JP6138674B2 - Liquid detergent composition for clothing - Google Patents

Description

  The present invention relates to a liquid cleaning composition for clothing.

  Various stains such as particle stains such as mud stains, stain stains such as spilled foods, and sebum stains adhere to clothing. Therefore, detergents for clothing are required to have high detergency against all these stains. Among them, particle dirt such as mud stain is effective with dispersion polymer and anionic surfactant, bleach stain and anionic surfactant are effective for stain stain such as spilled food, and sebum stain is non-ionic. It is generally known that it is effective to use a surfactant. Therefore, usually, a combination of a plurality of surfactants is used in a cleaning composition for clothing.

  As a detergent composition combined with a surfactant, Patent Document 1 discloses a detergent composition containing a polyoxyethylene alkyl ether sulfate ester type surfactant and a cationic surfactant. Patent Document 2 discloses (a) a nonionic surfactant having an average addition mole number of alkylene oxide of 16 to 35, and (b) an anionic surfactant having an alkyleneoxy group having 3 and / or 4 carbon atoms. And (c) a liquid detergent composition containing a specific solvent and having a high surfactant concentration. Patent Document 3 discloses a liquid detergent composition containing a nonionic surfactant, an anionic surfactant, and a cationic surfactant under predetermined conditions. Patent Document 4 discloses a coating detergent composition containing a nonionic surfactant, an anionic surfactant, and a cationic surfactant under predetermined conditions.

  On the other hand, in a fully automatic washing machine, there are models equipped with a washing course (sometimes called a speed course) that can shorten the washing time in addition to the standard course. In the course of shortening the washing time, the number of times of rinsing is reduced, or the time for washing clothes with the detergent composition is shortened.

JP-A-56-5895 JP 2011-208130 A JP 2012-87228 A JP 2012-87227 A

  In order to clean all dirt stains such as mud stains on clothes, stain stains such as food spills, and sebum stains to a satisfactory level, a combination of nonionic surfactants and anionic surfactants can be used. However, in reality, the characteristics of both the nonionic surfactant and the anionic surfactant are not exhibited as expected, and the three kinds of surfactants are not. In order to further improve the detergency against dirt, further studies are required. Therefore, there is a strong demand for a cleaning composition for clothing having excellent cleaning power against the above-mentioned three types of dirt.

  When a course for shortening the washing time is selected in the fully automatic washing machine, operations such as a reduction in the number of times of rinsing and a reduction in the washing time are performed. The operator expects the same dirt removal as a normal washing course even if the cleaning time is short. However, it has been found that the cleaning performance tends to decrease as the cleaning time decreases. On the other hand, even if a liquid detergent composition in which the content of the surfactant as the washing base is increased in the hope of improving the detergency, a sufficient effect commensurate with the economy can be obtained. Absent.

The present invention provides a liquid detergent composition for clothing having excellent detergency against stains such as spilled food. The present invention also provides a liquid detergent composition for clothing having excellent detergency against particle dirt such as mud dirt. Moreover, this invention provides the liquid cleaning composition for clothes which has the outstanding cleaning power with respect to the stain | pollution | contamination derived from a human body.
The present invention provides a liquid detergent composition for clothing having excellent detergency against any of soils of particles, stains, and soils derived from the human body.
Furthermore, the present invention provides a liquid detergent composition for clothing that exhibits sufficient detergency even when the washing time is short, in particular, detergency against sebum dirt.

The present invention
The following (a) component, (b) component, (c) component, (d) component and water are contained,
The total amount of the content of the component (a), the content of the component (b), and the content of the component (c) is 15% by mass or more and 70% by mass or less,
The mass ratio of the content of the component (c), the content of the component (a) and the total content of the component (b) is (c) component / [(a) component + (b) component]. 0.02 or more and 0.2 or less,
The mass ratio of the content of the component (b) and the content of the component (a) is (b) component / (a) component, and is 0.15 or more and 10 or less.
The present invention relates to a liquid cleaning composition for clothing.
(A) Component: Alkylbenzenesulfonic acid or salt thereof (b) Component: Anionic surfactant represented by the following general formula (1) RO-[(AO) _p / (EO) _q ] -SO ₃ M (1 )
[Wherein R represents a hydrocarbon group having 8 to 22 carbon atoms, AO represents an alkyleneoxy group selected from an alkyleneoxy group having 3 carbon atoms and an alkyleneoxy group having 4 carbon atoms, and EO represents an ethyleneoxy group. Represents a group, p and q represent the average number of added moles, p is a number of 0.5 or more and 5 or less, and q is a number of 0 or more and 10 or less. “/” Indicates that the AO group and the EO group may be bonded to either random or block. M is a cation. ]
(C) Component: Quaternary ammonium salt represented by the following general formula (2)

[Wherein R ¹ is a hydrocarbon group having 10 to 14 carbon atoms, R ² is a hydrocarbon group having 7 to 14 carbon atoms, a hydrocarbon group having 1 to 3 carbon atoms, and — (A ₁ O) _s —H (wherein A ¹ O is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms, and s is a number from 1 to 5). R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 3 carbon atoms and — (A ¹ O) _s —H (wherein A ¹ O, s Is the same group as described above. A plurality of (A ¹ O) present in the molecule may be the same or different. X ⁻ is a halogen ion, CH ₃ SO ₄ ^— or CH ₃ CH ₂ SO ₄ ^— . ]
Component (d): Nonionic surfactant represented by the following general formula (3) R ⁵ O— (EO) _t —H (3)
[Wherein R ⁵ represents a hydrocarbon group having 8 or more and 18 or less carbon atoms, EO represents an alkylene group, t represents an average number of added moles, and is a number of 1 or more and 10 or less. ]

  Moreover, this invention is a washing | cleaning liquid which contains water and the liquid cleaning composition for clothes of the said invention 0.01 mass% or more and 0.2 mass% or less and whose temperature is 0 degreeC or more and 35 degrees C or less. The bath ratio represented by the ratio of the mass of the clothing and the amount of the cleaning liquid (liter) is that the amount of the cleaning liquid (liter) / the mass of the clothing (kg) = 3 or more and 50 or less. The present invention relates to a method for washing clothing that is washed for 7 minutes or less.

ADVANTAGE OF THE INVENTION According to this invention, the liquid cleaning composition for clothing which has the outstanding cleaning power with respect to all stain | pollution | contamination of particle | grain stain | pollution | contamination, a stain | pollution | contamination stain | pollution | contamination, and the stain | pollution | contamination derived from a human body is provided. In addition, according to the present invention, there is provided a liquid detergent composition for clothing that exhibits sufficient detergency even when the washing time is short. In the liquid detergent composition for clothes of the present invention, a cleaning power equivalent to a standard course having a sufficient cleaning time can be achieved even when the cleaning time is shortened. Therefore, the cleaning time can be shortened. In addition, even if the cleaning time is short, the cleaning performance for particle dirt, stain dirt, and dirt derived from the human body can be maintained, and in particular, it is excellent in cleaning performance for uneaten dirt that is difficult to remove.
In the present invention, by using two kinds of specific anionic surfactants of the component (a) and the component (b), the specific quaternary which is the component (c) with respect to the content of the anionic surfactant. Even if the content of the ammonium salt is small, the permeability to the spilled dirt is increased, and the spilled dirt is excellent in cleaning performance. In addition, it is possible to improve the detergency of mud dirt and spilled dirt.

<(A) component>
The component (a) is not particularly limited. For example, the alkylbenzene sulfonic acid having 8 or more, 10 or more, and 20 or less, further 15 or less alkyl group, and further having a linear alkyl group or its Salt.

  Examples of the alkylbenzene sulfonate include alkali metal salts such as sodium and potassium, alkanolamine salts, and alkaline earth metal salts such as magnesium and calcium. From the viewpoint of detergency and storage stability of the composition. , An alkali metal salt, or an alkanolamine salt is preferable. When preparing the composition of the present invention, an alkylbenzene sulfonic acid (acid type) is added to the composition, and it may be neutralized with an alkali in the system to obtain an alkyl benzene sulfonate. It may be added to the product. A strong base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonium hydroxide can be used for neutralization of the alkylbenzene sulfonic acid.

<(B) component>
The component (b) is blended at a specific ratio with the component (a), and is used in combination with the component (c), so that the composition and the clothing containing the liquid detergent composition containing the component (b) and water Even when the contact time is short, the cleaning power against various types of dirt can be further enhanced. In particular, by blending the component (b) and the component (a) at a specific ratio, the permeability of the component (c) to the spilled dirt increases, and the detergency of the spilled dirt increases.

The anionic surfactant as the component (b) used in the present invention is a compound represented by the following general formula (1).
RO - _{[(AO) p / (EO)} q ] -SO ₃ M (1)
[Wherein R represents a hydrocarbon group having 8 to 22 carbon atoms, AO represents an alkyleneoxy group selected from an alkyleneoxy group having 3 carbon atoms and an alkyleneoxy group having 4 carbon atoms, and EO represents an ethyleneoxy group. Represents a group, p and q represent the average number of added moles, p is a number of 0.5 or more and 5 or less, and q is a number of 0 or more and 10 or less. “/” Indicates that the AO group and the EO group may be bonded to either random or block. M is a cation. ]

  In the general formula (1) of the component (b), R is a hydrocarbon group having 8 to 22 carbon atoms. R has a carbon number of 8 or more in view of sebum stain detergency, preferably 10 or more, more preferably 12 or more, and is preferably 16 or less and more preferably 14 or less in view of stain stain detergency. The hydrocarbon group for R is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, from the viewpoint of availability of raw materials. R is preferably a straight-chain hydrocarbon group from the viewpoint of detergency of particle dirt such as mud dirt. R is preferably an alkyl group having 12 to 14 carbon atoms and a linear alkyl group. In general formula (2), the carbon atom of R bonded to the oxygen atom is preferably a primary carbon atom.

  The alkyleneoxy group selected from the alkyleneoxy group having 3 carbon atoms and the alkyleneoxy group having 4 carbon atoms, which is AO in the general formula (1), includes an oxytrimethylene group, an oxypropane-1,2-diyl group, and oxybutane. Examples thereof include one or more groups selected from a -1,2-diyl group, an oxybutane-1,3-diyl group, an oxybutane-2,3-diyl group, and an oxytetramethylene group. From the viewpoint of availability, an oxypropane-1,2-diyl group [generally called a propyleneoxy group. ], An oxybutane-1,2-diyl group (also generally referred to as a butyleneoxy group) is more preferred, and an oxypropane-1,2-diyl group is still more preferred.

  P in the general formula (1) is an average added mole number of AO, and is a number of 0.5 or more and 5 or less. From the viewpoint that the washing rate can be improved, p is preferably 0.8 or more, more preferably 1 or more, more preferably 1.1 or more, more preferably 1.2 or more, and more preferably. Is 1.3 or more, more preferably 1.4 or more, still more preferably 1.5 or more, still more preferably 1.6 or more, still more preferably 1.7 or more, and even more. Preferably it is 1.8 or more. From the viewpoint of detergency against sebum dirt, p is 5 or less, preferably 4 or less, more preferably 3 or less.

  Q in the general formula (1) is an average added mole number of EO, and is a number of 0 or more and 10 or less. When q is not 0, q is preferably 0.5 or more, more preferably 0.8 or more, further preferably 1 or more, still more preferably 1.5 or more, from the viewpoint that the washing rate can be improved. The number is more preferably 1.8 or more, and still more preferably 2 or more. From the viewpoint of detergency against stain stains and sebum stains, it is 10 or less, preferably 8 or less, more preferably 5 or less, and even more preferably 3 or less. An anionic surfactant having q of 0 is also preferable from the viewpoint of ease of production.

In the anionic surfactant of the general formula (1), it is preferable that AO and EO are bonded together in a block from the viewpoint that the cleaning rate can be improved. In that case, it is preferable that block connection is made to RO- in the order of (AO) _p- (EO) _q- . That is, the anionic surfactants of the general formula (1), RO- (AO) p - (EO) a compound represented by _q -SO ₃ M are preferable.

  Moreover, M in General formula (1) is a cation. Preferable examples of M include hydrogen ions, alkali metal ions, alkaline earth metal ions, ammonium ions, and alkanol ammonium ions having 1 to 6 carbon atoms.

  Examples of alkali metal ions include sodium ions, potassium ions, and lithium ions. Examples of alkaline earth metal ions include magnesium ions. Examples of alkanol ammonium ions having 1 to 6 carbon atoms include monoethanol ammonium ions. And triethanolammonium ion. Among these, sodium ions, alkali metal ions of potassium ions or monoethanolammonium ions are preferable, and monoethanolammonium ions are more preferable in terms of detergency.

  The method for producing the anionic surfactant represented by the general formula (1) is not particularly limited. For example, an alcohol having 8 or more and 22 hydrocarbon groups, preferably 1 mol of a linear primary aliphatic saturated alcohol having 10 to 14 carbon atoms, an alkylene oxide having 3 carbon atoms and / or 4 carbon atoms. Alkylene oxide, preferably propylene oxide 0.5 mol or more, preferably 0.8 mol or more, more preferably 1 mol or more, still more preferably 1.5 mol or more, still more preferably 1.8 mol or more, and Intermediate compound (1) added in an amount of 5 mol or less, preferably 3 mol or less is obtained. Next, ethylene oxide is 0 mol or more, preferably 0.5 mol or more, more preferably 0.8 mol or more, more preferably 1 mol or more, still more preferably 1.5 mol or more, relative to the intermediate compound (1). Still more preferably, it is added in an amount of 1.8 mol or more and 10 mol or less, preferably 8 mol or less, more preferably 5 mol or less, still more preferably 3 mol or less to obtain the intermediate compound (2). Next, the anionic surfactant represented by the general formula (1) can be obtained by sulfating the intermediate compound (2) and neutralizing it in some cases. In the example of the production method, the order of adding the alkylene oxide, preferably propylene oxide, and ethylene oxide can be changed or randomly added to the raw material alcohol.

<(C) component>
The component (c) is a quaternary ammonium salt represented by the following general formula (2).

[Wherein R ¹ is a hydrocarbon group having 10 to 14 carbon atoms, R ² is a hydrocarbon group having 7 to 14 carbon atoms, a hydrocarbon group having 1 to 3 carbon atoms, and — (A ₁ O) _s —H (wherein A ¹ O is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms, and s is a number from 1 to 5). R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 3 carbon atoms and — (A ¹ O) _s —H (wherein A ¹ O, s Is the same group as described above. A plurality of (A ¹ O) present in the molecule may be the same or different. X ⁻ is a halogen ion, CH ₃ SO ₄ ^— or CH ₃ CH ₂ SO ₄ ^— . ]

  (C) a quaternary ammonium salt having a specific structure as component, (a) alkylbenzene sulfonic acid or a salt thereof as component, and (b) an anionic surfactant having a specific structure as component. By using in combination, both functions are not hindered even in a short-time cleaning, and higher cleaning power can be obtained against various types of dirt.

In general formula (2), R ¹ is a hydrocarbon group having 10 to 14 carbon atoms, and the hydrocarbon group is preferably an alkyl group, and the alkyl group includes a linear or branched alkyl group. R ¹ is preferably a linear alkyl group having 12 carbon atoms.

In the general formula (2), R ² is a hydrocarbon group having 7 to 14 carbon atoms, a hydrocarbon group having 1 to 3 carbon atoms, and — (A ¹ O) _s —H (wherein A ¹ O is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms, and s is a group selected from 1 to 5 inclusive. The hydrocarbon group for R ² is preferably an alkyl group or a benzyl group, and is preferably an alkyl group from the viewpoint of the ability to clean spilled dirt. Examples of the alkyl group include linear or branched alkyl groups. In the case of an alkyl group, R ² preferably has 1 or more, 3 or less, or 10 or more carbon atoms. Moreover, - it is also preferred that (A ¹ O) _s -H.

In general formula (2), R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 3 carbon atoms and — (A ¹ O) _s —H (where A ¹ O and s And a hydrocarbon group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and a methyl group, an ethyl group, and a propyl group are more preferable.

  Examples of the cationic surfactant as the component (c) include the following (c-1) to (c-4). From the viewpoint of improving detergency against various stains, it is preferable to use one or more compounds selected from (c-1), (c-2) and (c-4). More preferably, it is one or more compounds selected from (c-1) and (c-2), and the component (c) is preferably the compound (c-1) from the viewpoint of the detergency of spilled dirt.

(C-1) R ¹ in the general formula (2) is a linear alkyl group having 10 to 14 carbon atoms, and R ² , R ³ and R ⁴ are each an alkyl group having 1 to 3 carbon atoms. An ammonium salt. More specifically, one or more compounds selected from n-decyltrimethyl quaternary ammonium chloride, n-lauryltrimethyl quaternary ammonium chloride and n-myristyltrimethyl quaternary ammonium chloride may be mentioned.
(C-2) An ammonium salt in which R ¹ is a branched alkyl group having 10 to 14 carbon atoms, and R ² , R ³ and R ⁴ are each an alkyl group having 1 to 3 carbon atoms.
(C-3) R ¹ is a linear alkyl group having 10 to 14 carbon atoms, R ² is a benzyl group, R ³ and R ⁴ are each an alkyl group having 1 to 3 carbon atoms. Some ammonium salts. More specifically, one or more compounds selected from decyldimethylbenzylammonium chloride, lauryldimethylbenzylammonium chloride and myristyldimethylbenzylammonium chloride can be mentioned.
(C-4) R ¹ is a linear alkyl group having 10 to 14 carbon atoms, R ² is — (A ¹ O) _s —H, and R ³ and R ⁴ each have 1 or more carbon atoms. 3. An ammonium salt which is an alkyl group of 3 or less.

<(D) component>
The component (d) is a nonionic surfactant represented by the following general formula (3).
_{^{R 5 O- (EO) t -H}} (3)
[Wherein R ⁵ represents a hydrocarbon group having 8 or more and 18 or less carbon atoms, EO represents an alkylene group, t represents an average number of added moles, and is a number of 1 or more and 10 or less. ]

In general formula (3) of component (d), R ⁵ is a hydrocarbon group having 8 to 18 carbon atoms, and from the viewpoint of detergency, carbonization having 10 to 16 carbon atoms and further 14 or less carbon atoms. A hydrogen group is preferred. The hydrocarbon group for R ⁵ is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group, from the viewpoint of detergency. R ⁵ is preferably a linear or branched hydrocarbon group, and more preferably a linear hydrocarbon group, from the viewpoint of detergency and availability of raw materials. In the general formula (3), the carbon atom of R ⁵ bonded to the oxygen atom may be a primary carbon atom or a secondary carbon atom.

  Although the method of obtaining the compound of General formula (3) is not specifically limited, It can obtain by carrying out addition reaction of ethylene oxide to the alcohol which has a C8-C18 hydrocarbon group. The average added mole number t of ethylene oxide is 1 or more and 10 or less. From the viewpoint of detergency against stain stains, t is 1 or more, preferably 2 or more, more preferably 2.5 or more, and further preferably 3 or more. Moreover, it is 10 or less at the point which can improve a washing | cleaning rate, 9 or less, Furthermore, 8 or less are preferable.

As the component (d), R ⁵ in the general formula (3) is a linear primary or secondary alkyl group having 10 to 14 carbon atoms from the viewpoint of detergency against sebum stains or stain stains. A nonionic surfactant having an average added mole number t of 3 or more and 8 or less is preferred.

<Water>
The liquid detergent composition for clothing of the present invention contains water in order to make the state at 0 ° C. to 40 ° C. a liquid state. As the water, deionized water (sometimes referred to as ion-exchanged water) or water in which sodium hypochlorite is added in an amount of 1 mg / kg or more and 5 mg / kg or less to the ion-exchanged water can be used.

<Liquid detergent composition for clothing>
The liquid detergent composition for clothing of the present invention maintains the high detergency against particle stains such as mud stains, stain stains such as spilled stains and sebum stains. ) Component content and (b) component total mass ratio is (c) component / [(a) component + (b) component], 0.02 or more and 0.2 or less is there. The mass ratio is more preferably 0.03 or more, more preferably 0.04 or more, and more preferably 0.05 or more, from the viewpoint of detergency against mud dirt and spilled dirt. The mass ratio is preferably 0.15 or less, more preferably 0.14 or less, more preferably 0.13 or less, more preferably 0.12 or less, in terms of the detergency of leftovers and sebum stains. .1 or less is more preferable.
In the present invention, the combined surfactant of (a), (b) and (c) against sebum stains by using (c), (a) and (b) in combination. The penetrability is enhanced, and even if the content of the component (c) is less than the total of the components (a) and (b), the sebum stain cleaning property is enhanced.

  In the liquid detergent composition for clothing of the present invention, the component (a) and the component (b) are not salts, but are acid-type compounds, that is, the masses of compounds assuming that the counter ion is a hydrogen atom ion. The mass ratio and mass% are calculated as the mass of the component (a) and the component (b).

In addition, the liquid detergent composition for clothing of the present invention has a mass ratio between the content of the component (b) and the content of the component (a) in terms of both the washing speed and the detergency. / (A) component is 0.15 or more and 10 or less. The mass ratio is more preferably 0.4 or more, more preferably 0.5 or more, and more preferably 0.7 or more in terms of improvement in cleaning speed and cleaning power against uneaten dirt. In terms of cleaning power against mud dirt, the mass ratio is preferably 8 or less, more preferably 6 or less, more preferably 5 or less, more preferably 3 or less, and more preferably 2 or less.
In the present invention, the mass ratio of the content of the component (b) and the content of the component (a) is within a specific range, so that the (a) component, the component (b) and the component (c) against spilled dirt. Improves the permeability and improves the cleanability of spilled dirt.

  In addition, the liquid detergent composition for clothing of the present invention maintains a high detergency against particle dirt such as mud dirt, stain dirt such as spilled dirt and sebum dirt, and the content of component (d) ( The mass ratio of the content of component a) to the total content of component (b) is (d) component / [(a) component + (b) component], and is 0.1 or more and 2 or less. It is preferable. From the viewpoint of detergency against mud dirt and spilled dirt, 0.2 or more is preferable, 0.3 or more is more preferable, and 0.4 or more is even more preferable. In terms of detergency of uneaten dirt and sebum dirt, 1.5 or less is more preferable, 1.2 or less is more preferable, 1.0 or less is more preferable, 0.8 or less is more preferable, and 0.6 or less is More preferred.

  In the liquid detergent composition for clothing of the present invention, from the point that a higher flavoring effect is obtained with respect to a certain amount of use, and the amount of use per use of the composition can be reduced, the component (a) The total amount of the content, the content of the component (b) and the content of the component (c) is more preferably 20% by mass, more preferably 25% by mass, and more preferably 30% by mass in the composition. In addition, the amount of the liquid detergent composition for clothing is not too small and can be used in an appropriate manner, and the total content of the component (a), the component (b), and the component (c) is: In a composition, 60 mass% or less is preferable, 50 mass% or less is still more preferable, and 45 mass% or less is still more preferable.

  The content of water is the sum of the component (a), the component (b), the component (c), the component (d), and the optional components described later, when the total content of all blended raw materials is 100% by mass. Although it is the remainder excluding the content, when the composition of the present invention is added to water used for washing, the washing speed can be improved by quickly dispersing. From that viewpoint, in the composition of the present invention, the content of water is preferably 5% by mass or more, and more preferably 8% by mass or more in the composition.

  Moreover, it is preferable that the liquid detergent composition for clothes of this invention contains the organic solvent which has one or more hydroxyl groups in a molecule | numerator as a (e1) component at the point which can improve a washing | cleaning rate. The organic solvent is preferably an organic solvent having a hydroxyl group and an ether group in the molecule from the viewpoint that the washing rate can be improved.

Examples of the organic solvent having one or more hydroxyl groups in the molecule include one or more compounds selected from the following components (e1-1) to (e1-3).
(E1-1) component: C2 or more, 6 or less divalent or more and 6 or less alcohol (excluding (e1-3) component)
Examples thereof include divalent or trivalent alcohol selected from ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and glycerin.
(E1-2) Component: Polyalkylene glycol containing an alkylene glycol unit having 2 or more and 4 or less carbon atoms Examples include polyalkylene glycol selected from diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and tripropylene glycol. It is done.
(E1-3) component: a monoalkyl ether of (mono- or poly) alkylene glycol having an alkylene glycol unit having 2 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms, such as diethylene glycol monomethyl ether, From triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol and 1-ethoxy-2-propanol Examples include selected compounds.

  In the component (e1-3), the term “(mono or poly) alkylene glycol” means monoalkylene glycol or polyalkylene glycol. Further, “polyalkylene glycol” means that the alkylene glycol unit is contained in an amount of 9 or less in one molecule.

  The component (e1) is preferably an organic solvent selected from propylene glycol and diethylene glycol monobutyl ether, and more preferably diethylene glycol monobutyl ether.

  The content of the component (e1) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 13% by mass or more in the composition from the viewpoint that the washing rate can be improved. In view of economy and storage stability, the content of the component (e1) is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 25% by mass or less in the composition.

  The liquid detergent composition for clothing of the present invention preferably contains an alkaline agent (hereinafter referred to as the component (e2)) from the viewpoint of detergency. In addition to alkali metal hydroxide, alkali metal carbonate, and the like, the alkali agent is an alkanol group in which one or more and three or less is an alkanol group having 2 to 4 carbon atoms, and the rest Can be mentioned alkanolamines in which is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. Of these, the alkanol group is preferably a hydroxyalkyl group, more preferably a hydroxyethyl group. Other than the alkanol group, a hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable. Examples of the alkanolamine include alkanolamines such as 2-aminoethanol, N-methylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, and triethanolamine. . In the present invention, the component (e2) is preferably an alkanolamine selected from monoethanolamine and triethanolamine, and more preferably monoethanolamine.

  The liquid detergent composition for clothing of the present invention contains component (e2) in the composition of 0.01% by mass or more, further 0.5% by mass or more, and 10% by mass or less, and further 8% by mass or less. It is preferable to do. Among them, alkanolamine as component (e2) is 0.5% by mass or more, further 1% by mass or more, further 3% by mass or more, and 8% by mass or less, further 7% by mass or less, and further 6% by mass or less. It is preferable to do. In the present invention, the content of the alkali agent (e2) component, particularly the alkanolamine, is incorporated into the composition from other components such as the counter ion of component (a) or component (b). Minutes shall be included.

  The pH of the liquid detergent composition for clothing of the present invention at 20 ° C. is preferably 6 or more, more preferably 6.5 or more, and further preferably 7 or more, and 11 or less, further 9 or less, and further 8 or less in terms of detergency. Is preferred. The pH is measured by the method described in Item 8.3 of JIS K3362: 1998, and the temperature is measured at 20 ° C. described.

  The liquid detergent composition for clothing of the present invention can be used in a cleaning method having a cleaning time of 1 minute or more and 7 minutes or less. The liquid detergent composition for clothing of the present invention can provide a sufficient cleaning power in a normal and appropriate cleaning time of, for example, 10 minutes, and also has a cleaning time of 1 minute or more and 7 minutes or less. Demonstrates detergency almost equivalent to the detergency obtained with a washing time of 10 minutes. Therefore, the use of the liquid cleaning composition for clothing of the present invention in a cleaning method with a cleaning time of 1 minute or more and 7 minutes or less means that the cleaning power can be maintained even if the cleaning time is shortened by the operator. It will be noticeable.

[How to wash clothes]
The present invention is a cleaning liquid containing water and a liquid detergent composition for clothing of the present invention of 0.01% by mass or more and 0.2% by mass or less, and having a temperature of 0 ° C. or more and 35 ° C. or less. The bath ratio represented by the ratio of the mass to the amount of the cleaning liquid (liter) is the amount of the cleaning liquid (liter) / the mass of the clothing (kg) = 3 to 50, and the clothing is used for 1 minute to 7 minutes. Provided is a method for washing clothes, which is washed below.

  The cleaning liquid may contain 0.01 mass% or more, further 0.02 mass% or more, and 0.2 mass% or less, and further 0.1 mass% or less of the liquid cleaning composition for clothing of the present invention. preferable. The cleaning liquid has a total content of the component (a), the content of the component (b) and the content of the component (c) of 0.006% by mass or more, further 0.01% by mass or more, and 0.08%. It is preferable to contain not more than mass%, more preferably not more than 0.07 mass%.

  Any water may be used as water for preparing the cleaning liquid. For example, tap water, ion exchange water, well water, river water and the like can be mentioned. Moreover, as the hardness of water suitable for cleaning, German hardness is 1 ° DH or more and 10 ° DH or less.

  The temperature of the cleaning liquid is preferably 0 ° C. or higher, more preferably 3 ° C. or higher, further preferably 5 ° C. or higher in terms of improving the cleaning rate. 35 degreeC or less is preferable and 30 degreeC or less is more preferable at the point which does not drop the oil agent contained in the fiber itself which comprises clothing too much, and maintains the feel of a fiber.

  In recent years, the washing machine has become larger, and the value of the bath ratio represented by the ratio of the amount of washing liquid (liter) to the mass of clothing (kg), that is, the amount of washing liquid (liter) / the mass of clothing (kg) (hereinafter, There is a tendency that the value of this ratio may be a bath ratio). When the bath ratio is reduced, it is said that when a household washing machine is used, the mechanical force due to stirring is not easily transmitted to the clothing, and the cleaning power is reduced. The washing | cleaning method of the clothing of this invention can improve a washing | cleaning speed also on washing conditions with a small bath ratio. In terms of detergency, the bath ratio is preferably 4 or more, and more preferably 5 or more. In addition, the bath ratio is preferably 45 or less, more preferably 40 or less, further 30 or less, and further 20 or less in that the effect of improving the cleaning rate can be obtained.

  “The effect of improving the cleaning rate can be obtained more” means that the value of “relative value of 5 minutes / 10 minutes (cleaning rate)” described in “Evaluation of cleaning rate” shown in the following examples is 1 Means close to.

  The clothes washing method of the present invention can provide sufficient washing power even if the washing time is short. In terms of cleaning power, the cleaning time is 1 minute or longer, preferably 2 minutes or longer, and more preferably 3 minutes or longer. It is 7 minutes or less, and 5 minutes or less is preferable in that the effect of improving the cleaning rate is obtained.

  The garment washing method of the present invention is a method of garment comprising fibers according to the consumer's use, rather than a method of immersing in a liquid used for smelting while feeding the fiber with a roller or the like, as in the fiber scouring method. In this way, the effect of the present invention can be obtained for an object that does not require a uniform mechanical force. Further, the cleaning method of the present invention is suitable for the rotary cleaning method. The rotary cleaning method means a cleaning method in which clothes that are not fixed to a rotating device rotate around a rotation axis together with a cleaning liquid. The rotary cleaning method can be performed by a rotary washing machine. Therefore, in the present invention, it is preferable to wash clothes using a rotary washing machine.

<Liquid detergent composition for clothing>
In a 300 ml glass beaker, put a stirrer piece (made of Teflon (registered trademark)) having a diameter of 60 mm, the finished mass is 200 g, and the content shown in Table 1 is (a) component, (b) component or Component (b ′), component (c), and 95% by mass of the required amount of water were added. After the addition, the mixture was stirred for 20 minutes at 100 rpm. Thereafter, the components (d) and (e1) are added, and the pH of the composition is adjusted to the pH described in Table 1 with the component (e2), and the final finished mass (200 g) is obtained using the remaining water. Thus, a liquid detergent composition for clothing having the formulation examples shown in Table 1 was obtained. The pH was measured by the method described in Item 8.3 of JIS K3362: 1998 (the temperature of the composition at the time of measurement was 20 ° C.). In addition, the component used for preparation of a composition is as follows.

(A) Component (a-1): Alkylbenzenesulfonic acid having a linear alkyl group having 10 to 14 carbon atoms (average carbon number 12) (note that (a-1) component has a pH of 8.0 described in Table 1) In the liquid detergent composition, it is contained in the form of an acid salt.)

(B) Component (b-1): In the general formula (1), R is a linear primary alkyl group having 12 or 14 carbon atoms, AO is a propyleneoxy group, p is 2.0, q is 0, and M is Monoethanolammonium compound (the concentration in the table is the acid type concentration, and the monoethanolammonium salt as a salt was converted to the concentration of monoethanolamine and included in component (e2)).
(B-2): In the general formula (1), R is a linear primary alkyl group having 12 or 14 carbon atoms, AO is a propyleneoxy group, p is 2.0, q is 2.0, and M is monoethanol. is a compound of ammonium, AO and EO _{may, RO- (AO) 2.0 - (} EO) 2.0 - the concentration of the block bound to that (in the table in the order is the concentration of the acid type, monoethanol ammonium salts of counter salt Was converted to the concentration of monoethanolamine and included in component (e2)).

Component (b ′) (Comparative compound of component (b))
(B′-1): In general formula (1), R is a linear primary alkyl group having 12 or 14 carbon atoms, p is 0, q is 2.0, and M is monoethanolammonium (table The concentration inside was acid type concentration, and the monoethanolammonium salt as a salt was converted into the concentration of monoethanolamine and included in the component (e2)).

(C) Component (c-1): N-lauryl-N, N, N-trimethylammonium chloride [in general formula (2), R ¹ is a linear alkyl group having 12 carbon atoms, R ² , R ³ , R Compounds in which ⁴ is a methyl group and X ⁻ is Cl ⁻
(C-2): N-lauryl-N- (2-hydroxyethyl) -N, N-dimethylammonium chloride [in the general formula (2), R ¹ is a linear alkyl group having 12 carbon atoms, R ² is − (A ¹ O) _s —H (AO is an ethyleneoxy group, s is 1), R ³ and R ⁴ are each a methyl group, and X ⁻ is Cl ⁻ ]

(D) Component (d-1): Compound obtained by adding an average of 7 moles of ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms [Softanol 70 (trade name), manufactured by Nippon Shokubai Co., Ltd.]
(D-2): Compound having an average of 4 mol of ethylene oxide added to a primary alcohol having 12 carbons (d-3): Compound having an average of 6 mol of ethylene oxide added to a primary alcohol having 12 carbons

(E1) Component (e1-1-1): Propylene glycol (e1-3-1): Diethylene glycol monobutyl ether

(E2) Component (e2-1): Monoethanolamine

Water: ion-exchanged water containing sodium hypochlorite in an amount of 3 mg / kg

<Evaluation>
By using the liquid detergent composition for clothing of Table 1 for the following evaluation, it is possible to evaluate the cleaning power against various stains and the cleaning power when the cleaning time is shortened. Table 1 shows the results of each evaluation. In addition, in the table | surface, each mass ratio was shown considering the (b ') component as (b) component for convenience.

(1) Detergency evaluation <Preparation of contaminated cloth for evaluation>
-Preparation of sebum soil-contaminated cloth (model sebum artificially contaminated cloth) A model sebum artificially contaminated cloth having the following composition is attached to the cloth to prepare a model sebum artificially contaminated cloth. The model sebum artificial contamination liquid is adhered to the cloth by printing the artificial contamination liquid on the cloth using a gravure roll coater. The process of making the model sebum artificial contamination liquid by attaching the model sebum artificial contamination liquid to the cloth is performed at a gravure roll cell capacity of 58 cm ³ / m ² , a coating speed of 1.0 m / min, a drying temperature of 100 ° C., and a drying time of 1 min. . The cloth is cotton 2003 (manufactured by Tanigami Shoten).

* Composition of model sebum artificial contamination liquid: 0.4% by mass of lauric acid, 3.1% by mass of myristic acid, 2.3% by mass of pentadecanoic acid, 6.2% by mass of palmitic acid, 0.4% by mass of heptadecanoic acid, stearin 1.6% by mass of acid, 7.8% by mass of oleic acid, 13.0% by mass of triolein, 2.2% by mass of n-hexadecyl palmitate, 6.5% by mass of squalene, 1.9% by mass of egg white lecithin liquid crystal , Kanuma red soil 8.1% by mass, carbon black 0.01% by mass, water balance (total 100% by mass)

・ Preparation of spilled dirt (meat sauce-contaminated cloth) Apply 0.15 g of commercially available retort meat sauce (mammer) to cotton knitted cloth (manufactured by Tanigami Shoten), spread evenly under an environment of 25 ° C. and 43% RH. What was dried for 12 hours is subjected to the test.

・ Preparation of artificial mud soil-contaminated cloth Kanuma Horticultural Akadama soil was dried at 120 ° C ± 5 ° C for 4 hours, then pulverized, and one with a 150 mesh (100 µm) pass was dried at 120 ° C ± 5 ° C for 2 hours, ± 150 g Is dispersed in 1000 L of parklene to obtain a dispersion. After the gold dispersion # 2023 cloth (cotton cloth, 10 cm × 10 cm) was brought into contact with the obtained dispersion liquid, brushing was performed, and the dispersion liquid was removed. Get a contaminated cloth.

<Cleaning test>
・ Evaluation of sebum detergency (1) Evaluation of cleaning rate Five model sebum artificially contaminated cloths (6 cm × 6 cm) prepared above were subjected to a targotometer (Ueshima, MS-8212) at 85 rpm for 5 minutes or 10 Wash for minutes. Agitation at the time of washing was performed with a stirring rod with three blades for a targotometer (bottom diameter: 6.8 cm, maximum length of the blades being 4.0 cm in the radial direction from the stirring rod). The cleaning conditions are all liquid detergent composition concentration 0.033% by mass, the water temperature is 20 ° C., and the bath ratio is 20 (adjusted with a cloth obtained by cutting cotton 2003 (manufactured by Tanigami Shoten) into 6 cm × 6 cm). After washing, rinse with tap water (20 ° C.) for 3 minutes. The washing rate is measured by the above method (1), and the average value of 5 sheets is obtained. Based on the respective cleaning rates (average values) of 5 minutes and 10 minutes, the 5 minutes / 10 minute cleaning relative value is obtained by the following formula.
5 minutes / 10 minutes cleaning relative value (washing speed) = washing rate (%) at 5 minutes washing time / washing rate (%) at 10 minutes washing time
The value of “5 minutes / 10 minutes cleaning relative value (cleaning rate)” is preferably closer to 1.

(2) In the above-mentioned “Evaluation of cleaning speed”, the cleaning rate (average value) of cleaning times of 5 minutes and 10 minutes is compared with Comparative Formulation Example 1. Can be evaluated. A higher cleaning rate (average value) than Comparative Formulation Example 1 is preferred.

Washing test for spilled dirt (meat sauce-contaminated cloth) The liquid detergent composition for evaluation was directly applied to 5 sheets of the above-prepared meat sauce-contaminated cloth (6 cm × 6 cm), respectively, and left in that state for 5 minutes. After that, it is put into 1 L of tap water and washed at 85 rpm with a turgotometer (Ueshima, MS-8212, stirring member is the same as above). The washing conditions were a washing time of 10 minutes, a detergent composition concentration of 0.033% by weight during washing, and a water temperature of 20 ° C. After washing, the bottle was rinsed with tap water (20 ° C.) for 3 minutes.
The raw cloth before contamination and the reflectance at 550 nm before and after washing are measured with a colorimetric color difference meter (Nippon Denshoku Co., Ltd., Z-300A), and the washing rate (%) is obtained by the following equation (5 washings) Find the average rate).
Washing rate (%) = 100 × [(reflectance after washing−reflectivity before washing) / (reflectance of base fabric−reflectivity before washing)]

Based on the cleaning rate (%) of the composition of Comparative Formulation Example 1, the relative cleaning value is obtained by the following formula.
Relative washing value = [washing rate of comparative example or comparative example (%)]-[washing rate of comparative blending example 1 (reference composition) (%)]
The higher the relative cleaning value, the higher the cleaning power. A significant difference is observed if the relative wash value difference is 3 or more.

・ Detergency test of mud soil-contaminated cloth Five artificial mud soil-contaminated cloths (artificial contaminated cloth) prepared above are placed in 1 L of a detergent aqueous solution, and a stirring type detergency tester (Targotometer, manufactured by Ueshima Seisakusho Co., Ltd.) The stirring member is washed under the following conditions using the same as described above.
Washing condition Rotation speed: 100 rpm, washing time: 10 minutes, concentration of liquid detergent composition: 0.133% by mass, water hardness: 4 ° DH, water temperature: 20 ° C., rinsing: washing with tap water for 5 minutes The force is measured with a self-recording colorimeter (manufactured by Shimadzu Corporation) on the reflectance of the untreated cloth and before and after washing, and the washing rate (%) (measured average of 5 contaminated cloths) is calculated using the following formula. Is calculated. Washing rate (%) = [(reflectance after washing−reflectance before washing) / (reflectance of base fabric−reflectivity before washing)] × 100

Based on the cleaning rate (%) of the composition of Comparative Formulation Example 1, the relative cleaning value is obtained by the following formula.
Relative washing value = [washing rate of comparative example or comparative example (%)]-[washing rate of comparative blending example 1 (reference composition) (%)]
The higher the relative cleaning value, the higher the cleaning power. A significant difference is observed if the relative wash value difference is 3 or more.

Claims (5)

The following (a) component, (b) component, (c) component, (d) component and water are contained,
The total amount of the content of the component (a), the content of the component (b), and the content of the component (c) is 15% by mass or more and 70% by mass or less,
The mass ratio of the content of the component (c), the content of the component (a) and the total content of the component (b) is (c) component / [(a) component + (b) component]. 0.02 or more and 0.2 or less,
The mass ratio of the content of the component (b) and the content of the component (a) is (b) component / (a) component, and is 0.15 or more and 10 or less.
Liquid detergent composition for clothing.
(A) Component: Alkylbenzenesulfonic acid or salt thereof (b) Component: Anionic surfactant represented by the following general formula (1) RO-[(AO) _p / (EO) _q ] -SO ₃ M (1 )
[Wherein R represents a hydrocarbon group having 8 to 22 carbon atoms, AO represents an alkyleneoxy group selected from an alkyleneoxy group having 3 carbon atoms and an alkyleneoxy group having 4 carbon atoms, and EO represents an ethyleneoxy group. Represents a group, p and q represent the average number of added moles, p is a number of 0.5 or more and 5 or less, and q is a number of 0 or more and 10 or less. “/” Indicates that the AO group and the EO group may be bonded to either random or block. M is a cation. ]
(C) Component: Quaternary ammonium salt represented by the following general formula (2)

[Wherein R ¹ is a hydrocarbon group having 10 to 14 carbon atoms, R ² is a hydrocarbon group having 7 to 14 carbon atoms, a hydrocarbon group having 1 to 3 carbon atoms, and — (A ₁ O) _s —H (wherein A ¹ O is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms, and s is a number from 1 to 5). R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 3 carbon atoms and — (A ¹ O) _s —H (wherein A ¹ O, s Is the same group as described above. A plurality of (A ¹ O) present in the molecule may be the same or different. X ⁻ is a halogen ion, CH ₃ SO ₄ ^— or CH ₃ CH ₂ SO ₄ ^— . ]
Component (d): Nonionic surfactant represented by the following general formula (3) R ⁵ O— (EO) _t —H (3)
[Wherein R ⁵ represents a hydrocarbon group having 8 or more and 18 or less carbon atoms, EO represents an alkylene group, t represents an average number of added moles, and is a number of 1 or more and 10 or less. ]   The mass ratio of the content of the component (d), the content of the component (a) and the total content of the component (b) is (d) component / [(a) component + (b) component]. The liquid cleaning composition for clothing according to claim 1, which is 0.1 or more and 2 or less.   The liquid cleaning composition for clothes according to claim 1 or 2, which is used in a cleaning method having a cleaning time of 1 minute or more and 7 minutes or less.   A cleaning liquid containing water and a liquid detergent composition for clothing according to any one of claims 1 to 3 in an amount of 0.01% by mass to 0.2% by mass and having a temperature of 0 ° C or higher and 35 ° C or lower. Then, the bath ratio represented by the ratio of the amount of the cleaning liquid (liter) and the mass of clothing (kg) is the amount of the cleaning liquid (liter) / the mass of clothing (kg) = 3 to 50, A method for washing clothing, wherein the clothing is washed for 1 minute or more and 7 minutes or less.   The washing | cleaning method of the clothing of Claim 4 which performs washing | cleaning of clothing using a rotary washing machine.