WO2023054309A1 - Liquid cleaning agent composition - Google Patents

Abstract

A liquid cleaning agent composition containing an (A) component which is a non-soap surfactant, and a (B) component which is an ethylene oxide-equipped polyethyleneimine having an average number of 8-15 ethylene oxide moles added thereto, wherein: the (A) component content is greater than 0 mass% and no greater than 20 mass%; and the (A) component contains an (Ax) component, which is a compound represented by R11-O-(R12O)n-H (R11 represents a C12-16 alkyl group having a branched chain or a C12-16 straight-chain alkyl group, and if R11 is a straight-chain alkyl group, an oxygen atom is bonded to a secondary carbon atom in the straight-chain alkyl group. R12 represents a C2-4 alkylene group. In addition, n represents the average repeating number of R12O, and is 3-10.).

Description

liquid detergent composition

The present invention relates to a liquid detergent composition and a cleaning method using the same.
This application claims priority based on Japanese Patent Application No. 2021-158109 filed in Japan on September 28, 2021, the contents of which are incorporated herein.

In the washing of animal fiber products such as wool, the washing solution may not easily permeate the fibers, resulting in insufficient washing effect.
Therefore, a detergent composition containing both a surfactant that contributes to detergency and a surfactant that contributes to permeability has been proposed (for example, Patent Document 1).

Japanese Patent Application Laid-Open No. 2005-232363

It is desirable that the amount of the surfactant used for washing is small in order to prevent deterioration of the texture of the textile product. For example, if there is a large amount of surfactant in the washing liquid, the textile product after drying tends to lose its softness.
An object of the present invention is to provide a detergent composition that has good detergency, good permeability to animal textiles, and good softness of washed textiles after drying. do.

As a result of intensive research, the present inventors have found that the component (B), which is not a surfactant, contributes to the improvement of permeability, leading to the present invention.

The present invention has the following aspects.
[1] A liquid detergent composition comprising component (A), which is a non-soap surfactant, and component (B), which is an ethylene oxide adduct of polyethyleneimine and has an average number of added moles of ethylene oxide of 8 to 15. and the content of the component (A) is more than 0% by mass and 20% by mass or less with respect to the total mass of the liquid cleaning composition,
A liquid detergent composition in which the component (A) contains a component (Ax), which is a compound represented by the following general formula (ax1).
R ¹¹ —O—(R ¹² O) _n —H (ax1)
In formula (ax1), R ¹¹ represents a branched C 12-16 alkyl group or a C 12-16 linear alkyl group, and when R ¹¹ is the linear alkyl group, the oxygen atom is , is attached to a secondary carbon atom in said linear alkyl group. R ¹² represents an alkylene group having 2 to 4 carbon atoms. Further, n represents the average number of repetitions of R ¹² O and is 3-10.
[2] Furthermore, the component (C), which is a water-soluble polymer having at least one unit selected from the group consisting of an alkylene terephthalate unit and an alkylene isophthalate unit, and a (poly)oxyalkylene unit, [1] 3. The liquid detergent composition according to .

According to the present invention, it is possible to obtain a detergent composition that has good detergency, good permeability to animal textiles, and good softness of washed textiles after drying. be done.

(Liquid detergent)
The liquid detergent composition of the present invention (hereinafter also simply referred to as "liquid detergent") is a composition containing component (A) and component (B). Furthermore, it is preferable that the component (C) is included.

<(A) Component>
(A) Component is a non-soap surfactant. Component (A) may be used alone or in combination of two or more.
"Non-soap surfactants" are surfactants other than higher fatty acids or salts thereof (so-called soaps). A "higher fatty acid" is a saturated or unsaturated fatty acid having 8 to 24 carbon atoms. That is, component (A) is a surfactant excluding saturated or unsaturated fatty acids having 8 to 24 carbon atoms and salts thereof.
Component (A) includes nonionic surfactants, non-soap anionic surfactants, cationic surfactants, amphoteric surfactants, semipolar surfactants, and the like.
(A) component contains the below-mentioned (Ax) component. Furthermore, it preferably contains one or both of the (A1) component and (A2) component described below.

[(Ax) component]
The (Ax) component is a compound represented by the following general formula (ax1). The (Ax) component has a branched structure in the alkyl group (R ¹¹ —) among polyoxyalkylene type nonionic surfactants.
R ¹¹ —O—(R ¹² O) _n —H (ax1)

In formula (ax1), R ¹¹ represents a branched C 12-16 alkyl group or a C 12-16 linear alkyl group, and when R ¹¹ is the linear alkyl group, the oxygen atom is , is attached to a secondary carbon atom in said linear alkyl group. R ¹² represents an alkylene group having 2 to 4 carbon atoms. Also, n is the average repetition number of R ¹² O and is 3 to 10.

In formula (ax1), R ¹¹ is preferably a branched C 12-14 alkyl group or a C 12-14 linear alkyl group.
Examples of R ¹² O include an oxyethylene group, an oxypropylene group, and an oxybutylene group. Among them, from the viewpoint of liquid stability, an oxyethylene group or an oxypropylene group is preferable. more preferably both a group and an oxypropylene group. When both oxyethylene and oxypropylene groups are present, the oxyethylene and oxypropylene groups may be random or block.
n is the average repeating number of R ¹² O and is a number of 3 to 10, preferably 3 to 7, more preferably 3 to 5, and particularly preferably 3.

A commercial product may be used as the (Ax) component. Commercially available products include, for example, Diadol (registered trademark) manufactured by Mitsubishi Chemical Corporation (the number following C13 and C indicates the number of carbon atoms in the alcohol; the same shall apply hereinafter), and Neodol (registered trademark) manufactured by Shell. (mixture of C12 and C13), Sasol Safol (registered trademark) 23 (mixture of C12 and C13), EXXAL (registered trademark) 13 (C13), etc., equivalent to 3 to 10 moles adducts with ethylene oxide;
A C13 alcohol obtained by subjecting an alkene having 12 carbon atoms obtained by trimerizing butene to an oxo process is added with ethylene oxide corresponding to 3 or 5 moles, or 7 moles (Lutensol (registered trademark) TO3, Lutensol TO5, Lutensol TO7, manufactured by BASF);
C10 alcohol obtained by subjecting pentanol to Garbet reaction, to which ethylene oxide corresponding to 9 moles was added (Lutensol XP90, manufactured by BASF);
A C10 alcohol obtained by subjecting pentanol to a Garbet reaction and adding 7 moles of ethylene oxide (Lutensol XL70, manufactured by BASF);
A C10 alcohol obtained by subjecting pentanol to a Garbet reaction and adding 6 moles of ethylene oxide (Lutensol XA60, manufactured by BASF);
C12-14 secondary alcohols with ethylene oxide equivalent to 3, 5, 7 or 9 moles added (Softanol (registered trademark) 30, Softanol 50, Softanol 70, Softanol 90, manufactured by Nippon Shokubai Co., Ltd.) etc.
(Ax) component may be used individually by 1 type, and may combine 2 or more types.

[(A1) component]
The (A1) component is a nonionic surfactant other than the (Ax) component.
The (A1) component includes, for example, polyoxyalkylene-type nonionic surfactants other than the (Ax) component.
Examples of the component (A1) include compounds represented by the following formula (a1) (excluding compounds represented by the general formula (ax1); hereinafter also referred to as "component (a1)").
R ² -X-[(EO)s/(PO)t]-(EO)uR ³ (a1)
In formula (a1), R ² is a hydrocarbon group having 8 to 22 carbon atoms, X is O, COO, or CON, R ³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or is an alkenyl group of 2 to 6, s represents the average number of repetitions of EO, a number of 3 to 25, t represents the average number of repetitions of PO, a number of 0 to 6, u is the average number of EO It represents the number of repetitions and is a number from 0 to 25, EO represents an oxyethylene group, and PO represents an oxypropylene group.
[(EO)s/(PO)t] indicates that EO and PO may be random chains or block chains. The average repetition number can be measured by gas chromatography or the like.

In formula (a1), the hydrocarbon group for R ² may be linear or branched. You may have an unsaturated bond. The number of carbon atoms is preferably 8-22, more preferably 10-20, even more preferably 10-18. Examples of R ² include those derived from raw materials such as primary or secondary higher alcohols, higher fatty acids, and higher fatty acid amides.
The alkyl group for R ³ is preferably an alkyl group having 1 to 3 carbon atoms. The alkenyl group for R ³ is preferably an alkenyl group having 2 to 3 carbon atoms. R ³ is preferably a hydrogen atom.
In the formula (a1), X is preferably O or COO from the viewpoint of improving the detergency.

s is a number from 3 to 25, preferably from 3 to 20, more preferably from 3 to 18, and more preferably from 3 to 15. If s is within the above range, the detergency is likely to be improved.
t is preferably 0 to 6, more preferably 0 to 3.
u is preferably 0 to 25, more preferably 0 to 15, even more preferably 0 to 10.
s+u is preferably 3 to 30, more preferably 10 to 30, still more preferably 12 to 25, particularly preferably 12 to 22, and most preferably 12 to 18.

Component (a1) may be a commercially available product, or at least ethylene oxide out of ethylene oxide and propylene oxide is added to commercially available raw materials (primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides, etc.) by a known method. It may be added.
Specific examples of the component (a1) include natural alcohols such as CO-1214 (trade name) or CO-1270 (trade name) manufactured by P&G, and ethylene oxide equivalent to 12 mol or 15 mol is added. A product obtained by adding 15 moles of ethylene oxide to methyl coconut fatty acid (lauric acid/myristic acid = 8/2) using an alkoxylation catalyst (polyoxyethylene coconut fatty acid methyl ester (EO 15 moles)) etc.

[Linear AE]
As the component (a1), in particular, X is an oxygen atom, t is 0, ^R3 is a hydrogen atom, ^R2 is a linear alkyl group, and the oxygen atom as X is Linear polyoxyethylene alkyl ethers attached to primary carbon atoms (Linear AE) are preferred.
That is, linear AE is a compound represented by the following general formula (a1-1).
R ² -O-(EO)vH (a1-1)
In formula (a1-1), R ² is a linear alkyl group having 8 to 22 carbon atoms, v represents the average repeating number of EO and is a number of 10 to 30, EO represents an oxyethylene group, The oxygen atom attached to ^R2 is attached to a primary carbon atom in ^R2 .
In linear AE, R ² preferably has 8 to 22 carbon atoms, more preferably 10 to 18 carbon atoms. The average repeating number (v) of EO is preferably 10-30, more preferably 12-18.
When the (Ax) component and linear AE are used together, it is easy to achieve good detergency, good permeability, and good softness in a well-balanced manner.

[(A2) component]
The (A2) component is a non-soap anionic surfactant.
Component (A2) includes, for example, linear alkylbenzenesulfonic acid or its salt (LAS), α-olefinsulfonic acid or its salt (AOS), internal olefinsulfonic acid or its salt (IOS), hydroxyalkanesulfonic acid or its salt, Salts, linear or branched alkyl sulfates or salts thereof, polyoxyalkylene alkyl ether sulfates or salts thereof (AES), polyoxyalkylene alkenyl ether sulfates or salts thereof, alkanesulfonic acids having alkyl groups or salts thereof, α-sulfo fatty acid esters or salts thereof (MES), alkyl ether carboxylic acids or salts thereof, polyoxyalkylene ether carboxylic acids or salts thereof, alkylamide ether carboxylic acids or salts thereof, alkenyl amide ether carboxylic acids or salts thereof , acylaminocarboxylic acid or its salt, alkyl phosphate or its salt, polyoxyalkylene alkyl phosphate or its salt, polyoxyalkylene alkylphenyl phosphate or its salt, glycerin fatty acid ester monophosphate or its salt, etc. is mentioned.
Examples of the salt in component (A2) include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts; and alkanolamine salts such as monoethanolamine salts and diethanolamine salts.
The (A2) component may be produced by a conventional method, or may be a commercially available product.

As the component (A2), linear alkylbenzene sulfonic acid or its salt, α-olefin sulfonic acid or its salt, internal olefin sulfonic acid or its salt, polyoxyalkylene alkyl ether sulfate ester are used because they are excellent in improving the rinsability. or salts thereof, and one or more selected from the group consisting of polyoxyalkylene alkenyl ether sulfates or salts thereof.

As the straight-chain alkylbenzenesulfonic acid or salt thereof, those having a straight-chain alkyl group having 8 to 16 carbon atoms are preferable, and those having a straight-chain alkyl group having 10 to 14 carbon atoms are particularly preferable.
The α-olefin sulfonate and internal olefin sulfonate preferably have 10 to 20 carbon atoms.
Examples of polyoxyalkylene alkyl (alkenyl) ether sulfate esters or salts thereof include compounds represented by the following general formula (a2) (hereinafter also referred to as "component (a2)").
R ¹ -O-[(EO) _j /(PO) _k ]-SO ₃ ^- M ⁺ (a2)
In formula (a2), R ¹ is a linear or branched alkyl group having 8 to 20 carbon atoms or a linear or branched alkenyl group having 8 to 20 carbon atoms, and EO is an oxyethylene group. , PO is an oxypropylene group, j is a number of 0.5 or more indicating the average repetition number of EO, k is a number from 0 to 6 indicating the average repetition number of PO, and M ⁺ is a pair is a cation. [(EO) _j /(PO) _k ] indicates that there is no limitation on the arrangement order of EO and PO.

R ¹ is preferably a straight or branched alkyl or alkenyl group having 10 to 20 carbon atoms, more preferably a straight or branched alkyl or alkenyl group having 12 to 14 carbon atoms.
In particular, straight-chain alkyl groups having 10 to 20 carbon atoms are preferred, and straight-chain alkyl groups having 12 to 14 carbon atoms are more preferred.
j is preferably 0.5 to 5, more preferably 0.5 to 4, even more preferably 0.5 to 3.5, and particularly preferably 1.5 to 2.5.
k is preferably 0 to 3, more preferably 0.
j+k is preferably 0.5 or more, more preferably 0.5 to 5.
In [(EO) _j /(PO) _k ] in formula (a2), EO and PO may be arranged in a mixed manner. When EO and PO are mixed and arranged, they may be in a random form or in a block form. The addition mole number distribution of ethylene oxide and propylene oxide is not particularly limited.
Examples of M ⁺ include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as magnesium ion; and alkanolamine with monoethanolamine, diethanolamine and the like.
Component (a2) may be produced by a conventional method, or may be a commercially available product.

[Other surfactants]
Examples of component (A) other than the above include cationic surfactants, amphoteric surfactants, and semipolar surfactants.
Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts and the like. Counter ions for these salts include halogen ions, alkyl sulfate ions, and the like. Halogen ions include fluoride ions, chloride ions, bromide ions, iodide ions, and the like. The alkyl sulfate ion preferably has an alkyl group of 1 to 3 carbon atoms, such as methyl sulfate ion and ethyl sulfate ion.
Amphoteric surfactants include alkylcarboxybetaine, alkylsulfobetaine, alkylhydroxysulfobetaine, alkylamidobetaine, imidazolinium betaine and the like.
Examples of semipolar surfactants include amine oxide type surfactants such as lauryldimethylamine oxide and lauramidopropyldimethylamine oxide.
These may be produced by a conventional method, or may be commercially available products.

[(B) Component]
Component (B) is an ethylene oxide adduct of polyethyleneimine (hereinafter also referred to as "PEI"), and the average number of moles of ethylene oxide added is 8 to 15 mol.
In the present specification, the average number of added moles of ethylene oxide of component (B) means the average number of added moles of ethylene oxide per mole of active hydrogen possessed by PEI.
Component (B) may be used alone or in combination of two or more.

PEI is obtained by polymerizing ethyleneimine and has a branched chain structure containing primary, secondary and tertiary amine nitrogen atoms in its structure.
The weight average molecular weight of PEI is preferably 200-2000, more preferably 300-1500, more preferably 400-1000, and particularly preferably 500-800.
PEI preferably has 8 to 15 active hydrogens, more preferably 9 to 15, even more preferably 10 to 15, in one molecule.

The component (B) is obtained by adding ethylene oxide to PEI. Examples of this method include a method of adding ethylene oxide to the starting material PEI at 100 to 180° C. in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide and sodium methylate. .

The component (B) includes, for example, compounds represented by formula (b1-1). (B) As a component, a synthetic product may be used and a commercial item may be used.

In formula (b1-1), R ²² is an ethylene group. m represents the average repetition number of (R ²² O) and is a number from 8 to 15. m corresponds to the average number of added moles of ethylene oxide of component (B).

The weight average molecular weight of component (B) is preferably 1,000 to 80,000, more preferably 2,000 to 50,000, still more preferably 3,000 to 30,000, and particularly preferably 5,000 to 20,000.
In addition, the weight average molecular weight in this specification means the value obtained by gel permeation chromatography using polyethylene glycol as a standard substance.

[(C) Component]
Component (C) comprises at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units (hereinafter also referred to as (c1) units) and (poly)oxyalkylene units (hereinafter referred to as (c2) units It is a water-soluble polymer having
Here, "water-soluble" means that 10 g of sample is added to 1000 g of water (40 ° C.) and dissolved for 12 hours with a stirrer (thickness: 8 mm, length 50 mm) (200 rpm). Say.

The (c1) unit is at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units.
The alkylene terephthalate unit is a unit represented by formula (c1-1) below.

In formula (c1-1), R ³¹ is an alkylene group having 1 to 4 carbon atoms. R ³¹ preferably has 2 to 4 carbon atoms.
Examples of alkylene terephthalate units include ethylene terephthalate units, n-propylene terephthalate units, isopropylene terephthalate units, n-butylene terephthalate units, isobutylene terephthalate units, sec-butylene terephthalate units, and tert-butylene terephthalate units. Among these, isopropylene terephthalate units are preferred.
The component (A) may contain one type of these alkylene terephthalate units, or two or more types thereof.

The alkylene isophthalate unit is a unit represented by the following formula (c1-2).

In formula (c1-2), R ⁴¹ is an alkylene group having 1 to 4 carbon atoms. The number of carbon atoms in R ⁴¹ is preferably 2-4.
Examples of alkylene isophthalate units include ethylene isophthalate units, n-propylene isophthalate units, isopropylene isophthalate units, n-butylene isophthalate units, sec-butylene isophthalate units, and tert-butylene isophthalate units. be done. Among these, isopropylene isophthalate units are preferred.
The component (C) may contain one of these alkylene isophthalate units, or two or more of them.

Component (C) may have both alkylene terephthalate units and alkylene isophthalate units as (c1) units, or may have only one of alkylene terephthalate units and alkylene isophthalate units. . Component (C) more preferably contains both alkylene terephthalate units and alkylene isophthalate units.

A (poly)oxyalkylene unit ((c2) unit) is a generic term for a monooxyalkylene unit and a polyoxyalkylene unit.
The (c2) unit is represented by the following formula (c2-1).

-(R ⁵¹ O) _w - (c2-1)

In formula (c2-1), R ⁵¹ represents an alkylene group having 1 to 4 carbon atoms. The number of carbon atoms in R ⁵¹ is preferably 2-4.
w is an integer of 1-100, preferably 1-80, more preferably 1-50.

(c2) units include oxyethylene units, polyoxyethylene units, oxypropylene units, polyoxypropylene units, polyoxyethylene polyoxypropylene units and the like, and oxyethylene units or polyoxyethylene units are preferred.
The component (C) may contain one of these (c2) units, or two or more of them.

The component (C) may be any component as long as it has (c1) units and (c2) units, and may be a random copolymer or a block copolymer. Among these, a block copolymer is preferable as the component (C).
The component (C) is a unit other than the (c1) unit and the (c2) unit (e.g., a unit derived from a polymerization initiator, a polymerization terminator, etc., or a unit polymerizable with the (c1) unit or the (c2) unit. ) may be included. However, the total amount of (c1) units and (c2) units in component (C) is preferably 80 mol % or more, more preferably 90 mol % or more.

The (C) component includes, for example, compounds represented by the following general formula (C1) or the following general formula (C2).

In the formula (C1), each Z ¹ is independently a hydrogen atom or a methyl group, preferably both are methyl groups.
R ⁶¹ and R ⁶² are each independently an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms.
x ¹ is a number from 0 to 10 representing the average repeating number of structural units, preferably from 0.5 to 5, more preferably from 0.5 to 2.5. If it is more than the said lower limit, it will be excellent in the improvement effect of flexibility. If it is less than the above upper limit, it is easy to obtain a liquid detergent excellent in appearance stability.
y ¹ is a number representing the average repeating number of (R ⁶¹ O), each independently preferably from 1 to 100, more preferably from 1 to 80, still more preferably from 1 to 50, particularly preferably from 10 to 50; 20-30 is most preferred. If it is more than the said lower limit, it will be excellent in the permeability improvement effect. When the content is equal to or less than the above upper limit, the effect of improving flexibility is excellent.
In formula (C1), the ratio of x ¹ to y ¹ (x ¹ :y ¹ ) is preferably 1:5 to 1:20, more preferably 1:8 to 1:18. When (x ¹ :y ¹ ) is within the above range, the effect of improving flexibility and the effect of improving permeability are excellent.

In formula (C2), each Z ² is independently a hydrogen atom or a methyl group, preferably both are methyl groups.
R ⁶³ and R ⁶⁴ are each independently an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms.
^x2 is a number from 0 to 10 representing the average repeating number of structural units, preferably from 0.5 to 5, more preferably from 0.5 to 2.5. If it is more than the said lower limit, it will be excellent in the improvement effect of flexibility. If it is less than the above upper limit, a liquid detergent excellent in appearance stability is likely to be applied.
y ² is a number representing the average repeating number of (R ⁶³ O), each independently preferably 1 to 100, more preferably 1 to 80, still more preferably 1 to 50, particularly preferably 10 to 50; 20-30 is most preferred. If it is more than the said lower limit, it will be excellent in the permeability improvement effect. When the content is equal to or less than the above upper limit, the effect of improving flexibility is excellent.
In formula (C2), the ratio of x ² to y ² (x ² :y ² ) is preferably 1:5 to 1:20, more preferably 1:8 to 1:18. When (x ² :y ² ) is within the above range, the effect of improving flexibility and the effect of improving permeability are excellent.

The mass average molecular weight of component (C) is preferably 500-10,000. If the weight average molecular weight is within the above range, the solubility and dispersibility in water is excellent. In addition, it is easy to improve the water absorbency of hydrophobic fibers such as animal fiber products.
The lower limit of the mass average molecular weight of component (C) is more preferably 800 or more, and even more preferably 1000 or more.
The upper limit of the mass average molecular weight of component (C) is more preferably 9,000 or less, and even more preferably 8,000 or less.
Therefore, the mass average molecular weight of component (C) is more preferably 800-9000, and even more preferably 1000-8000.

The mass average molecular weight of component (C) is a value obtained by converting the value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent, using PEG (polyethylene glycol) as a calibration curve.

Component (C) is readily available on the market. Also, the component (C) may be synthesized by methods described in various publications. Publications describing the method for producing component (C) include, for example, Journal of Polymer Science, Vol. 3, pp. 609-630 (1948), Journal of Polymer Science, Vol. 8, pp. 1-22 ( 1951), JP-A-61-218699, and the like.
Commercially available products of component (C) include, for example, TexCare (registered trademark) SRN-100 (trade name, manufactured by Clariant Japan K.K., mass average molecular weight: 2000 to 3000) and TexCare SRN-300 (trade name, Clariant Japan). Co., Ltd., mass average molecular weight: 7000), Repel-O-Tex (registered trademark) Crystal (trade name, manufactured by Rhodia, mass average molecular weight: undetermined), Repel-O-Tex QCL (trade name, manufactured by Rhodia, mass average molecular weight: undetermined) and the like. Among these, TexCare SRN-100 is preferred because it is highly soluble in water and shows little decrease in washing performance after storage. A 70% by mass aqueous solution of TexCare SRN-100 is particularly preferred, and a commercially available product thereof includes TexCare SRN-170C (trade name, manufactured by Clariant Japan KK).

<Water>
The liquid detergent of the present invention preferably contains water as a solvent from the viewpoints of ease of handling during production and solubility in water during use.

<Optional component>
The liquid detergent of the present invention may contain optional components within the range that does not impair the effects of the present invention.
Examples of optional components include those commonly used in liquid detergents, such as fatty acids having 12 to 18 carbon atoms or salts thereof, water-miscible organic solvents, chelating agents, enzymes, hydrotropes, antifoaming silicones, and detergents. General-purpose dyes or pigments used as character builders, stabilizers, alkali agents, texture improvers, preservatives, fluorescent agents, dye transfer inhibitors, pearlescent agents, antioxidants, antibacterial agents, coloring agents, emulsifying agents, fragrances , insoluble particles, pH adjusters, and extracts of natural products. These components may be used singly or in combination of two or more.

Examples of fatty acids having 12 to 18 carbon atoms include single fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid and oleic acid, and mixed fatty acids such as coconut oil fatty acid and beef tallow fatty acid. .
A combination of a fatty acid having a hydrocarbon group of 12 carbon atoms and a fatty acid having a hydrocarbon group of 14 to 18 carbon atoms is preferable, and a fatty acid having a carbon number of 12 and two or more hydrocarbon groups having 14 to 18 carbon atoms. with a fatty acid is more preferred.
The ratio of the mass of the fatty acid with 14 to 18 carbon atoms to the mass of the fatty acid with 12 carbon atoms, [fatty acid with 14 to 18 carbon atoms]/[fatty acid with 12 carbon atoms] is preferably 0.03 or more and 10 or less, 0.05 or more and 0.8 or less are preferable, and 0.06 or more and 0.5 or less are more preferable.

The fatty acid having 12 to 18 carbon atoms may be present in the form of a salt in the liquid cleaning agent or in the cleaning solution obtained by dissolving the liquid cleaning agent in water. Salt forms include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; and alkanolamine salts such as monoethanolammonium and diethanolammonium.
Commercially available products include sodium palmate ((coconut fatty acid) manufactured by NOF Corporation) neutralized with sodium hydroxide, which is a pH adjuster), and C16 soap ((sodium palmitate) manufactured by Kanto Kagaku Co., Ltd.). etc.

As used herein, a water-miscible organic solvent refers to an organic solvent that dissolves in 1 L of deionized water at 25° C. in an amount of 50 g or more.
By blending the water-miscible organic solvent, the stability of the liquid detergent during low-temperature storage and antiseptic power can be enhanced.
Water-miscible organic solvents include alcohols such as ethanol, 1-propanol, 2-propanol and 1-butanol; glycols such as propylene glycol, butylene glycol and hexylene glycol; polyglycols such as dipropylene glycol; monobutyl ether (butyl carbitol), diethylene glycol dimethyl ether, alkyl ethers such as 3-methoxy-3-methyl-1-butanol, phenoxyethanol and the like. Among these, ethanol, propylene glycol, diethylene glycol monobutyl ether (butyl carbitol), 3-methoxy-3-methyl-1-butanol, and phenoxyethanol are preferred because of their availability, stability of the liquid detergent, fluidity, etc. preferable.

Metal ion scavengers (chelating agents) include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid and the like.
Hydrotropic agents include p-toluenesulfonic acid or its salts, cumenesulfonic acid or its salts, benzoates, phenoxyethanol, and urea.
Examples of alkaline agents include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine.

For example, a silicone oil having a modified group can be used as a texture improver. Specific examples include polyether-modified silicone, aminopolyether-modified silicone, amidepolyether-modified silicone, and alkylpolyether-modified silicone. By blending the silicone oil having a modified group, the friction of the textile product in the bath is reduced, and the texture after drying is improved.
Examples of commercially available silicone oils having a modifying group include "CF1188N", "BY16-878", "BY16-891", "BY16-893", and "FV2090-01" manufactured by Dow Corning Toray Co., Ltd. "SILSTYLE104", "SF8417", "SF8418", "BY16-837", "BY16-906", "FZ-2203", "FZ-3789", etc., "KF-877" manufactured by Shin-Etsu Chemical Co., Ltd., "KF-889", "X-22-3939A", etc., "WetSoft (registered trademark) CTA", "WetSoft AE200", "WetSoft NE810", "WetSoft NE820", "WetSoft WP201" manufactured by Asahi Kasei Wacker Silicone Co., Ltd. etc.

Any of oil type, oil compound type, emulsion type, and self-emulsifying type can be used as antifoaming silicone.
Oil-type antifoaming silicone is an antifoaming agent composed of 100% unmodified silicone oil and containing no silica. Commercially available products include SH200 (Dow Corning Toray Co., Ltd.).
Oil compound type antifoaming silicone is an antifoaming agent in which water-insoluble particles such as finely divided silica are blended with silicone oil. Commercially available products include 8590 Additive (Dow Corning Toray Co., Ltd.), AF-8014 Antifoam (Dow Corning Toray Co., Ltd.), AC-8066 Antifoam (Dow Corning Toray Co., Ltd.), ACP-3073 Antifoam ( Dow Corning Toray Co., Ltd.), KS-66 (Shin-Etsu Chemical Co., Ltd.), and the like.
Solution-type antifoaming silicone is an antifoaming agent obtained by dissolving silicone oil in a solvent such as isoparaffin. Commercially available products include KS-602A (Shin-Etsu Chemical Co., Ltd.).
Emulsion-type antifoaming silicone is an antifoaming agent obtained by emulsifying a silicone oil compound with a nonionic active agent. Commercially available products include FS Antifoam 93 (Dow Corning Toray Co., Ltd.), KM-90 (Shin-Etsu Chemical Co., Ltd.), KM-73 (Shin-Etsu Chemical Co., Ltd.), KM-7750 (Shin-Etsu Chemical Co., Ltd.). , KM-7752 (Shin-Etsu Chemical Co., Ltd.) and the like.
Self-emulsifying antifoaming silicone is an antifoaming agent composed of a hydrophilic modified silicone oil and an oil compound. Commercially available products include KS-537 (Shin-Etsu Chemical Co., Ltd.).

Examples of antiseptics include "Cason CG" (trade name) manufactured by Dow Chemical Co., Ltd., "Acticide MBS" (trade name) manufactured by Thor Japan, and "NIPACIDE BIT 20" (trade name) manufactured by Clariant. .
Antioxidants include dibutylhydroxytoluene (BHT), distyrenated cresol, sodium sulfite, sodium hydrogen sulfite, and the like.
Perfumes include, for example, perfume ingredients described in JP-A-2002-146399.
Examples of pH adjusters include sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine, and the like.

Examples of antibacterial agents include diphenyl, alcohol, phenol, aldehyde, carboxylic acid, ester, ether, nitrile, peroxide/epoxy, halogen, pyridine/quinoline, triazine, and isothiazolone. organic antibacterial agents such as antibacterial agents, imidazole/thiazole, anilide, biguanide, disulfide, thiocarbamate, carbohydrate, tropolone, and organometallic antibacterial agents; inorganic antibacterial agents such as metal oxides and silver mentioned. Specific examples include diclosan, triclosan, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylenebiguanide hydrochloride, 8-oxyquinoline, polylysine and the like.

Extracts of natural products such as dog pagoda, urticaria, echinacea, scutellaria baicalensis, yellowfin, coptis, allspice, oregano, pagoda, chamomile, honeysuckle, clara, key mussel, kay, bay bay, magnolia, burdock, comfrey, jassho, burnet, Peony, ginger, goldenrod, sambucus nigra, sage, mistletoe, hosoba okera, thyme, hollyhock, clove, unshu mandarin, tea tree, barberry, houttuynia cordata, nanten, nymph, yellow rush, shirogaya, boletus, hollanda gourd, hops, honshitan, mountain grape , Murasaki sanguinea, Phyllanthus japonicum, Lily leopard, Mountain perilla, Eucalyptus, Lavender, Rose, Rosemary, Balan, Japanese cedar, Gilead balsam, Hakusen, Broom, Michiyanagi, Jingyo lily, Liquid lily, Vortex ginseng, Yamabishi, Yabugarashi, Glycyrrhiza, St. John's wort, etc. plants.

<Content of each component>
The content of component (A) is more than 0% by mass and 20% by mass or less, preferably 3 to 20% by mass, more preferably 5 to 20% by mass, and 5 to 15% by mass, relative to the total mass of the liquid detergent. % is more preferred. If the content of component (A) exceeds 0% by mass, good detergency is likely to be obtained. If the content of component (A) is equal to or less than the above upper limit, good flexibility can be easily obtained after washing and drying.

The ratio of component (Ax) to the total mass of component (A) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. If the ratio of the component (Ax) is at least the above lower limit, the effect of improving permeability is excellent.
Although the upper limit of the ratio of component (Ax) to the total mass of component (A) may be 100% by mass, it is preferably 70% by mass or less, and 60% by mass, in order to easily obtain good flexibility after washing and drying. % by mass is more preferred, and 50% by mass or less is even more preferred.

When the component (A) contains one or both of the component (A1) and the component (A2), the effect of improving flexibility is excellent.
The total amount of components (Ax), (A1) and (A2) is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, relative to component (A). 100 mass % may be sufficient.

Furthermore, when the (A1) component contains linear AE, the detergency and softness improving effect are excellent.
The ratio of linear AE to component (A1) is preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more. 100 mass % may be sufficient.

The mass ratio represented by ((A1) component + (A2) component) / (Ax) component (hereinafter also referred to as "(A1 + A2) / Ax ratio") is preferably 0.1 to 20, and 1 to 10 more preferred. When the (A1+A2)/Ax ratio is equal to or higher than the lower limit, the cleaning effect is excellent. If the (A1+A2)/Ax ratio is equal to or less than the upper limit, the effect of improving permeability is excellent.

The content of component (B) is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, even more preferably 1 to 3% by mass, relative to the total mass of the liquid detergent.
The component (B) contributes to improving permeability, detergency and softness. It is believed that the components (B) and (A) form composite micelles to improve detergency. It is also believed that the component (B) is adsorbed on the fibers to improve permeability and flexibility.
When the content of component (B) is at least the above lower limit, the effect of improving permeability, detergency and flexibility is excellent. If the content of component (B) is equal to or less than the above upper limit, it is easy to secure the degree of freedom in blending other components.

The mass ratio represented by component (B)/component (A) (hereinafter also referred to as "B/A ratio") is 0.05 or more, preferably 0.1 or more, and 0.3 or more. is particularly preferred. If the B/A ratio is at least the above lower limit, the cleansing effect and the effect of improving permeability are excellent. The upper limit of the B/A ratio is, for example, 10, preferably 1. If the B/A ratio is equal to or less than the upper limit, the effect of improving flexibility is excellent.

The content of component (C) is preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass, even more preferably 0.5 to 3% by mass, relative to the total mass of the liquid detergent.
(C) A component contributes to the improvement of permeability and a softness|flexibility. It is believed that the component (C) coats the fiber surface.
If the content of component (C) is at least the above lower limit, the effect of improving permeability and flexibility is excellent. If the content of component (C) is equal to or less than the above upper limit, it is easy to secure the degree of freedom in blending other components.

The lower limit of the mass ratio represented by component (C)/component (A) (hereinafter also referred to as "C/A ratio") is, for example, 0.001, preferably 0.01. If the C/A ratio is at least the above lower limit, the effect of improving permeability is excellent. The upper limit of the C/A ratio is, for example, 10, preferably 1. If the C/A ratio is equal to or lower than the upper limit, the cleaning effect is excellent.

The water content is not particularly limited, but is preferably 30 to 95% by mass, more preferably 50 to 90% by mass, and even more preferably 70 to 85% by mass relative to the total mass of the liquid detergent.
20 mass % or less is preferable with respect to the total mass of a liquid cleaning agent, and, as for content of an arbitrary component, 10 mass % or less is more preferable.
The total content of each component of the liquid detergent does not exceed 100% by mass.

<pH>
The liquid detergent preferably has a pH of 4 to 10, more preferably 4 to 9, and even more preferably 4 to 8 at 25°C. When the pH is in such a range, the storage stability of the liquid detergent can be maintained satisfactorily.
The pH is measured with a pH meter (for example, "HM-30G" (product name) manufactured by Toa DKK Co., Ltd.) or the like.
A liquid detergent is manufactured according to a conventional method. As a production method, for example, components (A), (B), (C) and, if necessary, other components are added to a part of water, the pH is adjusted, and then the rest of the water is added. method.

<How to use>
When washing objects with the liquid detergent of the present invention, the liquid detergent is dissolved in water to form a washing solution, and after the objects to be washed are immersed in this washing solution, the objects to be washed and the washing solution are separated. . After separating the object to be washed and the cleaning liquid, the object to be washed is dried to complete the washing. After separating the object to be washed and the washing liquid, dehydration treatment may be performed before drying. Moreover, after separating the object to be washed and the cleaning liquid, dehydration treatment and rinsing treatment may be performed before drying.
The content of the liquid detergent in the cleaning liquid is not particularly limited. The amount of liquid detergent added to water is preferably 3 to 15 mL of liquid detergent per 10 L of water, for example.

By immersing the object to be washed with dirt in the cleaning liquid, the dirt is transferred to the cleaning liquid.
After that, by separating the object to be washed from the cleaning liquid containing the transferred dirt, the object to be washed from which the dirt has been washed is obtained. The method of separating the object to be washed from the cleaning liquid may be a method of draining the cleaning liquid or a method of removing the object to be washed from the cleaning liquid.

Examples of items to be washed include textile products such as clothes, fabrics, sheets, curtains, and carpets.
The material of the textile product is not particularly limited, and may be any of animal fibers (wool, feathers, etc.), natural fibers such as cotton, silk, hemp, etc., and chemical fibers such as polyester, acrylic, nylon, rayon, polyamide, and the like.
Since the liquid detergent of the present invention has excellent permeability, it is suitable for washing textile products containing animal fibers (such as wool).

In the method of washing textiles as an object to be washed (washing method), the concentration of the component (A) in the washing solution is preferably 10-150 ppm, more preferably 30-150 ppm.
In the washing method, the bath ratio in the step of immersing the article to be washed in the washing liquid (washing step) is preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more. When the bath ratio is at least the above lower limit, the efficiency of contact between the object to be washed (textiles) and the cleaning liquid can be further increased, and the cleaning effect can be further enhanced. The upper limit of the liquor ratio is not particularly limited, but is set to 50, for example. The bath ratio is a mass ratio expressed by [mass of cleaning liquid]/[mass of object to be washed].
Moreover, the immersion time for immersing the textile product in the cleaning liquid is preferably 3 minutes or longer, and more preferably 5 minutes or longer.

When the article to be washed is a textile product, an external force may be applied to the article to be washed in the washing liquid in the washing step of transferring dirt to the washing liquid. The method of applying an external force to the article to be washed may be, for example, a method of applying a mechanical force using a washing machine, or a hand-washing method such as rubbing, pressing, beating, grasping, pinching, or shaking.
In the dehydration treatment, water contained in the washed items is reduced. For example, dehydration is performed by applying centrifugal force or pressing force.
The bath ratio after the dehydration treatment is less than 1, preferably 0.7 or less, and even more preferably 0.5 or less.
In the rinsing treatment, the article to be washed is brought into contact with a rinsing liquid in which the concentration of the liquid detergent is lower than that of the cleaning liquid. The rinsing liquid may be water containing no liquid cleaning agent, or may be, for example, a liquid in which a small amount of liquid cleaning agent is dispersed in water. A dehydration treatment may be performed either or both before the rinsing treatment and after the rinsing treatment.

Since the liquid detergent of the present invention has a low surfactant content, the cleaning liquid obtained by dissolving the liquid detergent in water causes little foaming and is excellent in rinsability. Also, as shown in the examples below, good detergency and flexibility can be obtained without a rinsing step. Therefore, the rinsing process can be simplified by using the liquid detergent of the present invention. Specifically, one or both of the amount of rinsing water and the number of times of rinsing can be reduced. No rinsing step is required. For example, it is also possible to use a cleaning method in which the object to be washed is immersed in a cleaning solution in which a liquid detergent is dissolved in water, the object to be washed and the cleaning solution are separated, and then dried without rinsing.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
Materials used in the examples are shown below.

<Materials used>
[(Ax) component]
Ax-1: manufactured by BASF, trade name “Lutensol TO-7”, C ₁₃ H ₂₇ O(CH ₂ CH ₂ O) ₇ H, in the formula (ax1), R ¹¹ has 13 carbon atoms and has a branched chain a compound in which an alkyl group, R ¹² O is an oxyethylene group, and n is 7;
Ax-2: manufactured by Nippon Shokubai Co., Ltd., trade name “Softanol 30”, in the formula (ax1), R ¹¹ is a linear alkyl group having 12 to 14 carbon atoms, and the oxygen ^atom is a compound bonded to a secondary carbon atom, wherein R ¹² O is an oxyethylene group and n is 3;
Ax-3: manufactured by Nippon Shokubai Co., Ltd., trade name “SOFTANOL EP5035”, in the formula (ax1), R ¹¹ is a branched C 12-14 alkyl group, R ¹² O oxyethylene group, n is 3 .5.

[(A1) Component]
A1-1: Linear AE, polyoxyethylene alkyl ether (15EO), ethylene oxide equivalent to 15 moles added to natural alcohol.
In the above formula (a1), R ² is a linear alkyl group having 12 carbon atoms and a linear alkyl group having 14 carbon atoms, X is O, R ³ is a hydrogen atom, s = 15, t = 0, u = 0 some compound.
A1-2: Linear AE, polyoxyethylene alkyl ether (12EO), 12 mol equivalent of ethylene oxide added to natural alcohol. In the above formula (a1), ^R2 is a linear alkyl group having 12 carbon atoms and a linear alkyl group having 14 carbon atoms, X is O, ^R3 is a hydrogen atom, s = 12, t = 0, u = 0 some compound.
A1-3: Linear AE, polyoxyethylene alkyl ether (6EO), ethylene oxide equivalent to 6 moles added to natural alcohol. In the above formula (a1), R ² is a linear alkyl group having 12 carbon atoms and a linear alkyl group having 14 carbon atoms, X is O, R ³ is a hydrogen atom, s = 6, t = 0, u = 0 some compound.
A1-4: EP nonion, natural alcohol (mass ratio of primary alcohol having 12 carbon atoms/primary alcohol having 14 carbon atoms = 7/3), 8 mol ethylene oxide, 2 mol propylene oxide, 8 mol block addition in order of ethylene oxide. In the above formula (a1), R ² is an alkyl group having 12 carbon atoms/alkyl group having 14 carbon atoms = 7/3, X is O, R ³ is a hydrogen atom, s = 8, t = 2, u = 8. some compound.
A1-5: manufactured by Lion Corporation, trade name “MEE”, polyoxyethylene fatty acid methyl ester (fatty acid carbon number 12-14, average added mole number of ethylene oxide 15), in the formula (a1), R ² is carbon A compound in which one or more alkyl groups selected from alkyl groups having number 11 and alkyl groups having 13 carbon atoms, X is COO, ^R3 is a methyl group, s=15, t=0 and u=0. Made by Lion Corporation, trade name "MEE".

[(A2) component]
A2-1: Polyoxyethylene alkyl ether sulfate (polyoxyethylene alkyl ether sulfate ester salt. R ¹ in the formula (a2) is a linear alkyl group having 12 and 14 carbon atoms, j is 2, k is 0 , M ⁺ is a sodium ion, manufactured by PT. Kao Indonesia Chemicals, trade name “EMAL 270”).
A2-2: Monoethanolamine salt of polyoxyethylene polyoxypropane-1,2-diylalkyl ether sulfate (AEPS).
A2-3: Sodium linear alkylbenzene sulfonate (LAS), trade name “Lipon LS-250”, manufactured by Lion Corporation.
A2-4: Sodium α-olefin sulfonate (AOS), trade name “Liporan LB-840”, manufactured by Lion Corporation.
A2-5: IOS, an inner olefin sulfonate synthesized by the method described in Example 7 of JP-A-2001-247534.

[(B) Component]
B-1 PEI (10EO): ethylene oxide adduct of polyethyleneimine obtained in Production Example 1 below (weight average molecular weight of polyethyleneimine: 800, number of active hydrogens in one molecule of polyethyleneimine: 10, active hydrogen: 1 Average added moles of ethylene oxide per mole: 10).

[(C) component]
C-1: Clariant Japan Co., Ltd., trade name "TexCare SRN-170C", weight average molecular weight: 2000 to 3000, pH (5% by mass aqueous solution at 20°C) 4, viscosity (20°C) 300 mPa·s.
TexCare SRN-170C is a 70% by mass aqueous solution of TexCare SRN-100 (trade name, manufactured by Clariant Japan, weight average molecular weight: 2000 to 3000). Note that TexCare SRN-100 corresponds to the compound represented by formula (C1).

[Optional component]
Coconut fatty acid: Coconut fatty acid (trade name, manufactured by NOF Corporation).
POE-modified silicone: CF1188N (trade name, manufactured by Dow Corning Toray Co., Ltd.), polyether-modified silicone.
Silicone emulsion: manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KM-90".
Solvent 1: Ethanol (manufactured by Nippon Alcohol Sales Co., Ltd., trade name "specific 95 degree synthetic alcohol").
Solvent 2: 3-methoxy-3-methyl-1-butanol (manufactured by Kuraray, trade name “Solfit”).
Sodium benzoate: Sodium benzoate (manufactured by Toagosei Co., Ltd.).
Citric acid: liquid citric acid (trade name, manufactured by Lion Specialty Chemicals Co., Ltd.), chelating agent.
Perfume: Perfume composition A described in Tables 11 to 18 of JP-A-2002-146399.
BHT: SUMILZER BHT-R (trade name, manufactured by Sumitomo Chemical Co., Ltd.), dibutylhydroxytoluene.
Pigment: Kayanol Milling (trade name, manufactured by Nippon Kayaku Co., Ltd.), Acid Red 138.
NaOH: Sodium hydroxide (manufactured by Toagosei Co., Ltd.).
pH adjuster: sulfuric acid (manufactured by Toagosei Co., Ltd.), sodium hydroxide (manufactured by Toagosei Co., Ltd.).
[water]
Water: purified water.

<Production Example 1: Production of ethylene oxide adduct (10EO) of polyethyleneimine>
An autoclave containing polyethyleneimine (manufactured by BASF, trade name “Lupasol FG”) and water was vacuum degassed and then replaced with nitrogen. While the autoclave was being heated, ethylene oxide corresponding to 10 mol per 1 mol of nitrogen atom was added for ethoxylation to obtain an ethylene oxide adduct of polyethyleneimine.

<Evaluation method>
[Evaluation of detergency]
As the soiled cloth, wet artificial soiled cloth (manufactured by Laundry Science Association, 28.3% oleic acid, 15.6% triolein, 12.2% cholesterol oleate, 2.5% liquid paraffin, 2.5% squalene , cholesterol 1.6%, gelatin 7.0%, mud 29.8%, carbon black 0.5%) was cut into a 5 cm x 5 cm square.
A Terg-O-tometer (manufactured by UNITED STATES TESTING) was used as a cleaning tester.
As a washing liquid, one prepared by adding 1200 μL (1.2 mL) of the liquid detergent of each example to 900 mL of water and stirring for 30 seconds was used.
900 mL of the cleaning liquid, 10 sheets of the dirty cloth, and the washed knitted cloth were put into the cleaning tester, and after adjusting the bath ratio (mass of the cleaning liquid/total mass of the cloth to be washed) to 30 times, the speed was adjusted to 60 rpm. , 15° C. for 10 minutes. After that, it was transferred to a two-tank washing machine (Toshiba Corporation, product name "VH-30S") and dehydrated for 1 minute to set the bath ratio of the washed material to 0.5 (dehydration step). After that, the items to be washed were air-dried.
The reflectance is calculated for each of the dirty cloth before washing, the dirty cloth after washing, and the unsoiled cloth (here, unsoiled cloth means the original white cloth (original cloth) without dirt). It was measured with a color difference meter (manufactured by Nippon Denshoku Co., Ltd., product name "SE200 type"), and the cleaning rate (%) was determined by the following formula (i).
Washing rate (%) = (K/S of dirty cloth before washing - K/S of dirty cloth after washing) / (K/S of dirty cloth before washing - K/S of unsoiled cloth )×100 (i)
[In the formula (i), K / S is (1-R / 100) 2 / (2R / 100), R is the dirty cloth before washing, the dirty cloth after washing or the unsoiled cloth represents the reflectance (%) of K is the extinction coefficient, S is the scattering coefficient, and R is the absolute reflectance. ]
The average value of the cleaning rate of 10 soiled cloths was obtained. The obtained average values were evaluated according to the following evaluation criteria. In the following evaluation criteria, ⊚ and ∘ were regarded as passed.
(Evaluation criteria)
⊚: Cleaning rate is 50% or more.
◯: Cleaning rate is 45% or more and less than 50%.
Δ: Cleaning rate is 40% or more and less than 45%.
x: The cleaning rate is less than 40%.

[Evaluation of permeability]
Penetration was evaluated using the improved Draves method (edited by Motoi Minagawa, "Encyclopedia of Detergents and Washes" 2003 (Asakura Shoten), see page 191). The specific operation method is as follows.
Into a 500 mL graduated cylinder, 500 mL of a cleaning liquid (1.2 mL of the liquid cleaning agent of each example dissolved in 900 mL of tap water) prepared at 20° C. was placed.
A 56 cm long wire device having an annular (45 mm diameter) wire anchor at one end was prepared, and a snake pin hook was attached to the anchor with a nylon thread. Wool (Kokan Haramaki, manufactured by Kokan Gunze Co., Ltd.) cut to 1 cm×10 cm and conditioned to 65% humidity was hooked on the tip of the hook. The anchor part hooked with the wool was immersed until it reached the bottom of the graduated cylinder, creating a state in which the wool cloth stood up in the graduated cylinder. The settling time (seconds) required for the tip of the wool (the end of the wool opposite to the one hooked on the wire) to settle to the bottom of the graduated cylinder after the anchor reached the bottom of the graduated cylinder was measured. A shorter sedimentation time means better permeability.
Evaluation was made according to the following criteria. ◎◎, ◎ and 〇 were regarded as passed.
(Evaluation criteria)
⊚: The time required for the wool to settle is less than 20 seconds.
A: The time required for the wool to settle is 20 seconds or more and less than 50 seconds.
Good: The time required for the wool to settle is 50 seconds or more and less than 100 seconds.
Δ: The time required for the wool to settle is 100 seconds or more and less than 300 seconds.
x: The time required for the wool to settle is 300 seconds or longer.

[Evaluation of flexibility]
In order to adjust the bath ratio (mass of washing liquid / total mass of cloth to be washed) to 30 times, 3 commercial cotton towels (100% cotton) in a fully automatic electric washing and drying machine (Toshiba AW-8V2), Two cotton-skinned shirts (manufactured by B.V.D., about 400 g total weight of all washed cloths) were added.
16 mL of the liquid detergent of each example was added to the above-mentioned washing machine, and a washing operation was performed in which washing and dehydration were performed sequentially in a weak water flow course. Washing (time: 10 minutes), spin-drying (time: 5 minutes), and water volume (set to low water level, water volume: approx. 12 L) were adjusted and washed. After washing, the towels taken out were left in a constant temperature and humidity room at 25° C. and 65% RH to dry. This was used as a test cloth for flexibility evaluation.
As the evaluation control cloth, 16 mL of 20% nonionic surfactant (15 mol equivalent of ethylene oxide added to natural alcohol CO-1270 manufactured by P&G) was used in the same manner as the test cloth. Treated cotton towels were used.
The softening effect was evaluated sensorily by comparing the comparison fabric in pairs according to the following evaluation criteria, and the average value of 6 expert panelists was obtained. A case where the average value was 3 points or more was regarded as a pass.
(Scoring criteria)
5 points: Much softer than the control fabric.
4 points: Considerably softer than the control fabric.
3 points: Softer than the control fabric.
2 points: Slightly softer than the control fabric.
1 point: Equivalent to the control fabric.
(Evaluation criteria)
◎: 4 points or more, ○: 3 points or more and less than 4 points, △: 2 points or more but less than 3 points, ×: less than 2 points.

[Examples 1 to 19, Comparative Examples 1 to 6]
The blending amounts of each component were adjusted as shown in Tables 1 to 4, and the liquid detergents of Examples 1 to 19 and Comparative Examples 1 to 6 were prepared according to the following procedure.

Component (A) and water were mixed until uniform, then component (B) was added and the mixture was stirred until uniform, optional components were added, and the mixture was sufficiently stirred to obtain a liquid detergent.
In Tables 1 to 4, the blending amount (% by mass) of each component is the ratio to the total mass of the liquid detergent, and unless otherwise specified, the value is shown in terms of pure content. Ingredients whose blending amounts are not listed in the table are not blended.
"Appropriate amount" means that the pH adjuster is blended so that the pH of the liquid detergent at 25°C becomes the value shown in Tables 1-4. "Balanced" means that water is blended so that the total amount (% by mass) of all compounding components contained in the liquid detergent of each example is 100% by mass. That is, the blending amount of water is the remainder obtained by subtracting the total blending amount (in terms of pure content) of the blending components other than water from the total mass of the liquid cleaning agent.
The liquid detergent of each example was evaluated for detergency, permeability and softness by the methods described above. Results are shown in the table.

As shown in Tables 1-4, the liquid detergents of Examples 1-19 were excellent in detergency, permeability and flexibility.
Comparative Example 1 containing no component (A) was inferior in detergency and permeability.
Comparative Examples 2 and 3, in which the content of component (A) exceeded 20% by mass, were inferior in flexibility.
Comparative Examples 4 and 5, which did not contain the (Ax) component, were inferior in permeability.
Comparative Example 6 containing no component (B) was inferior in detergency, permeability and softness.

Claims (2)

1. A liquid detergent composition comprising component (A), which is a non-soap surfactant, and component (B), which is an ethylene oxide adduct of polyethyleneimine and has an average number of moles of ethylene oxide added of 8 to 15,
   The content of the component (A) is more than 0% by mass and 20% by mass or less with respect to the total mass of the liquid cleaning composition,
   A liquid detergent composition in which the component (A) contains a component (Ax), which is a compound represented by the following general formula (ax1).
   R ¹¹ —O—(R ¹² O) _n —H (ax1)
   In formula (ax1), R ¹¹ represents a branched C 12-16 alkyl group or a C 12-16 linear alkyl group, and when R ¹¹ is the linear alkyl group, the oxygen atom is , is attached to a secondary carbon atom in said linear alkyl group. R ¹² represents an alkylene group having 2 to 4 carbon atoms. Further, n represents the average number of repetitions of R ¹² O and is 3-10.
2. Furthermore, at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and (C) component, which is a water-soluble polymer having (poly)oxyalkylene units, according to claim 1 Liquid detergent composition.