL of LP diluted solution (manufactured by Wako Pure Chemical Industries, Ltd.). Inactivated. The diluted solution was serially diluted, mixed with SCDLP agar medium, statically cultured at 37 ° C. (1 day), the number of colonies obtained was counted, and the live of Comparative Example 1-1 in Table 1 was obtained. The bactericidal activity value was obtained by subtracting the common logarithm of the viable cell count of Example 1 from the common logarithm of the cell count (logarithmic value). The strain used was Moraxella osloensis ATCC 19976, a Moraxella bacterium.

  In this evaluation, if the bactericidal activity value is 0.1 or more, it can be understood that the bactericidal performance is significantly improved. The higher the value of the bactericidal activity value is preferred, and in this evaluation, if the bactericidal activity value is 1.8 or more, it is considered that a sufficient bactericidal effect in actual washing of clothes is expressed, preferably 2.0 or more, More preferably, it is 2.2 or more. In this evaluation, those having a bactericidal activity value of 2.0 or more can be judged to show a practically useful high bactericidal effect.

* Concentrated hardness adjustment water: 66.7 g / L of calcium chloride (anhydrous) (Wako Pure Chemical Industries, Ltd.), magnesium chloride (hexahydrate) (Wako Pure Chemical Industries, Ltd.) with respect to ion-exchanged water Concentrated hardness adjusted water having a Ca / Mg ratio (mass ratio) of 4/1 and a hardness of 4000 ° DH, obtained by adding 2) to 29.6 g / L.

  In Table 1, from comparison between Example 1-3, Comparative Example 1-2, and Comparative Example 1-3, component (A) and component (B) do not exhibit sufficient bactericidal properties alone, It turns out that bactericidal property improves markedly by using together. Moreover, even if it is a compound which has the structure of the same quaternary ammonium salt, even if it uses together with (A) component when the compound which does not correspond to (B) component is used, Comparative Examples 1-5-1- As shown in FIG. 8, sufficient bactericidal properties cannot be obtained. Therefore, it can be seen that excellent bactericidal properties are specifically expressed by selecting the component (B) of the present invention and combining it with the component (A).

[Example 2]
Bactericidal properties were evaluated in the same manner as in Example 1 using the clothing detergent composition shown in Table 2. Moreover, the detergency was evaluated by the following method. The results are shown in Table 2. In Table 2, in Comparative Example 2-2, (A) / (B) was obtained with the component (B ′) as the component (B). In Table 2, the pH of the composition was adjusted with monoethanolamine.

(2) Detergency evaluation <Production of artificially contaminated cloth>
The artificial soiling cloth used was a 6cm x 6cm cotton / polyester broad blended dyeing cloth (cotton / polyester ratio = 35/65 purchased from Tanigami Shoten). Gravure coating.
-Model sebum stain A model sebum stain having the following composition was used.
Lauric acid 0.44%, myristic acid 3.15%, pentadecanoic acid 2.35%, palmitic acid 6.31%, heptadecanoic acid 0.44%, stearic acid 1.6%, oleic acid 7.91 mass%, triolein 13.33 mass%, n-hexadecyl palmitate 2.22 mass%, squalene 6.66 mass%

<Cleaning conditions>
Detergent composition for clothing 0 shown in Table 2 in 1 liter of water having a hardness of 4 ° DH (Ca / Mg = 6/4, mass ratio), 0.2 g of model sebum soil, 0.3 ml of glacial acetic acid 5 pieces of artificial model sebum soil-contaminated cloth were put into a cleaning solution (20 ° C.) containing 25 g. Next, a 6 cm × 12 cm cotton / polyester broad blended dyeing cloth was introduced and the bath ratio was adjusted to 20. Washing was performed at 85 rpm for 10 minutes with a targotometer.

Detergency was measured with a colorimetric colorimeter (Nippon Denshoku Co., Ltd., Z-300A) for the reflectance at 550 nm before and after washing, and the washing rate (%) was determined by the following formula. . The average value was obtained by measuring each of the five contaminated cloths. A cleaning rate of 30% or more is an acceptable line, and a higher numerical value is more preferable.
Washing rate (%) = 100 × [(reflectance after washing−reflectivity before washing) / (reflectance of base fabric−reflectivity before washing)]

Claims (3)

The following (A) component and (B) component are contained, the content of (A) component is 2 mass% or more and 50 mass% or less, and the molar ratio of (A) component / (B) component is 1 or more, A detergent composition for clothing which is 50 or less.
(A) Component: Anionic surfactant (B) having a group selected from a sulfonic acid group, a sulfate ester group, and a salt thereof Component: A quaternary ammonium compound represented by the following general formula (1)

[Wherein R ¹ , R ² and R ³ are each independently a hydrocarbon group having 5 to 8 carbon atoms, R ⁴ is a hydrocarbon group having 4 to 8 carbon atoms, ¹ , R ² , R ³ and R ⁴ have a total carbon number of 19 or more and 30 or less, and X ⁻ is an anion. ] The cleaning composition for clothes according to claim 1, wherein the component (B) is one or more quaternary ammonium compounds selected from tetrahexylammonium chloride and tetrahexylammonium bromide. The component (A) is an alkylbenzene sulfonate having an aliphatic alkyl group having 10 to 18 carbon atoms, a sulfate ester salt having an aliphatic alkyl group having 10 to 18 carbon atoms, and 10 to 18 carbon atoms. have the following aliphatic alkyl group, the average number of moles of added alkylene oxide is 1 or more, one or more anionic surfactant selected from polyoxyalkylene alkyl ether sulfate is 10 or less, according to claim 1 Or the cleaning composition for clothes of 2 .