JP6231378B2 - 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 in which a surfactant and a solvent are combined, Patent Document 1 discloses (a) a nonionic surfactant having an average addition mole number of alkylene oxide of 16 to 35, (b) a carbon number of 3 and / or Or an anionic surfactant having 4 alkyleneoxy groups, and (c) a liquid detergent composition containing a specific solvent and having a high surfactant concentration.

  On the other hand, in order to perfume the washed clothes, it has been conventionally performed to add a fragrance to the cleaning agent. For example, Patent Document 2 discloses a liquid detergent composition containing a fragrance compound having LogP of 3 or more. Moreover, also in the said patent document 1, the fragrance | flavor is used as an arbitrary component.

  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 the clothes with the detergent composition is usually 10 minutes or longer, and is shortened to 7 minutes or less.

JP 2011-208130 A JP 2012-87228 A

  According to the investigation by the present inventors, when a course for shortening the washing time is selected in the fully automatic washing machine, operations such as reduction in the number of times of rinsing and shortening of the washing time are performed. In that case, it was newly found that the scent of the scent is changed from the dehydrated clothing immediately after washing, and the strength of the scent is reduced. Even if the washing time is short, the worker expects the scent to remain in the garment in the same manner as a normal washing course. Therefore, it is desired that the garment can be sufficiently flavored even when the washing time is short. However, even if a liquid detergent composition with an increased fragrance content is used in the hope that the fragrance will be equivalent to that of a normal laundry course and the strength will be improved, it will be sufficient for the economy. Cannot be obtained.

  The present invention provides a liquid detergent composition for clothing that can impart a fragrance derived from a flavor more strongly to clothing after dehydration after the washing step even if the washing time is short.

The present invention contains the following component (a), component (b), component (c) and water, and the mass ratio of the content of component (a) to the content of component (c) is component (c) / (A) component is 0.1 or more and 8 or less, and the total of the content of (a) component and the content of (c) component is 0.5% by mass or more and 5% by mass or less, It is related with the liquid cleaning composition for clothes whose sum of content of a) component and (b) component is 3 mass% or more and 70 mass% or less.
(A) Component: Fragrance compound whose LogP is 3 or more and 5 or less (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. ]
Component (c): one or more compounds selected from carboxylic acids having 3 to 8 carbon atoms and salts thereof

  In addition, the present invention is a cleaning liquid prepared by adding the liquid cleaning composition for clothing of the present invention in a ratio of 0.1 g to 2 g with respect to 1 liter of water, and the mass (kg) of clothing Washing the clothes for 1 minute or more and 7 minutes or less under the condition that the bath ratio represented by the amount of the washing liquid (liter) is the amount of the washing liquid (liter) / the mass of the clothing (kg) = 3 or more and 50 or less, The present invention relates to a method for washing clothes.

  ADVANTAGE OF THE INVENTION According to this invention, even if washing | cleaning time is short, the liquid cleaning composition for clothing which can provide the fragrance derived from a fragrance | flavor more strongly to the clothing after dehydration after a washing | cleaning process is provided. In the liquid detergent composition for clothing of the present invention, a fragrance equivalent to a standard course having a sufficient washing time can be left on the clothing even if the washing time is short. Therefore, the cleaning time can be shortened.

  The present inventors blended the component (a) and the component (c) at a specific mass ratio, and blended the component (b), so that the fragrance equivalent to the standard course having a sufficient washing time can be obtained. We found that even if it is short, it can be achieved. Hereinafter, the present invention will be described. The meaning of “scenting equivalent to a standard course with sufficient contact time can be achieved with the same strength and even with a short washing time” means “fast flavoring speed” or It may be expressed as “the perfume speed can be improved”.

<(A) component>
(A) A component is a fragrance | flavor compound whose LogP is 3-5. In view of the remaining fragrance, the LogP of the component (a) is preferably 3.2 or more. Moreover, 4.8 or less is preferable and 4.6 or less is more preferable. Here, Log P is a coefficient indicating the affinity of an organic compound for water and 1-octanol. 1-octanol / water partition coefficient P is a distribution equilibrium when a trace amount of compound is dissolved as a solute in a two-liquid solvent of 1-octanol and water, and is a ratio of the equilibrium concentration of the compound in each solvent. Generally shown in the form of their logarithmic LogP for the base 10.

  LogP values for many compounds are reported, and many values are listed in databases available from Daylight Chemical Information Systems, Inc. (Daylight CIS), etc., which can be referred to. When there is no measured LogP value, it is most convenient to calculate with the program “CLOGP” available from Daylight CIS. This program outputs the value of “calculated LogP (ClogP)” calculated by the Hansch, Leo fragment approach together with the measured LogP value, if any.

  The fragment approach is based on the chemical structure of the compound and takes into account the number of atoms and the type of chemical bond (cf. A. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, PG Sammens, JB Taylor and CA Ramsden, Eds., P.295, Pergamon Press, 1990). Since this CLogP value is currently the most general and reliable estimate, it can be used in place of the measured LogP value when selecting a compound. In the present invention, if there is a measured value of LogP, it is used, and if not, a CLogP value calculated by the program CLOGP v4.01 is used.

For example, i) α-pinene (4.2), β-pinene (4.2), camphene (4.2), limonene (4.4), terpinolene (4.4), myrcene (4.3), p -A hydrocarbon compound used as a perfume selected from Cymen (4.1),
ii) Sandal Mysore Core (3.9), Santalol (3.9), l-Menthol (3.2), Citronellol (3.3), Dihydromyrcenol (3.0), Ethyllinalool (3.1), Mugor (3.0), Neroridol (4.6) Alcohol used as a fragrance, selected from
iii) Aldehyde C-111 (4.1), Greenal (3.1), Citral (3.1), Citronellal (3.3), Amylcinnamic aldehyde (4.3), Hexylcinnamic aldehyde (4.9), Lilyal (3.9), Dihydrojasmon (3.1 ), Ionone α (3.7), methylionone α (4.2), methylionone G (4.0), an aldehyde compound used as a fragrance, a ketone compound used as a fragrance,
iv) Fragrance selected from heptyl acetate (3.4), citronellyl acetate (4.2), geranyl acetate (3.7), linalyl acetate (3.5), ethyl cinnamate (3.0), benzyl salicylate (4.2), isobutyl salicylate (3.9) Ester compounds used as
v) a phenolic compound used as a perfume selected from thymol (3.4) and banitrope (3.1),
vi) Examples include ether compounds used as perfumes selected from citronellyl ethyl ether (4.4), anethole (3.3), neroline yarayara (3.2), estellagol (3.1), and methylisoeugenol (3.0). The values in () are LogP values.

  The component (a) is a fragrance compound having a log P of 3 or more and 5 or less having a cyclic structure in that it easily dissolves in the polyoxyalkylene group as the component (b) and easily contacts the clothing together with the component (b) in the cleaning liquid. It is preferable to contain. Examples of the cyclic structure include C5, C6, C7, or C10 cyclic hydrocarbon groups.

Specifically, as the fragrance compound having a LogP having a cyclic structure of 3 or more and 5 or less,
vii) a hydrocarbon compound used as a perfume selected from α-pinene (4.2), β-pinene (4.2), camphene (4.2), limonene (4.4), terpinolene (4.4), p-cymene (4.1),
viii) Alcohol used as a fragrance selected from Sandal Mysore Core (3.9), Santa Roll (3.9), 1-Menthol (3.2),
ix) selected from amylcinnamic aldehyde (4.3), hexylcinnamic aldehyde (4.9), liliar (3.9), dihydrojasmon (3.1), ionone α (3.7), methylionone α (4.2), methylionone G (4.0), Aldehyde compounds used as perfumes, ketone compounds used as perfumes,
x) an ester compound used as a perfume selected from ethyl cinnamate (3.0), benzyl salicylate (4.2), and isobutyl salicylate (3.9);
xi) a phenolic compound used as a perfume selected from thymol (3.4) and banitrope (3.1),
xii) The ether compound used as a fragrance | flavor chosen from anethole (3.3), nerolin yarayara (3.2), estella gall (3.1), and methyl isoeugenol (3.0) can be mentioned.

  In the present invention, as a fragrance compound other than the component (a), a fragrance having a LogP of less than 3, preferably 2.8 or less can be used. Examples of fragrances having a Log P of less than 3 include terpineol (2.6), geraniol (2.8), linalool (2.6), myrcenol (2.6), nerol (2.8), cis-jasmon (2.6), phenylethyl acetate (2.1), Allyl amyl glycolate (2.5), rifarom (2.3), cis-3-hexyl acetate (2.3), styryl acetate (2.3), ot-butylcyclohexanone (2.3), pt-butylcyclohexanone (2.3), Acetyl eugenol (2.8), cinnamyl acetate (2.4), eugenol (2.4), isoeugenol (2.6), mussins (2.9), anisole (2.1), methyl eugenol (2.8), coumarin (1.4), phenylethyl alcohol (1.2) ) And the like.

In the present invention, in the total fragrance compound, the ratio of the component (a) is 40% by mass or more, further 50% by mass or more, further 60% by mass or more, 90% by mass or less, further 80% by mass or less, and further 75% by mass. The following is preferable.
In the present invention, the ratio of the component (a) having a cyclic structure in the component (a) is preferably 30% by mass or more, further 40% by mass or more, further 50% by mass or more, and 80% by mass or less.

  Perfume compounds include "Fundamental knowledge of perfume and fragrance" (by Nakajima Motoki, published by Sangyo Tosho Co., Ltd., 1996, 2nd edition) and "Factual knowledge of perfume" (by Motoichi Into, published by Toyo Keizai Shinposha, 1985) Year 2nd edition) can be referred to.

<(B) component>
The component (b) is used in combination with the component (a), so that the liquid detergent composition containing the component (b) and the composition containing water and the clothes can be dehydrated after contact even if the contact time is short. Aroma can be imparted to the clothing immediately after.

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 is 8 or more carbon atoms in that the fragrance derived from the fragrance component (a) is scented from the dehydrated clothing after the washing step, preferably 10 or more, more preferably 12 or more, and 16 or less, Furthermore, 14 or less is preferable. 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 imparting a fragrance derived from the fragrance compound which is the component (a) and the availability of raw materials. R is preferably an alkyl group having 12 to 14 carbon atoms, and more preferably a linear alkyl group. In the general formula (1), 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 (generally called a butyleneoxy group) is more preferred, and an oxypropane-1,2-diyl group is most 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 of enhancing the residual fragrance of the clothes after dehydration after the washing step, p is preferably 0.8 or more, more preferably 1 or more, still more preferably 1.5 or more, and still more preferably. Is 1.8 or more. From the viewpoint of enhancing the residual scenting property on the clothes after dehydration after the washing step, p is 5 or less, preferably 4 or less, more preferably 3 or less.

  Q in the general formula (1) is the average added mole number of EO, and is 0 or more from the point that the fragrance derived from the fragrance as the component (a) is strongly scented from the clothes after dehydration after the washing step. The number is 10 or less. q is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1 or more, and still more preferably 2 or more. From the viewpoint of enhancing the residual fragrance of the clothes after dehydration after the washing step, q is 10 or less, preferably 8 or less, more preferably 5 or less, and even more preferably 3 or less.

The anionic surfactant of the general formula (1) is preferably such that AO and EO are bonded together in blocks in that the fragrance derived from the component (a) can be strongly imparted to the clothing. 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 alkylene oxide having 3 to 8 carbon atoms and / or an alcohol having a hydrocarbon group having 22 to 22 carbon atoms, preferably 1 mol of a linear primary aliphatic saturated alcohol having 10 to 14 carbon atoms, 4 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 the intermediate compound (1) added in the 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 one or more compounds selected from carboxylic acids having 3 to 8 carbon atoms and salts thereof. (C) By using the component (a) and the component (b) together under the predetermined conditions, the dehydration after the washing step can be performed even at a short contact time of 1 minute or more and 7 minutes or less. The fragrance derived from the fragrance compound as the component (a) can be strongly imparted to the garment.

Specific examples of the component (c) include one or more compounds selected from the following (c1) and (c2).
(C1) One or more compounds selected from divalent carboxylic acids having 3 to 7 carbon atoms, trivalent carboxylic acids having 4 to 7 carbon atoms, and salts thereof .
Specific examples include one or more compounds selected from malonic acid, succinic acid, glutaric acid, citric acid, and salts thereof.
(C2) One or more compounds selected from monovalent carboxylic acids having 7 or 8 total carbon atoms and having an aromatic group in the molecule, and salts thereof.
Specific examples include one or more compounds selected from benzoic acid, methylbenzoic acid, salicylic acid, phthalic acid, isophthalic acid, terephthalic acid, and salts thereof.

  Examples of the salt of component (c) include alkali metal salts such as sodium salts, potassium salts, alkaline earth metal salts such as magnesium salts, alkanolamine salts such as monoethanolamine salts and triethanolamine salts.

  From the viewpoint of enhancing the residual fragrance of the clothes after dehydration after the washing step, the component (c) is preferably at least one compound selected from citric acid, malic acid, succinic acid, benzoic acid, and salts thereof. One or more compounds selected from citric acid, benzoic acid, and salts thereof are more preferable, and one or more compounds selected from benzoic acid and salts thereof are particularly preferable.

<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 mass ratio of the content of the component (a) and the content of the component (b) is (a) component / (b) component, and is 0 in terms of enhancing the residual fragrance to the clothing after dehydration after the washing step. .015 or more is preferable, and 0.02 or more is more preferable. Moreover, 0.08 or less is preferable and 0.06 or less is more preferable at the point which scents the fragrance derived from (a) component from the clothes after dehydration after a washing | cleaning process.

  In the present invention, the component (b) and the component (c) may be acid or salt, and the acid type compound, that is, the mass of the compound assuming that the counter ion of the carboxyl group is a hydrogen atom ion. (B) A mass ratio or mass% is calculated as the mass of the component.

  In the liquid cleaning composition for clothing of the present invention, the total amount of the content of the component (a) and the content of the component (b) obtains a higher flavoring effect with respect to a certain amount used, and From the point which can reduce the usage-amount of a composition once, it is 3 mass% or more, 10 mass% or more is preferable and 15 mass% or more is more preferable. Moreover, the total of the content of (a) component and the content of (b) component is 70 mass% or less at the point which can use it by moderate use without using too little the amount of liquid cleaning composition for clothes. Yes, 60 mass% or less is preferable, 40 mass% or less is more preferable, and 30 mass% or less is still more preferable.

  Moreover, in the liquid detergent composition for clothes of this invention, since the fragrance derived from (a) component can be strongly provided with respect to the clothes after dehydration after a washing | cleaning process, content of (a) component and ( The mass ratio of the content of the component c) to the component (c) / component (a) is 0.1 or more and 8 or less. The mass ratio is preferably 0.15 or more, more preferably 0.2 or more, and more preferably 0.5 or more in that the fragrance derived from the component (a) is scented from the clothes after dehydration after the washing step. Preferably, 1.0 or more is more preferable, and 1.3 or more is more preferable. From the economical viewpoint, the mass ratio is preferably 7 or less, more preferably 6 or less, and still more preferably 5 or less.

  Moreover, in the liquid detergent composition for clothes of this invention, since the fragrance derived from (a) component can be strongly provided with respect to the clothes after dehydration after a washing | cleaning process, content of (a) component and ( c) The total content of the components is 0.5% by mass or more and 5% by mass or less. (A) 0.6 mass% or more is preferable, 0.7 mass% or more is more preferable, and 0.8 mass% or more is preferable at the point which scents the fragrance derived from a component from the clothes after dehydration after a washing process. More preferably, 1.0 mass% or more is more preferable, and 1.5 mass% or more is more preferable. From an economical viewpoint, 4.5 mass% or less is preferable, and 4 mass% or less is more preferable.

  The component (c) is at least one selected from (c1) a divalent carboxylic acid having a total carbon number of 3 to 7 and a trivalent carboxylic acid having a total carbon number of 4 to 7 In the case of a compound and one or more compounds selected from these salts [hereinafter referred to as component (c1)], the mass ratio of the content of component (a) to the content of component (c1) is ( c1) component / (a) component, which is 0.1 or more and 8 or less, and the mass ratio is preferably 0.15 or more in that the fragrance derived from the component (a) is perfumed from clothing. The above is more preferable, and 0.5 or more is more preferable. In terms of economy, the mass ratio is preferably 7 or less, more preferably 6 or less, and still more preferably 5 or less.

  Component (c) is (c2) one or more compounds selected from monovalent carboxylic acids having 7 or 8 total carbon atoms and having an aromatic group in the molecule and salts thereof [hereinafter referred to as component (c2) The mass ratio of the content of the component (a) and the content of the component (c2) is (c2) component / (a) component and is 0.1 or more and 8 or less, a) The mass ratio is preferably 0.15 or more, more preferably 0.2 or more, and even more preferably 0.5 or more, in that the fragrance derived from the component is scented from the clothes after dehydration after the washing step. In terms of economy, the mass ratio is preferably 7 or less, more preferably 6 or less, and still more preferably 5 or less.

  The content of water is an optional component such as the component (a), the component (b), the component (c), and the component (d) described later, when the total content of all blended raw materials is 100% by mass. The balance excluding the total content. When the composition of the present invention is added to water used for washing, the composition can be quickly dispersed to further improve the flavoring rate. 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.

The liquid detergent composition for clothing of the present invention is a nonionic interface of the following component (d), in that the clothing after dehydration after the washing step can be further scented with the scent derived from the component (a). An activator can be included.
(D) Component: Nonionic surfactant represented by the following general formula (2) R ¹ O— (EO) _m —H (2)
[Wherein, R ¹ represents a hydrocarbon group having 8 or more and 18 or less carbon atoms, EO represents an alkylene group, m represents an average number of added moles, and is 1 or more and 10 or less. ]

In the general formula (2) of the component (d), R ¹ is a hydrocarbon group having 8 to 18 carbon atoms, and the fragrance derived from the fragrance as the component (a) is added to the clothes after dehydration after the washing step. A hydrocarbon group having 10 or more carbon atoms and 16 or less carbon atoms, and further 14 or less carbon atoms is preferable because it can be imparted. The hydrocarbon group for R ¹ is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, from the viewpoint of availability of raw materials. R ¹ is preferably a linear or branched hydrocarbon group, more preferably a linear hydrocarbon group, from the viewpoint of availability of raw materials. In the general formula (2), the carbon atom of R ¹ 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 (2) 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 m of ethylene oxide is 1 or more and 10 or less. From the viewpoint that the flavoring speed can be improved, m is 1 or more, 2 or more, further 2.5 or more, and further preferably 3 or more. Moreover, it is 10 or less at the point of the intensity | strength of fragrance, 9 or less, Furthermore, 8 or less are preferable.

As the component (d), from the viewpoint of improving the availability of raw materials and the perfume rate, R ¹ in the general formula (2) is a linear primary or secondary alkyl group having 10 to 14 carbon atoms. A nonionic surfactant having an average added mole number of m of 3 or more and 8 or less is preferable.

  By using the component (d) in combination with the component (b), it is possible to enhance the residual fragrance of the clothes after dehydration after the washing step of the component (a). When the component (d) is contained, the mass ratio between the content of the component (b) and the content of the component (d) is (d) component / (b) component, 0.1 or more, and further 0.2 The above is preferable, and 10 or less, further 8 or less, further 5 or less, and further 4 or less are preferable.

  In addition, the liquid detergent composition for clothing of the present invention is an organic solvent having one or more hydroxyl groups in the molecule as the component (e1) in that it increases the residual fragrance to the clothing after dehydration after the washing step. It is preferable to contain. The organic solvent is preferably an organic solvent having a hydroxyl group and an ether group in the molecule from the viewpoint that the flavoring speed 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 more preferably 13% by mass or more in the composition from the viewpoint of enhancing the residual fragrance to the clothes after dehydration after the washing step. Is more preferable. 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 particularly 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 liquid detergent composition for clothing of the present invention is a fatty acid of the following (f) component and further its component in that the clothing after dehydration after the washing step can be further scented with the scent derived from the component (a). Salts can be included.
(F) Component: Fatty acids having 12 to 18 carbon atoms and salts thereof

  (F) The fatty acid component is combined with one or more ions selected from calcium ions and magnesium ions, which are hardness components in the cleaning liquid, and the hydrophobicity is increased, combined with the component (c), (a) A fragrance compound as a component can be adsorbed to clothing.

  The component (f) is preferably a fatty acid having 14 or more and 18 or less carbon atoms having an unsaturated group, from the viewpoint that a fragrance derived from the fragrance as the component (a) can be imparted to the clothing after dehydration after the washing step. When the fatty acid has an unsaturated group, the component (a) is easily taken into the aggregate formed by the component (f) in the washing liquid in the washing step, and is easily adsorbed to the clothing together with the component (f). The content of the fatty acid having 14 to 18 carbon atoms having an unsaturated group in the component (f) is preferably 10% by mass or more, more preferably 15% by mass or more, and more preferably 20% by mass or more. . And in the point which can give the fragrance derived from the fragrance | flavor which is (a) component to the clothing after dehydration after a washing | cleaning process, C14 or more and 18 or less fatty acid containing an unsaturated group in a component are contained. The amount is preferably 60% by mass or less, more preferably 50% by mass or less, and more preferably 40% by mass or less.

In the liquid detergent composition for clothing of the present invention, the component (f) relative to the content of the component (c) from the point that the fragrance derived from the fragrance as the component (a) can be imparted to the clothing after dehydration after the washing step The mass ratio of the content of (f) component / (c) component is preferably 2 or more and 8 or less. The mass ratio is more preferably 3 or more, and more preferably 3.5 or more, from the viewpoint that the fragrance derived from the fragrance as the component (a) can be imparted to the clothing after dehydration after the washing step. The mass ratio is preferably 7.5 or less, more preferably 7 or less, and more preferably 6.5 or less in that it makes it difficult to feel an oily odor derived from the component (f) from the clothing.
In addition, let the mass of (f) component be the mass which converted the counter ion of the fatty acid ion into the acid type.

  The pH at 20 ° C. of the liquid detergent composition for clothing of the present invention 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, from the viewpoint of storage stability of the fragrance. Furthermore, 8 or less is preferable. 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 has a scent strength equivalent to that of 10 minutes in addition to obtaining sufficient detergency in a normal moderate washing time of, for example, 10 minutes. It can be applied to clothes after dehydration after the washing process. Therefore, the use of the liquid cleaning composition for clothing of the present invention in a cleaning method having a cleaning time of 1 minute or more and 7 minutes or less means that the scent imparting effect is maintained even if the cleaning time is shortened to the operator. It will be more noticeable.

[How to wash clothes]
The present invention is a cleaning liquid prepared by adding the liquid detergent composition for clothing of the present invention at a ratio of 0.1 g to 2 g with respect to 1 liter of water. Washing of clothing, in which the bath ratio expressed in amount (liter) is the amount of washing liquid (liter) / mass of clothing (kg) = 3 to 50, and the clothing is washed for 1 minute or more and 7 minutes or less Provide a method.

  The water for preparing the cleaning liquid is not particularly limited, and examples thereof include tap water, river water, well water, spring water, and ion exchange water. In particular, it is preferable to use water containing a hardness component such as calcium ion or magnesium ion because the fragrance derived from the component (a) can be strongly scented from the clothes after dehydration after the washing step.

  Hardness components such as magnesium ions and calcium ions in water are ionically bonded to the carboxylic acid of component (c) to appropriately hydrophobize component (c), and a highly hydrophobic fragrance having a Log P of 3 or more and 5 or less It is easy to mix with the component (a) and the amount of the compound group with high hydrophobicity apparently increases, so that it is easy to adhere to the clothes after dehydration after the washing process even in a short washing time. It is done. (A) From the point which a component adheres to clothing even for a short time and raises residual fragrance property, the hardness of water exceeds 0 degree DH in German hardness, and 10 degrees DH or less is preferable. More preferably, it is 1 ° DH or more and 8 ° DH or less.

  The amount of the liquid detergent composition for clothing is preferably 0.1 g or more in terms of mass with respect to 1 liter of water in that the preferred aroma derived from the component (a) can be strongly imparted to the clothing after dehydration after the washing step. 0.2 g or more is preferable. 2 g or less is preferable, 1.5 g or less is more preferable, and 1 g or less is still more preferable at the point which can make the fragrance fragrant | scented from the clothes after dehydration after a washing process moderately.

  Even if the washing | cleaning time of the clothing of this invention is short, the fragrance derived from the component (a) can be strongly scented from the clothing after dehydration after the washing step. The washing time is 1 minute or more from the viewpoint of improving the residual fragrance, preferably 2 minutes or more, and more preferably 3 minutes or more. It is 7 minutes or less, and 5 minutes or less is preferable in that the effect of improving the flavoring rate can be obtained more.

  The temperature of the cleaning liquid is preferably 0 ° C. or higher and 40 ° C. or lower in terms of imparting scent to the clothing after dehydration after the cleaning step. (A) 0 degreeC or more is preferable, 3 degreeC or more is more preferable, and 5 degreeC or more is still more preferable at the point which makes the fragrance derived from a component strongly scent from the clothes after dehydration after a washing process. 35 degreeC or less is preferable and 30 degreeC or less is more preferable at the point which raises the residual fragrance property of the clothing after the washing | cleaning process after dehydration.

  In recent years, with the increase in the size of washing machines, the value of the bath ratio (the amount of washing liquid (liter)) / the mass of clothing (kg) represented by the ratio of the mass of clothing and the amount of washing liquid (liter) tends to decrease. is there. When the bath ratio is small, when a household washing machine is used, the mechanical force due to stirring is not easily transmitted to the clothing, and the component (a) in the cleaning liquid is less likely to adhere uniformly to the entire clothing. The washing | cleaning method of the clothing of this invention can improve the residual scent property of the whole clothing after the dehydration after a washing | cleaning process also on washing conditions with a small bath ratio. The bath ratio is 3 or more and 50 or less in that the improvement of the residual scent of the clothes after dehydration after the washing step is good, and 4 or more is preferable in that the component (a) can be uniformly attached to the clothes. 5 or more is more preferable. 45 or less are preferred, 40 or less are more preferred, 30 or less are still more preferred, and 20 or less are still more preferred at the point which raises the residual fragrance property of clothes after dehydration after a washing process more.

  In the cleaning method of the present invention, the cleaning liquid is 0.01% by mass or more, further 0.02% by mass or more, and 0.2% by mass or less, and further 0.1% by mass of the liquid detergent composition for clothing of the present invention. % Or less is preferable. Further, the cleaning liquid has a total content of the component (a) and the content of the component (b) of 0.002% by mass or more, further 0.004% by mass or more, 0.02% by mass or less, and further 0.01 It is preferable to contain a mass% or less.

  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 superior flavoring effect of the present invention can be obtained for an object that does not require 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.

(1) Preparation of liquid detergent composition for clothing A stirrer piece (made of Teflon (registered trademark)) having a diameter of 60 mm is put into a 300 ml glass beaker, and the resulting mass is 200 g, and the contents shown in Table 1 are obtained. Thus, (a) component, (b) component or (b ′) component, (c) component, 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, if necessary, the components (d) and (e1) are added, 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) to obtain a liquid detergent composition for clothing shown in Table 1. 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.). The following evaluations were performed using the obtained compositions. The components in the table are as follows. The results are shown in Table 1. In addition, Table 3 shows formulation examples that are considered to achieve the effects of the present invention.

(A) Component (a-1): Perfume composition described in Table 2 [(a) component, LogP content of 67 or more by mass is a perfume compound]

(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 an average of 2.0, q is 0, M Is a compound of monoethanolammonium [the compounding amount in the table is the compounding amount of the acid type corresponding to the component (b), and the monoethanolamine as a salt was added to the 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 - order in the amount of the block bound to that [in the table in (b) the amount of component equivalent acid form Yes, monoethanolamine as a salt was added to the component (e2). ].
(B-3): 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 0.7 on average, q is 2.0, and M is mono. a compound of the ethanol ammonium, AO and EO _{may, RO- (AO) 0.7 - (} EO) 2.0 - the amount of block binding to that [in the table in the order of the amount of component (b) corresponding acid form And the monoethanolamine as a salt was added to the component (e2). ].

Component (b ′) (Comparative compound of component (b))
(B′-1): In the 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 [in the table The compounding amount was an acid type compounding amount corresponding to the component (b ′), and monoethanolamine as a salt was added to the component (e2). ].

(C) Component (c-1): Citric acid (c-2): Sodium benzoate

(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) Component: Monoethanolamine

(F) Component (f-1): Fatty acid having the following composition
Lauric acid 50% by mass, myristic acid 20% by mass, stearic acid 10% by mass, oleic acid 20% by mass, content of fatty acid having unsaturated group is 20% by mass
(F-2): Fatty acid having the following composition
Lauric acid 30% by mass, myristic acid 20% by mass, stearic acid 10% by mass, oleic acid 40% by mass, content of unsaturated fatty acid 40% by mass

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

(2) Flavor evaluation <Preparation of evaluation cloth>
A model sebum artificial contamination liquid having the following composition was adhered to the cloth to prepare an evaluation cloth. The model sebum artificial contamination liquid was attached to the cloth by printing the artificial contamination liquid on the cloth using a gravure roll coater. The process of preparing the model sebum artificial contamination liquid by attaching the model sebum artificial contamination liquid to the cloth is performed at a cell capacity of gravure roll 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. It was. The cloth used was 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)

<Incense evaluation method>
Into a stainless beaker having a cylindrical shape with an inner diameter of 12 cm and a height of 16 cm, 0.35 g of the liquid detergent composition for clothing described in Table 1 is introduced into 1 liter of water having a German hardness of 4 ° DH, and an evaluation cloth (6 cm × 6 cm) was added, and cotton # 2003 (6 cm × 6 cm) was added and adjusted so that the bath ratio was 20. Targotometer (Ueshima, MS-8212, a disk with a diameter of 6.8 cm is placed at the end of the stirring bar so that the rotation axis of the disk and the rotation axis of the stirring bar are the same axis, and a maximum diameter of 8 cm on the disk. Was washed at 85 r / min for 5 minutes. Thereafter, the evaluation cloth was taken out and dehydrated for 1 minute (National fully automatic washing machine NA-F60E), and five evaluation cloths were superposed to obtain an evaluation cloth (5). An evaluation cloth (10) prepared under the same washing conditions as described above was obtained except that the washing time for flavoring was 10 minutes. Using the evaluation cloth (10) as a reference, the fragrance tone and fragrance strength of the evaluation cloth (5) were evaluated using the evaluation panel for fragrance (10 women in their 30s) according to the following evaluation standards, and the average value was calculated. .

-Evaluation of incense tone An average value of 1.2 or more was considered acceptable. A difference of 0.2 or more is recognized as an advantageous difference.
+2: The fragrance scented from the evaluation cloth (5) has the same fragrance as that of the evaluation cloth (10).
+1: From the evaluation cloth (5), there is a scent similar to that of the evaluation cloth (10), but also a slightly different scent.
0: From the evaluation cloth (5), the scent similar to that of the evaluation cloth (10) is slightly scented, but clearly different scent is strongly scented.

・ Evaluation of fragrance strength An average value of 1.2 or more was accepted. A difference of 0.2 or more is recognized as an advantageous difference.
+2: The intensity of the fragrance from the evaluation cloth (5) is as strong as the evaluation cloth (10).
+1: The strength of the fragrance from the evaluation cloth (5) is slightly weaker than that of the evaluation cloth (10).
0: The strength of the fragrance from the evaluation cloth (5) is clearly weaker than that of the evaluation cloth (10).

* 1 Numbers in the table indicate mass% as component (a).
* 2 The amount required for pH adjustment including the amount of monoethanolamine incorporated from component (b).

Claims (7)

The following (a) component, (b) component, (c) component and water are contained, and mass ratio of content of (a) component and content of (c) component is (c) component / (a) The component is 0.1 or more and 8 or less, the sum of the content of the component (a) and the content of the component (c) is 0.5% by mass or more and 5% by mass or less, and the component (a) It is related with the liquid cleaning composition for clothes whose sum total of content and content of (b) component is 3 mass% or more and 70 mass% or less.
(A) Component: Fragrance compound whose LogP is 3 or more and 5 or less (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. ]
Component (c): one or more compounds selected from carboxylic acids having 3 to 8 carbon atoms and salts thereof, and one or more compounds selected from the following (c1) and (c2)
(C1) One or more compounds selected from divalent carboxylic acids having 3 to 7 carbon atoms, trivalent carboxylic acids having 4 to 7 carbon atoms, and salts thereof .
(C2) One or more compounds selected from monovalent carboxylic acids having 7 or 8 total carbon atoms and having an aromatic group in the molecule, and salts thereof. Further, as the component (d), a nonionic surfactant represented by the following general formula (2) is contained, and the mass ratio between the content of the component (b) and the content of the component (d) is (d). The liquid detergent composition for clothes according to claim 1, which is component / component (b) and is 0.1 or more and 10 or less.
R ¹ O— (EO) _m —H (2)
[Wherein, R ¹ represents a hydrocarbon group having 8 or more and 18 or less carbon atoms, EO represents an alkylene group, m represents an average number of added moles, and is 1 or more and 10 or less. ]   Further, as the component (f), a fatty acid having 12 to 18 carbon atoms and a salt thereof are contained, and the mass ratio of the content of the component (f) to the content of the component (c) is (f) component / (c The liquid cleaning composition for clothing according to claim 1 or 2, wherein the composition is 2 or more and 8 or less.   The liquid detergent composition for clothing according to claim 3, wherein the content of the fatty acid having 14 to 18 carbon atoms having an unsaturated group in the component (f) is 10% by mass to 70% by mass.   The liquid cleaning composition for clothes according to any one of claims 1 to 4, which is used in a cleaning method having a cleaning time of 1 minute or more and 7 minutes or less.   A washing liquid prepared by adding the liquid detergent composition for clothing according to any one of claims 1 to 5 at a ratio of 0.1 g or more to 2 g or less per 1 liter of water, and the mass (kg) of the clothing. The bath ratio expressed by 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 clothes are washed for 1 minute or more and 7 minutes or less. , How to wash clothes.   The method for washing clothes according to claim 6, wherein the clothes are washed using a rotary washing machine.