JP5341023B2 - Liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition excellent in detergency, deodorizing property of a textile product such as clothing, and preservation stability, concerning a liquid detergent composition to be blended with a surfactant in a high concentration. <P>SOLUTION: The liquid detergent composition includes a 35-85 mass% surfactant (A), a 0.1-5 mass% hydrotrope agent (B), 0.3-10 mass% hydrogen peroxide (C), 2-40 mass% water-miscible solvent (D) and water, and which contains specific two kinds of nonionic surfactant (a1), (a2), and a cationic surfactant (a3) respectively in a specific range as the surfactant (A), wherein the mass ratio of (a3)/(B) is 0.1-3, and pH at 20&deg;C described in the 8.3rd term of JIS K 3362:1998 is 3-7. <P>COPYRIGHT: (C)2012,JPO&amp;INPIT

Description

  The present invention relates to a liquid detergent composition detergent. Furthermore, it is related with the liquid cleaning composition for textiles with the high effect which suppresses the dry odor after washing clothes etc ..

  In recent years, environmental awareness has increased, and there is a strong demand for the appearance of cleaning agents that have a low environmental impact. So-called concentrated type cleaning agents with higher cleaning component concentrations than conventional cleaning agents reduce the size of the cleaning agent itself, reduce the amount of container resin, reduce transportation costs, reduce waste after use, etc. It is thought that it is very effective for reducing.

  However, in a normal liquid detergent, there is a problem that if the concentration of a surfactant as a washing component is increased (for example, 40% by mass or more), thickening or gelation occurs and the usability is significantly impaired. This is because an increase in the concentration of the surfactant forms a remarkably high phase such as liquid crystal or crystal in the composition. In addition, in such a surfactant high concentration system, there is a method of obtaining a low viscosity composition by adding a large amount of a solvent in order to suppress high viscosity, but the composition is diluted with water when diluted with water, particularly cold water. As it goes on, the diluted composition forms liquid crystals and causes poor solubility. Further, when the surfactant concentration is increased, there are problems in solubility and stability such that the composition is easily solidified during low-temperature storage. On the other hand, various techniques are known. Patent Document 1 achieves a high concentration by using a special organic solvent and a polyoxyethylene-polyoxypropylene alkyl ether type nonionic surfactant as a main agent. doing. Patent Document 2 discloses a liquid detergent composition containing an ethylene oxide addition type nonionic surfactant of a primary alcohol and an ethylene oxide addition type non-nonion of a secondary alcohol in a specific ratio, and further using an organic solvent in combination. Has been. Further, Patent Document 3 discloses a surfactant system comprising a polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether type nonionic surfactant and a secondary alkyl (or secondary alkenyl group) polyoxyethylene alkyl ether, and Liquid detergent compositions containing alkanolamines are disclosed.

  On the other hand, in recent years, awareness of hygiene has been increasing, and in the laundry detergent field, products that have demonstrated the antibacterial effect of suppressing the generation of dry odors in clothes after washing and off-flavors when washing is stored for long periods of time. Is on the market. As a method of imparting antibacterial properties, a method of blending a compound known as a so-called antibacterial agent, a method of blending a cationic surfactant having a specific structure such as benzalkonium chloride, or a specific bleaching agent is contained. A method is mentioned. Moreover, the technique which uses these components together is also known, for example, patent document 4 describes a technique for suppressing the off-flavor of room drying containing antibacterial metal-containing fine particles, surfactant, and water. It is described that the composition contains a nonionic surfactant as a main base and contains a cationic surfactant as hydrogen peroxide or an organic antibacterial antibacterial agent. For example, Patent Documents 5 and 6 disclose liquid bleach compositions containing a nonionic surfactant as a main base and containing a cationic surfactant and hydrogen peroxide. Patent Documents 5 and 6 disclose examples in which a polyoxyethylene polyoxypropylene alkyl ether type nonionic surfactant is used as a nonionic surfactant. These liquid bleach detergent compositions are intended for bleaching power against stains adhering to textile products, and it is necessary to shift the pH from acidic to alkaline when dissolved in water to make a washing solution. It is necessary to use a relatively large amount of the system compound and polyol.

JP-A-8-157867 JP-A-9-169994 JP 11-2441092 A JP 2006-328170 A JP 2007-39595 A JP 2007-106903 A

  Patent Documents 5 and 6 are intended to enhance the bleaching effect, and are transferred from a stable acidic composition to an alkalinity that exhibits a bleaching effect upon dilution during use (hereinafter sometimes referred to as pH jump). The emphasis is on. Therefore, it is necessary to use a boron compound such as boric acid in combination with a polyol compound such as sorbitol, and there is a limitation not only in composition but also in stability in increasing the surfactant concentration. In addition, the above-mentioned patent document describes a nonionic surfactant containing an ethyleneoxy group and a propyleneoxy group in the structure, and the nonionic surfactant has excellent stability in a liquid detergent composition. Indicates. However, it has been found that the nonionic surfactants described in these patent documents do not sufficiently exhibit the antibacterial effect of the cationic surfactant, and the deodorizing effect on clothing and the like is not sufficient.

  An object of the present invention is to provide a liquid detergent composition that is excellent in detergency, deodorizing property and storage stability of textile products such as clothing in a liquid detergent composition containing a surfactant at a high concentration. It is.

In the present invention, the surfactant (A) [hereinafter referred to as component (A)] is 35 to 85% by mass, the hydrotrope agent (B) [hereinafter referred to as component (B)] is 0.1 to 5% by mass, Hydrogen peroxide (C) 0.3 to 10% by mass, water miscible solvent (D) 2 to 40% by mass, and water,
As surfactant (A), the following (a1)-(a3) component is contained in the following range,
The mass ratio (a3) / (B) of the component (a3) to the component (B) is 0.1 to 3,
The pH at 20 ° C. described in 8.3 of JIS K3362: 1998 is 3-7.
The present invention relates to a liquid detergent composition.
(A1) component: Nonionic surfactant 15-75 mass% represented by following General formula (1)
R ^a1 O — [(C ₂ H ₄ O) _m / (AO) _n ] H (1)
[Wherein R ^a1 is a chain hydrocarbon group having 8 to 22 carbon atoms, the carbon atom of R ^a1 bonded to the oxygen atom of R ^a1 O is a primary carbon atom, and AO has 3 to 3 carbon atoms. 5 alkyleneoxy group. m and n are average addition mole numbers, m is a number of 14-30, n is a number of 1-5. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded randomly or in blocks. ]
(A2) Component: (b) Nonionic surfactant represented by the general formula (2) 0.5 to 20% by mass
R ^a2 O (C ₂ H ₄ O) _x H (2)
[Wherein R ^a2 is a chain hydrocarbon group having 8 to 22 carbon atoms, and the carbon atom of R ^a2 bonded to the oxygen atom of R ^a2 O is a secondary carbon atom. x is an average addition mole number, and is a number of 2-7. ]
Component (a3): a cationic surfactant represented by the following general formula (3) 0.1 to 5% by mass

Wherein, R ^a31 is a hydrocarbon group having 6 to 22 carbon atoms, in R ^a31 - (A'O) _s - may contain. A′O is an ethyleneoxy group or a propyleneoxy group, s represents an average addition mole number of A′O and is 0 to 10, and R ^a32 , R ^a33 and R ^a34 are each independently a methyl group, ethyl A group, a benzyl group, or a hydroxyalkyl group having 1 to 3 carbon atoms, and X is a halogen atom, CH ₃ SO ₄ or CH ₃ CH ₂ SO ₄ . ]

  According to the present invention, despite having a high concentration of a surfactant as a cleaning component, it has excellent stability (especially storage stability at low temperatures), and cleaning performance of textiles such as clothing and fresh drying. The liquid detergent composition excellent in the deodorizing effect by suppression of an odor can be provided.

<Surfactant (A)>
The liquid detergent composition of the present invention contains two kinds of specific nonionic surfactants and specific cationic surfactants as the surfactant (A). That is, the nonionic surfactant of the component (a1) is a main base, the nonionic surfactant of the component (a2) characterized by a secondary carbon atom, and the main agent exhibiting a deodorizing effect on fresh drying ( a3) A cationic surfactant as a component is contained as an essential component. As component (A), other surfactants include (a1) component, nonionic surfactants other than component (a2), anionic surfactants and amphoteric surfactants. Activators are limited because they inhibit the deodorant effect. Specific components will be described below.

<(A1) component>
The component (a1) of the present invention is a nonionic surfactant represented by the following general formula (1).
R ^a1 O — [(C ₂ H ₄ O) _m / (AO) _n ] H (1)
[Wherein R ^a1 is a chain hydrocarbon group having 8 to 22 carbon atoms, the carbon atom of R ^a1 bonded to the oxygen atom of R ^a1 O is a primary carbon atom, and AO has 3 to 3 carbon atoms. 5 alkyleneoxy group [hereinafter also referred to as AO group. ]. m and n are average addition mole numbers, m is a number of 14-30, n is a number of 1-5. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded randomly or in blocks. ]

The component (a1) is obtained by subjecting a primary alcohol having 8 to 22 carbon atoms to addition reaction of ethylene oxide [hereinafter sometimes referred to as EO] and alkylene oxide having 3 to 5 carbon atoms in a random or block manner. be able to. R ^a1 in formula (1) is preferably a linear alkyl group.

Further, m in the general formula (1) is the average number of added moles of ethyleneoxy group (C ₂ H ₄ O, hereinafter also referred to as EO group), from the viewpoint of storage stability, solubility, and washing performance. The lower limit is 14 or more, preferably 16 or more, more preferably 18 or more, and the upper limit is 30 or less, preferably 27 or less, more preferably 24 or less. n is the average number of moles of AO groups added, and the lower limit is 1 or more, preferably 2 or more, and the upper limit is 5 or less, preferably 4 or less, more preferably 3 or less, from the viewpoint of cleaning performance.

  The AO group in the general formula (1) is obtained by addition reaction of an alkylene oxide having 3 to 5 carbon atoms, and the portion bonded by the addition reaction has a structure of methyl branch, ethyl branch or propyl branch. Those are preferred. Further, an alkyleneoxy group having 3 carbon atoms and / or an alkyleneoxy group having 4 carbon atoms are preferable, and specifically, a trimethyleneoxy group, an oxypropane-1,2-diyl group, an oxybutane-1,2-diyl group, Examples thereof include oxybutane-1,3-diyl group, oxybutane-2,3-diyl group, and oxytetramethylene group. In particular, the AO group is preferably an oxypropane-1,2-diyl group (hereinafter, in the present invention, the oxypropane-1,2-diyl group may be a propyleneoxy group or a PO group).

  In the present invention, in particular, the average added mole number m of EO group is 16 to 27, more preferably 17 to 24, particularly 18 to 22, the AO group is a propyleneoxy group, and the average added mole number n is 1. -4, more preferably 2-4, and especially 2-3 non-ionic surfactants are not only low-temperature storage stability and washing performance, but also cationic surfactants adsorbing to fibers Is also preferable.

  The ability of cationic surfactants to adsorb to fibers by increasing the number of moles of EO groups added to the conventional non-ionic surfactants commonly used in liquid detergent compositions for textile products And can exhibit an excellent deodorizing effect due to sufficient antibacterial properties. Further, the AO group in the component (a1) is included for detergency. Since EO groups generally exhibit hydrophilicity, increasing the number of moles added of EO groups tends to disperse in water rather than the interface such as the fiber surface and tends to make it difficult to obtain sufficient detergency. On the other hand, when the added mole number of EO group is small, it becomes difficult to dissolve in water. The present inventors have surprisingly found that even when the number of moles of EO group added is increased, the detergency can be secured by using a cationic surfactant in combination, and further, such a nonionic surfactant is an AO group. It has been found that better detergency can be obtained by having In addition, the present inventors have reported that the non-ionic surfactants used in the past as a cause of not obtaining a sufficient deodorizing effect even when combined with a cationic surfactant, It was found that the added mole number of was involved. Since the component (a1) of the present invention can sufficiently exhibit the antibacterial properties of the cationic surfactant, it is possible to obtain a liquid detergent composition having an excellent deodorizing effect on textiles.

  In the general formula (1), “/” means that the relationship between the EO group and the AO group of the component (a1) of the present invention may be either a random bond or a block bond. The AO group may be separated as a plurality of block bodies.

Examples of the nonionic surfactant represented by the general formula (1) include nonionic surfactants represented by the following general formulas (1-1) to (1-6).
R ^a1 O— (AO) _n — (C ₂ H ₄ O) _m H (1-1)
R ^a1 O— (C ₂ H ₄ O) _m — (AO) _n H (1-2)
R ^a1 O — [(C ₂ H ₄ O) _m11 · (AO) _n ] — (C ₂ H ₄ O) _m12 H (1-3)
_{^{R a1 O- (C 2 H 4}} O) m11 - [(AO) n · (C 2 H 4 O) m12] H (1-4)
_{^{R a1 O- (C 2 H 4}} O) m11 - (AO) n - (C 2 H 4 O) m12 H (1-5)
_{^{R a1 O- (C 2 H 4}} O) m11 - [(AO) n · (C 2 H 4 O) m13] - (C 2 H 4 O) m12 H (1-6)
[Wherein R ¹ , m, n, and AO have the above-mentioned meanings, and m11, m12, and m13 are average added mole numbers, each of which is not 0, and m = m11 + m12 + m13 or m = m11 + m12 is there. “·” Indicates a random bond. ]

The nonionic surfactants represented by the general formulas (1-1) to (1-6) can be prepared by considering the reaction ratio of the alkylene oxide to R ^a1 OH and the reaction sequence. In the general formulas (1-1) to (1-6), the average number of added moles of each alkyleneoxy group may be the number of moles of each alkylene oxide used for R ^a1 OH during the reaction, or Any of the average addition mole number of the alkyleneoxy group of the obtained compound may be sufficient. In addition, m11 and m12 are independently preferably 1 to 20, more preferably m11 is 3 to 20, and m12 is more preferably 1 to 15, particularly m11 is 4 to 15, and m12 is preferably 3 to 15. M13 is preferably from 0.1 to 10. The range of m11, m12, and m13 shall depend on each range condition of m and n of General formula (1) thru | or each preferable range condition.

As described above, R ^a1 in the general formula (1) may be an alcohol derived from natural fats and oils. Moreover, since it is derived from natural fats and oils, the alkyl group may be composed of a substantially even number of carbon atoms. From the viewpoint of storage stability, nonionic surfactants of the above general formula (1-2), (1-4), (1-5) or (1-6) are preferred, and among these, the general formula (1- The nonionic surfactant of 5) or (1-6) is more preferable, and the nonionic surfactant of general formula (1-5) is most preferable.

The component (a1) of the present invention reacts, for example, an alkylene oxide having 3 to 5 carbon atoms and ethylene oxide according to the structure of the general formulas (1-1) to (1-6) with respect to R ^a1 OH. It is obtained by. From the target structure, the blending order and conditions may be examined, and the addition reaction may be performed in a block or random manner. In addition, the reaction ratio of the alkylene oxide having 3 to 5 carbon atoms and ethylene oxide per mole of R ^a1 OH is in the range of m and n in the general formula (1), that is, m = 14 to 30, n = 1 to is 5, it is possible to bring the preferred ranges of conditions and the description of the m = m11 + m12 + m13 or m = m11 + m12. In other words, the reaction ratio of the alkylene oxide having 3 to 5 carbon atoms to be added to the aliphatic alcohol and ethylene oxide may be within the numerical ranges of m and n, m11, m12, and m13.

In general, the ratio of each ethylene oxide or propylene oxide added to 1 mol of R ^a1 OH and the average number of added moles of the alkyleneoxy group represented by each general formula are substantially the same. However, depending on the production method, it may be different in the present invention.

  The most preferred nonionic surfactant as the component (a1) of the present invention is the structure of the general formula (1-5) or (1-6), and particularly the structure of the general formula (a-5). Furthermore, in general formula (1-5), m11 / (m11 + m12) is preferably 0.2 to 0.8.

As the optimum production conditions further narrowing down the ranges of m11, m12, m13 and n, a production method having the following steps A to D can be mentioned.
Step A: Addition reaction of ethylene oxide at a ratio of 4 mol to 14 mol, preferably 8 to 12 mol (the numerical range may be defined as m11 in the above formula) per mol of R ^a1 OH .
Step B: Next, 1 to 3 mol of propylene oxide, preferably 2 to 3 mol (numeric range may be defined as n in the above formula) and 0 to 4 mol of ethylene oxide (numeric range is in the above formula) (Which may be defined as m13) in a random or block addition reaction. Particularly preferably, propylene oxide alone is added and reacted in an amount of 2 to 3 mol (the numerical range may be defined as n in the above formula).
Step C: Thereafter, ethylene oxide is again subjected to addition reaction of 4 to 14 mol, preferably 8 to 12 mol (the numerical range may be defined as m12 in the above formula).
Process D: The process for the catalyst used for reaction is performed. For example, when an alkali catalyst is used, it is neutralized with an acid, and when it is a solid catalyst, filtration is performed.

  In the present invention, the component (a1), the component (a2) described later, and the other optional component (a5) include a small amount of unreacted alcohol, reaction catalyst (for example, potassium hydroxide, metal compound) and an agent for neutralization thereof. (For example, acetic acid or lactic acid) and polyalkylene glycol having an ethyleneoxy group formed by the presence of water in the reaction system and an alkyleneoxy group having 3 or 4 carbon atoms may be mixed in, but smells etc. It may be present as long as it does not affect the present invention due to the above-mentioned problems, manufacturing restrictions in consideration of economy and safety, and other various circumstances.

M and n for the component (a1) can be determined by NMR or liquid chromatographic analysis. The alkyleneoxy group is short, for example, the alkyl group is less than 8 moles of ethylene oxide per mole of linear primary alcohol. In the case of a compound obtained by an addition reaction at a ratio of, gas chromatographic analysis may be used. Or in this invention, m, n, etc. may be the ratio of the C3-C5 alkylene oxide and ethylene oxide with which it reacted per mol of R < ^a1 > O-H.

  In the liquid cleaning composition of the present invention, the content of the component (a1) is 15 to 75% by mass, preferably 25 to 60% by mass, and more preferably 35 to 50% by mass from the viewpoint of cleaning performance. In the case where the component (a1) is a nonionic surfactant represented by the general formula (1-1), the content in the composition is from the viewpoint of stability at low temperature and solubility when diluted with cold water. It is preferably 45% by mass or less, particularly 40% by mass or less. Further, when the component (a1) is a nonionic surfactant of the general formula (1-2), the composition is similarly used from the viewpoints of stability at low temperatures and dilution solubility in cold water during washing. The content is preferably 50% by mass or less.

<(A2) component>
The liquid detergent composition of the present invention contains a nonionic surfactant (a2) represented by the following general formula (2).
R ^a2 O (C ₂ H ₄ O) _x H (2)
[Wherein R ^a2 is a chain hydrocarbon group having 8 to 22 carbon atoms, and the carbon atom of R ^a2 bonded to the oxygen atom of R ^a2 O is a secondary carbon atom. x is an average addition mole number, and is a number of 2-7. ]

In the general formula (2) of the component (a2), R ^a2 is a chain hydrocarbon group having 8 to 22 carbon atoms, preferably a hydrocarbon group having 10 to 18 carbon atoms, and more preferably 12 to 16 carbon atoms. R ^a2 is preferably a linear alkyl hydrocarbon group. The first feature of the nonionic surfactant of the general formula (2) is that the carbon atom of R ^a2 bonded to the oxygen atom of R ^a2 O is the second carbon atom. For the production of a nonionic surfactant in which the carbon atom of R ^a2 bonded to the oxygen atom is a secondary carbon atom, ethylene oxide is added to a secondary alcohol, or ethylene oxide is reacted with a 1-olefin or an internal olefin, A method of reacting polyethylene glycol with olefin or a known production method by introducing a hydroxyl group into n-paraffin and adding ethylene oxide can be used.

  The average addition mole number x of the ethyleneoxy group is 2 to 7, preferably 2.5 or more. More preferably, it is 6.5 or less, and more preferably 5 or less.

  The component (a2) is usually obtained as a mixture containing unreacted alcohol. Since unreacted alcohol affects the problem of odor and the storage stability of the composition, it is preferably reduced by distillation or the like. In the present invention, the ratio of the unreacted alcohol, that is, the aliphatic alcohol having a hydrocarbon group having 8 to 22 carbon atoms, is preferably 5% by mass or less, more preferably 3% by mass or less with respect to the component (a2). 0.5 mass% or less is most preferable. Moreover, the ratio of the unreacted alcohol, that is, the alcohol having a hydrocarbon group having 8 to 22 carbon atoms is 5% by mass or less with respect to the total of the component (a1), the component (a2) and the component (a5). Preferably, 3 mass% or less is more preferable, 1 mass% or less is more preferable, and 0.5 mass% or less is the most preferable. However, the lower limit is considered after considering the environment such as the energy required for the distillation process.

  Although the liquid detergent composition of this invention contains 0.5-20 mass% of (a2) component, Preferably it is 1-15 mass%, More preferably, it is 4-12 mass%, More preferably, it is 7-10. % By mass.

<(A3) component>
The cationic surfactant as the component (a3) of the present invention is a quaternary ammonium type surfactant represented by the following general formula (3).

Wherein, R ^a31 is a hydrocarbon group having 6 to 22 carbon atoms, in R ^a31 - (A'O) _s - may contain. A′O is an ethyleneoxy group or a propyleneoxy group, s represents an average addition mole number of A′O and is 0 to 10, and R ^a32 , R ^a33 and R ^a34 are each independently a methyl group, ethyl A group, a benzyl group, or a hydroxyalkyl group having 1 to 3 carbon atoms, and X is a halogen atom, CH ₃ SO ₄ or CH ₃ CH ₂ SO ₄ . ]

Formula (a3) the number of carbon atoms of R ^a31 in 8 to 20, more preferably from 10 to 18, 14 to 16 being most preferred.

In addition, X ⁻ in the general formula (3), which is a counter ion of the component (a3), is preferably CH ₃ SO ₄ ^— or CH ₃ CH ₂ SO ₄ ^— from the deodorizing effect on fresh drying.

  While the component (a3) is a main agent exhibiting a deodorizing effect on fresh-drying, the property of improving the detergency of a nonionic surfactant having an average added mole number of EO groups of the component (a1) of 14 or more is also It is an important component in showing.

  As the cationic surfactant of the component (a3), for example, the following (a3-1) to (a3-4) can be used, but it contains a compound selected from (a3-1) and (a3-3). Is more preferable. When (a3-1) is contained, it is most preferable to occupy 50% by mass or more, particularly 60% by mass in the component (a3).

(A3-1) A quaternary ammonium salt in which R ^a31 in the general formula (3) is a linear alkyl group having 6 to 22 carbon atoms, and R ^{a32 to} R ^a34 are each a methyl group or an ethyl group .
(A3-2) A quaternary ammonium salt in which R ^a31 in General Formula (3) is a branched alkyl group having 6 to 22 carbon atoms, and R ^{a32 to} R ^a34 are each a methyl group or an ethyl group .
(A3-3) R ^a31 in the general formula (3) is a linear alkyl group having 6 to 22 carbon atoms, R ^a32 is a benzyl group, and R ^a33 and R ^a34 are a methyl group or an ethyl group , respectively. Quaternary ammonium salt.
(A3-4) R ^a31 in the general formula (3) is a linear alkyl group having 6 to 22 carbon atoms, R ^a31 contains — (AO) _s —, s is 1 to 5, ^A quaternary ammonium salt in which ^{a32 to Ra34} are each a methyl group or an ethyl group .

  The cationic surfactant as component (a3) exhibits antibacterial properties, and suppresses the growth of bacteria on the fiber during raw drying and suppresses the generation of odor. The component (a3) exhibits an excellent dry-drying odor control effect in combination with the component (a1), and further exhibits antibacterial properties by using the compound (a-4) or (a4) component described later in combination. can do.

  The liquid detergent composition of the present invention contains component (a3) in an amount of 0.1 to 5% by mass, preferably 0.2 to 4% by mass, and more preferably 0.5 to 3% by mass.

<Other surfactants>
<Compound (a-4) or (a4) component>
As component (A), polyoxyethylene lauryl ether (a-4) [hereinafter referred to as compound, wherein the number of added moles of ethyleneoxy group is 2, 3, 4, 5 or 6, especially the number of added moles is 4 or 5. May be referred to as (a-4). The liquid detergent composition of the present invention preferably contains 0.5 to 8% by mass, more preferably 0.8 to 6% by mass, and most preferably 1 to 5% by mass of the compound (a-4). Such a compound may be blended as a single product, but 2 to 7 mol, preferably 3 to 5 mol, of ethylene oxide is added under a catalyst per 1 mol of lauryl alcohol or an aliphatic alcohol mixture containing lauryl alcohol. Nonionic surfactant (a4) [hereinafter referred to as (a4) component which is polyoxyethylene lauryl ether (average added mole number of ethyleneoxy group is 2 to 7, preferably 3 to 5)) obtained by . ] May be blended. (A4) A component contains 0.8-10 mass% in a composition, More preferably, it is 1-8 mass%, Most preferably, it contains 2-6 mass%. Compound (a-4) or (a4) component can further suppress a raw dry odor by using together with (a3) component.

<(A5) component>
The component (A) is an anion such as an anionic surfactant (hereinafter sometimes referred to as (a5-1) component) and / or an amphoteric surfactant (hereinafter also referred to as (a5-2) component). And a surfactant having a functional group (hereinafter, the anionic surfactant and the amphoteric surfactant may be collectively referred to as component (a5)). However, the content of the component (a5) in the composition is limited. When mix | blending from a liquid-stability viewpoint mentioned later, as anionic surfactant (a5-1), the following (a5-1-1)-(a5-1-5) can be mention | raise | lifted as a preferable compound.
(A5-1-1) An alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 20.
(A5-1-2) An alkyl group derived from a linear primary alcohol or linear secondary alcohol having 10 to 20 average carbon atoms or an alkyl group derived from a branched alcohol, and having an average addition mole number of an alkyleneoxy group of 1 A polyoxyethylene alkyl ether sulfate salt (a5-1) which contains an ethyleneoxy group as an alkyleneoxy group and may contain a propyleneoxy group in an average addition mole number of 0.2-2 mol. -3) Alkyl or alkenyl sulfate salts having an average alkyl group or alkenyl group having 10 to 20 carbon atoms.
(A5-1-4) A fatty acid salt having an average carbon number of 8 to 20.
(A5-1-5) An alkyl group derived from a linear primary alcohol or linear secondary alcohol having 10 to 20 average carbon atoms or an alkyl group derived from a branched alcohol, and having an average addition mole number of an alkyleneoxy group of 1 A polyoxyethylene alkyl ether carboxylate which contains an ethyleneoxy group as an alkyleneoxy group and may contain a propyleneoxy group in an average addition mole number range of 0.2 to 2 mol.

  Examples of the salt constituting the component (a5-1) include alkali metal salts such as sodium and potassium, alkanolamine salts, and alkaline earth metal salts such as magnesium and calcium. It is preferable from the point of suppression of a raw dry odor.

  As the amphoteric surfactant (a5-2), sulfobetaine or carbobetaine having an alkyl group having 8 to 22 carbon atoms, fatty acid amidopropyl (or hydroxypropyl) betaine having an alkyl group having 7 to 21 carbon atoms, or The same carbobetaine can be mentioned.

  The component (a5), particularly the component (a5-1), not only compensates for the reduction in detergency due to the hydrophilicity of the component (a1), but also at a low temperature of the composition under high-concentration surfactant conditions. It has the property of suppressing gelation or solidification and stabilizing the composition system. On the other hand, when using together with the cationic surfactant of the component (a3), it is preferable to use the component (a1) and the component (a5) at a specific ratio in order to sufficiently exert the deodorizing effect on the dry odor.

  Therefore, when the component (a5) is used in combination, the mass ratio (a1) / (a5) of the component (a1) to the component (a5) is preferably 10 to 100, more preferably 9 to 100. In particular, the mass ratio of the component (a5-1) to the component (a1) preferably satisfies this range. In particular, the content of the component (a5-1) in the composition is preferably 5% by mass or less, more preferably 3% by mass or less, and most preferably 1% by mass or less. When (a5-1) component is mix | blended with a composition, you may mix | blend as an alkali metal salt or mix | blend as an acid type compound, and you may neutralize with an alkali metal hydroxide etc. later. In this invention, the compounding quantity and compounding ratio regarding (a5-1) component shall be based on the mass converted into the acid type compound.

<Surfactants other than the components (a1) to (a5)>
Examples of other surfactants include nonionic surfactants other than the components (a1), (a2) and (a3), such as alkyl (poly) glycoside, alkyl (poly) glyceryl ether, etc. Be careful not to impair this effect.

  In the liquid detergent composition of the present invention, from the viewpoint of detergency, the component (A) is 35 to 85% by mass, preferably 40 to 80% by mass, more preferably 45 to 75% by mass, and still more preferably 50 to 70%. Contains by mass%.

<(B) component>
The liquid detergent composition of the present invention is mixed with a hydrotrope agent for the stability of the composition. The hydrotrope of the present invention is an organic compound having an anionic group, and further contains 1 to 2 alkyl groups selected from methyl group, ethyl group or propyl group, and 1 sulfonic acid group or carboxylic acid group. And alkylbenzene carboxylic acid or alkyl benzene sulfonic acid or a salt thereof, and benzoic acid or a salt thereof. More specifically, paratoluenesulfonic acid, cumenesulfonic acid, metaxylenesulfonic acid, and benzoic acid, and the salt is preferably an alkali metal salt. In the present invention, paratoluenesulfonic acid or an alkali metal salt thereof is preferable, and it may be blended as an acid and neutralized with an alkali agent in the composition. (B) A component can provide stability, without inhibiting suppression of a raw dry odor.

  The component (B) is preferably blended as an alkali metal salt, but the liquid detergent composition of the present invention is preferably 0.1 to 5% by mass when the component (B) is converted to an acid type compound. Is contained in an amount of 0.5 to 4% by mass, more preferably 1 to 3% by mass.

  In the liquid detergent composition of the present invention, from the viewpoint of stability and deodorizing effect, the mass ratio (a3) / (B) of the component (a3) to the component (B) is 0.1 to 3, preferably It is 0.3-2, More preferably, it is 0.5-1.5. This mass ratio is calculated based on the mass obtained by converting the component (B) into an acid type compound.

<(C) component>
The liquid detergent composition of the present invention contains hydrogen peroxide as the component (C) in order to suppress a raw dry odor. We have also found that hydrogen peroxide acts as a low-temperature stabilizer when the surfactant (A) is 40% by mass or more, particularly 50% by mass or more.

  The liquid detergent composition of the present invention contains 0.3 to 10% by mass of hydrogen peroxide, preferably 0.5 to 8% by mass, more preferably 1 to 6% by mass.

<(D) component>
The liquid detergent composition of the present invention contains a water-miscible organic solvent as the component (D). The water-miscible organic solvent referred to in the present invention refers to a solvent that dissolves 50 g or more in 1 liter of ion-exchanged water at 25 ° C., that is, a solvent having a dissolution degree of 50 g / L or more.

  As the component (D), a water-miscible organic solvent having a hydroxyl group and / or an ether group is preferable.

  Examples of the water-miscible organic solvent include (d1) alkanols such as ethanol, 1-propanol, 2-propanol and 1-butanol, (d2) glycols such as propylene glycol, butylene glycol and hexylene glycol, and (d3) diethylene glycol. , Glycols such as triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, (d4) diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, tripropylene glycol Rumonomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methylglycerol ether, 2-methylglycerol ether, 1,3-dimethylglycerol ether, 1-ethylglycerol ether, 1,3- Alkyl ethers such as diethyl glyceryl ether, triethyl glyceryl ether, 1-pentyl glyceryl ether, 2-pentyl glyceryl ether, 1-octyl glyceryl ether, 2-ethylhexyl glyceryl ether, diethylene glycol monobutyl ether, (d5) 2-phenoxyethanol, diethylene glycol mono Phenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, phenol Carboxymethyl propylene glycol, 2-benzyloxy ethanol, aromatic ethers such as diethylene glycol monobenzyl ether, and the like.

  The component (D) is effective as a viscosity modifier and gelation inhibitor of the composition, and the above (d1) alkanols, (d2) glycols, (d4) alkyl ethers, (d5) aromatic ethers One or more selected from the group consisting of (d2) glycols, (d4) alkyl ethers, and (d5) aromatic ethers is more preferable. Viscosity adjustment and gelation can be suppressed.

  In addition, in the liquid detergent composition of the present invention, (d4) alkyl ethers and / or (d5) aromatic ethers are preferable, in particular diethylene glycol monobutyl ether, in order to stabilize hydrogen peroxide and suppress a dry-dry odor. , Diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, or phenoxypropylene glycol. In particular, diethylene glycol monobutyl ether and / or triethylene glycol monophenyl ether are more preferable.

  The liquid detergent composition of this invention contains 2-40 mass% of (D) component, Preferably it is 4-20 mass%, More preferably, it contains 5-10 mass%.

  Hereinafter, other components that can be used in the present invention will be shown. In the present invention, in addition to the components (A) to (D), it is preferable from the viewpoint of detergency that the following polymer is blended as the component (E). In addition, it may be called an alkali agent [hereinafter referred to as component (F). ] Is added as a neutralizing agent when an anionic surfactant, a chelating agent, or the like is added as an acid agent. However, since it serves as a counter ion for the anion, the liquid detergent composition of the present invention basically contains Does not contain as a free alkali agent.

<(E) component>
As the component (E), a water-soluble polymer is preferably blended for the purpose of improving the deodorizing effect. As the polymer, a polymer containing a structural unit having a carboxylic acid group is preferable. Examples thereof include polyacrylic acid, acrylic acid-maleic acid copolymer, and a copolymer of acrylic acid or maleic acid and an olefin having 2 to 5 carbon atoms. In the present invention, in a high-concentration surfactant system, a polymer weight containing both a structural unit composed of a monomer having a carboxylic acid group and a structural unit composed of a monomer having a polyoxyethylene chain, in particular. Coalescence is more preferred. Examples thereof include polymers described in JP-A-10-60476 and JP-A-2004-155937. (E) As for the mixture ratio in the composition of a component, 0.1-5 mass% is preferable, More preferably, it is 0.5-4 mass%.

<(F) component>
In the liquid detergent composition of the present invention, from the viewpoint of the stability of hydrogen peroxide, etc., it is a medium for adjusting the pH when an anionic surfactant, hydrotrope, chelating agent, etc. are blended with an acid type compound. It is preferable to use an alkali agent [hereinafter referred to as the component (F)] as the compatibilizer. Since the liquid detergent composition of the present invention has a pH of 7 or less, it is considered that there is almost no free alkaline agent. The alkali agent used for neutralization is preferably an alkali metal hydroxide, particularly preferably potassium hydroxide and / or sodium hydroxide.

  In addition, water-miscible organic amine compounds, particularly alkanolamine compounds having a total carbon number of 6 or less such as monoethanolamine, diethanolamine and triethanolamine [hereinafter also referred to as (F ') component]. ], When used as a neutralizing agent, the water-miscible organic amine compound containing an alkanolamine in the composition is less than 1% by mass, more preferably 0.5% by mass or less, particularly from the viewpoint of the effect of suppressing the dry odor. It is preferable that it is 0.08 mass% or less. The component (F ′) is counted when it is added as an anionic compound salt in addition to the alkaline agent (neutralizing agent for pH adjustment).

[(G) component]
The liquid detergent composition of the present invention may contain a chelating agent [hereinafter referred to as (G) component]. Examples of the chelating agent for component (G) include nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid, and diencoric acid. Aminopolyacetic acid or a salt thereof, diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid, carboxymethyltartaric acid, etc. Polycarboxylic acids other than acetic acid or salts thereof, aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonate) And organic phosphonic acids or salts thereof of acid) and the like, salts and the like alkali metal salts. In the present invention, a salt blended with an acid and neutralized with an alkali agent in the system may be used. In particular, 1-hydroxyethylidene-1,1-diphosphonic acid is preferred.

  In the present invention, from the viewpoint of the stability of hydrogen peroxide, it is preferable to contain a chelating agent so that a trace amount of heavy metal ions derived from raw water does not promote decomposition of hydrogen peroxide. On the other hand, since many chelating agents have a property of suppressing pH fluctuation at the time of dilution, the content is preferably a small amount and an effective agent. As such a chelating agent, the aforementioned organic phosphonic acid or a salt thereof is preferable, and the salt is preferably a potassium salt or a sodium salt. The content of the component (G) in the composition is preferably 0.05 to 3% by mass, more preferably 0.08 to 2% by mass, and still more preferably 0.1 to 1% when converted to an acid type compound. % By mass.

Furthermore, the components shown in the following (i) to (viii) can be blended in the liquid detergent composition of the present invention to such an extent that the effects of the present invention are not impaired.
(I) Tetraacetylethylenediamine, bleach activators such as bleach activators represented by general formulas (I-2) to (I-7) in JP-A-6-316700, (ii) cellulase, amylase, pectinase, Enzymes such as protease and lipase (iii) Sources of calcium ions (calcium ion supply compounds), enzyme stabilizers such as bihydroxy compounds and formic acid (iv) Fluorescent dyes such as Tinopearl CBS (trade name, manufactured by Ciba Specialty Chemicals) and White Fluorescent dye commercially available as Tex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.) (v) Antioxidants such as butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium bisulfite (vi) No. 11-513067 Anti-gelling polymers described in the publication, in particular having a weight average molecular weight of 600 to 5000 Further polypropylene glycol or polyethylene glycol 1000 to 4000. The weight average molecular weight can be determined using a light scattering method, and can be measured with a dynamic light scattering photometer (DLS-8000 series, manufactured by Otsuka Electronics Co., Ltd.).
(Vii) Water such as paraffins such as octane, decane, dodecane and tridecane, olefins such as decene and dodecene, alkyl halides such as methylene chloride and 1,1,1-trichloroethane, and terpenes such as D-limonene Immiscible organic solvent.
(Viii) Other antifoaming agents such as pigments, fragrances, antibacterial preservatives, and silicones

Although the density | concentration as a parameter | index at the time of mix | blending the said arbitrary component in the liquid detergent composition of this invention below is shown, it adjusts suitably to such an extent that this effect is not impaired, and excludes when it is not suitable for a mixing | blending.
The content of the bleach activator (i) is preferably 0.01 to 10% by mass. The content of the enzyme (ii) is preferably 0.001 to 2% by mass. The content of the enzyme stabilizer (iii) is preferably 0.001 to 2% by mass. The content of the fluorescent dye (iv) is preferably 0.001 to 1% by mass. The content of the antioxidant (v) is preferably 0.01 to 2% by mass. The polyalkylene glycol-based anti-gelling polymer (vi) is preferably 0.01 to 2%. The water immiscible organic solvent (vii) is preferably 0.001 to 2% by mass. The other components of (viii) can be blended at a known concentration, for example.

  The liquid detergent composition of the present invention desirably contains substantially no boron compound such as boric acid. Here, “substantially not containing” a boron compound refers to excluding, for example, a case where it is mixed from an enzyme preparation or the like as an enzyme stabilizer. It means that it is less than 0.1% by mass, especially less than 0.01% by mass in terms of boric acid in the composition.

  The balance of the composition of the present invention is water. The water is preferably sterilized deionized water.

  The liquid detergent composition of the present invention has a pH at 20 ° C. of 3 to 7, described in 8.3 of JIS K3362: 1998, more preferably 3.5 to 7, and particularly preferably 4 to 6.5. Furthermore, the pH of an aqueous solution obtained by dissolving 2 ml of the liquid detergent composition of the present invention in 3 L of water at 4 ° DH and 20 ° C. is preferably 5 to 8.5, particularly 6 to 8. Is more preferable.

  The viscosity at 20 ° C. of the liquid detergent composition of the present invention is preferably 10 to 1,000 mPa · s, more preferably 50 to 600 mPa · s, and still more preferably 100 to 300 mPa · s in terms of ease of handling. It is preferable to adjust so that it may become such a range with (D) component.

  In the present invention, the viscosity is measured with a B-type viscometer. Select a rotor that matches the viscosity. It rotates at a rotational speed of 60 r / min, and the viscosity 60 seconds after the start of rotation is taken as the viscosity of the liquid detergent composition or diluent.

  The liquid cleaning composition of the present invention is used as a cleaning composition for textile products. In particular, it is a liquid detergent composition for textile products used in household life such as clothing, towels, foot-wiping mats, bed sheets products, etc., and is particularly suitable as a detergent for textile products that can be washed with water.

  The following compounding ingredients were mixed with the compositions shown in Tables 1 and 2 to obtain compositions of Examples and Comparative Examples. The following evaluations were performed using the obtained compositions. The results are shown in Tables 1-2.

<Blending ingredients>
In the description of the following components, ethylene oxide is abbreviated as EO and propylene oxide is abbreviated as PO. Further, the anionic organic compound in the form of a salt is shown in the table as the concentration converted to the acid type compound. The pH of the composition was adjusted with an aqueous sodium hydroxide solution or an aqueous hydrochloric acid solution.

(A) component (a1) component a1-1: polyoxyethylene (9) polyoxypropylene (2) polyoxyethylene (9) alkyl ether (numbers in parentheses are the average number of moles added) [carbon number 10-14 9 mol of ethylene oxide, 2 mol of propylene oxide, and 9 mol of ethylene oxide in the order of 9 mol per 1 mol of the linear primary saturated alcohol of general formula (1-5), m11 = 9, n = 2, m12 = 9. Compound (a-4) is not included. ]
A1-2: polyoxyethylene (8) polyoxypropylene (2) polyoxyethylene (8) alkyl ether (numbers in parentheses are average added moles) [linear primary saturated alcohol 1 having 10 to 14 carbon atoms] Eight moles of ethylene oxide, two moles of propylene oxide and eight moles of ethylene oxide per block are added in the order of a block. In the general formula (1-5), a compound of m11 = 8, n = 2, m12 = 8 is there. Compound (a-4) is not included. ]
A1-3: polyoxyethylene (15) polyoxypropylene (2) polyoxyethylene (15) alkyl ether (numbers in parentheses are the average number of moles added) [linear primary saturated alcohol 1 having 10 to 14 carbon atoms] A block addition of 15 moles of ethylene oxide, 2 moles of propylene oxide and 15 moles of ethylene oxide per mole, in the general formula (1-5), a compound of m11 = 15, n = 2, m12 = 15 is there. Compound (a-4) is not included. ]
A1-4: polyoxyethylene (20) polyoxypropylene (2) alkyl ether (numbers in parentheses are the average number of moles added) 20 ethylene oxide per mole of linear primary saturated alcohol having 10 to 14 carbon atoms In the formula (1-2), a compound in which m and propylene oxide are added in block order in the order of 2 mol, m = 20 and n = 2. Compound (a-4) is not included. ]
A1-5: polyoxyethylene (14) polyoxypropylene (2) polyoxyethylene (4) alkyl ether (numbers in parentheses are average added moles) [linear primary saturated alcohol 1 having 10 to 14 carbon atoms] 14 moles of ethylene oxide, 2 moles of propylene oxide, and 4 moles of ethylene oxide per block, in the order of block addition, in the general formula (1-5), a compound of m11 = 14, n = 2, m12 = 4 is there. Compound (a-4) is not included. ]

(A2) Component a2-1: In General Formula (2), R ^a2 is a linear alkyl group having 12 to 14 carbon atoms bonded to an oxygen atom and a second carbon atom, and x is 7. Nonionic surfactant (7 to 12 moles of EO added per mole of secondary linear saturated alcohol having 12 to 14 carbon atoms, after which unreacted alcohol was removed by distillation. R ^a2 OH content was 0.1 mass %Less than.)

(A3) component a3-1: linear alkyl (carbon number 12) trimethylammonium ethyl sulfate a3-2: linear alkyl (carbon number 14) dimethylethylammonium ethyl sulfate a3-3: linear alkyl (carbon number) 18) Trimethylammonium methyl sulfate

(A4) component a4-1: polyoxyethylene (4) lauryl ether [numbers in parentheses are the average number of moles added] [4 moles of ethylene oxide per mole of lauryl alcohol (linear primary alcohol having 12 carbon atoms) The ratio of the compound (a-4) in a4-1 being 60% by mass, and the ratio of the compound having an ethyleneoxy group addition mole number of 4 or 5 in a4-1 Is 19% by mass. ]
A4-2: polyoxyethylene (7) lauryl ether [numbers in parentheses are the average number of moles added] [7 moles of ethylene oxide added per mole of lauryl alcohol (linear primary alcohol having 12 carbon atoms) In a4-2, the proportion of the compound (a-4) is 30% by mass, and the proportion of the compound having an ethyleneoxy group addition mole number of 4 or 5 in a4-2 is 13% by mass. %. ]

(A5) Component / a5-1-i: Palm oil fatty acid (Lunac L-55 (trade name), manufactured by Kao Corporation)
A5-1-ii: alkylbenzenesulfonic acid having a linear alkyl group having 10 to 14 carbon atoms (average carbon number of 11.7) a5-1-iii: polyoxyethylene alkyl ether sulfate [10 to 14 carbon atoms] Linear alkyl (average carbon number 12.3), EO average addition mole number 3, sodium salt] (however, the concentration in the table is the concentration as an acid type compound)

(B) Component b-1: Sodium paratoluenesulfonate (however, the concentration in the table is the concentration as an acid type compound)

(C) Component / c-1: Hydrogen peroxide

(D) component d-1: diethylene glycol monobutyl ether (also called butoxy diglycol)
D-2: propylene glycol d-3: triethylene glycol monophenyl ether (PHG-30; manufactured by Nippon Emulsifier)
D-4: ethanol

(Other)
-High molecular polymer: high molecular compound synthesized by the method of Synthesis Example 1 of page 4 paragraph 0020 of JP-A-10-60476-Fluorescent dye: Tinopearl CBS-X (trade name) (manufactured by Ciba Specialty Chemicals)
Enzyme: Everase 16.0L-EX (trade name) (protease, manufactured by Novozyme)
Organic phosphonic acid: 1-hydroxyethylidene-1,1-diphosphonic acid

(1) Detergency evaluation (1-1) Preparation method of cocoon pieces 衿 As a soil test cloth, the ones with the same degree of soiling were selected from those collected by cutting the heel part of a cotton / polyester blended shirt worn for 3 days. . The selected wrinkle stain test cloth is cut in half and sewn one by one on a 30 cm × 30 cm cotton cloth (hereinafter referred to as a scissors piece). 12 sheets). One of the half-cut sheets was used as the detergent shown in the examples, and the other six sheets were used as index detergents for determining the cleaning power.

(1-2) Washing water preparation method To make calcium / magnesium = 8/2 as a hardness component, the water used for washing is calcium chloride dihydrate 25.14 g and magnesium chloride hexahydrate 8. 400 ° DH hard water obtained by dissolving 70 g with 2966.13 g of ion exchange water was used, diluted with ion exchange water at the time of use of the detergency test and adjusted to 4 ° DH.

(1-3) Determination Method For the cleaning test, water prepared by the above method was used using a washing machine (NA-FV8001; Panasonic). Detergency was determined by 10 panelists (male in their 30s). 6 pieces of scissors cleaned with the liquid detergent composition (evaluation detergent) in Tables 1 and 2 and scissors cleaned in the same manner except that the detergent is replaced with the indicator detergent described in JIS K 3362: 1998 The degree of cleaning with 6 sheets was judged visually. Judge which of the pair of pieces is superior in cleaning power, +1 points when the detergent using the evaluation detergent has better cleaning power, and better cleaning power when using the indicator detergent The case is set to “−1” (the total evaluation score per panelist is in the range of “+6” to “−6”). Each panel was evaluated by 10 panelists, and the detergency was evaluated by the total of the 10 panelists. When the total score is +5 to -5, it can be judged that the cleaning power of the evaluation detergent and the index detergent is equivalent, and when it is +6 or more, it can be judged that the evaluation detergent is superior in cleaning power, and when it is -6 or less It can be judged that the detergent is inferior in cleaning power. Moreover, it can be judged that the larger the numerical value, the better the cleaning power.

(2) Storage stability evaluation A 50 mL sample bottle (No. 6 wide-mouthed standard bottle, made of glass, cylindrical shape with a diameter of 40 mm and a height of 80 mm) was filled with 40 mL of the liquid detergent composition, capped, and then 5 It was left to stand in a constant temperature room at 20 ° C. for 20 days. The stability of the composition was determined by visually observing the appearance and following criteria.
A: A uniform liquid phase in which no liquid crystal or crystals are formed, and the liquid stability is excellent.
X: Liquid crystal formation, crystal formation, separation, or precipitation is observed.

(3) Evaluation of deodorizing effect (treatment method)
Three types of used towels (material: cotton) collected from households are cut individually and washed using the liquid detergent composition shown in Tables 1 and 2 (tartometer 85 rpm × 10 minutes, two rinses, bath ratio) 15) and then dried in a constant temperature room at 30 ° C. and 70% humidity for 12 hours.

(Evaluation of deodorizing effect)
The smell of towel pieces (3 households) dried in a temperature-controlled room was determined by 10 panelists (10 men and women in their 20s and 30s) according to the following criteria, and the average score was obtained.
Odorless …… 0
I feel a slight smell but I don't mind ... 1
I smell ... 2
It smells remarkably ... 3
It smells intense ...... 4

Claims (5)

Surfactant (A) [hereinafter referred to as component (A)] is 35 to 85% by mass, contains 1 to 2 alkyl groups selected from a methyl group, an ethyl group or a propyl group, and contains a sulfonic acid group or a carboxylic acid group. 0.1 to 5% by mass of hydrotrope agent (B) [hereinafter referred to as component (B)] selected from alkylbenzene carboxylic acid or alkylbenzene sulfonic acid or salt thereof, and benzoic acid or salt thereof having one One or more water-miscible organic solvents selected from 0.3 to 10% by mass of hydrogen (C), ethanol, propylene glycol, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, and phenoxypropylene glycol (D) 2-40% by mass, as well as water,
As surfactant (A), the following (a1)-(a3) component is contained in the following range,
The mass ratio (a3) / (B) of the component (a3) to the component (B) is 0.1 to 3,
The pH at 20 ° C. described in 8.3 of JIS K3362: 1998 is 3-7.
Liquid detergent composition.
(A1) component: Nonionic surfactant 15-75 mass% represented by following General formula (1)
R ^a1 O — [(C ₂ H ₄ O) _m / (AO) _n ] H (1)
[Wherein R ^a1 is a chain hydrocarbon group having 8 to 22 carbon atoms, the carbon atom of R ^a1 bonded to the oxygen atom of R ^a1 O is a primary carbon atom, and AO has 3 to 3 carbon atoms. 5 alkyleneoxy group. m and n are average addition mole numbers, m is a number of 14-30, n is a number of 1-5. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded randomly or in blocks. ]
(A2) Component: (b) Nonionic surfactant represented by the general formula (2) 0.5 to 20% by mass
R ^a2 O (C ₂ H ₄ O) _x H (2)
[Wherein R ^a2 is a chain hydrocarbon group having 8 to 22 carbon atoms, and the carbon atom of R ^a2 bonded to the oxygen atom of R ^a2 O is a secondary carbon atom. x is an average addition mole number, and is a number of 2-7. ]
Component (a3): a cationic surfactant represented by the following general formula (3) 0.1 to 5% by mass

Wherein, R ^a31 is a hydrocarbon group having 6 to 22 carbon atoms, in R ^a31 - (A'O) _s - may contain. A′O is an ethyleneoxy group or a propyleneoxy group, s represents an average addition mole number of A′O and is 0 to 10, and R ^a32 , R ^a33 and R ^a34 are each independently a methyl group, ethyl A group, a benzyl group, or a hydroxyalkyl group having 1 to 3 carbon atoms, and X is a halogen atom, CH ₃ SO ₄ or CH ₃ CH ₂ SO ₄ . ] The liquid detergent composition of Claim 1 whose (a1) component is a nonionic surfactant whose m in General formula (1) is a number of 16-30 . Further, as component (A), an anionic surfactant and / or an amphoteric surfactant (a5) [hereinafter referred to as component (a5)] is contained, and (a1) mass ratio of component (a1) to component (a1) / The liquid detergent composition according to claim 1 or 2 , wherein (a5) is 10 to 100. The liquid detergent composition according to any one of claims 1 to 3 , wherein the content of the water-miscible organic amine compound selected from alkanolamine compounds having a total carbon number of 6 or less is less than 1% by mass. The component (D) according to any one of claims 1 to 4, comprising a water-miscible organic solvent selected from diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, and phenoxypropylene glycol. Liquid detergent composition.