RU2588123C2 - Liquid detergent composition - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to a liquid detergent composition for textile products. Described is a liquid detergent composition containing non-ionic surfactant (A), a cationic surfactant (B) and hydrogen peroxide (D) within certain intervals and water, where component (A) contains a non-ionic compound (A1) of formula (A1) in amount of 0.5 to 10 wt% of composition, weight ratio of an anionic surfactant (c1), different from a fatty acid or salt thereof, to component (B), (c1)/(B) ranges from 0 to 1, and composition has pH 3.0-7.0 at 20°C measured in accordance with standard JIS K3362:1998, section 8.3: R-O-(C₂H₄O)_x-H (A1), where R is a linear alkyl group containing 12 carbon atoms, and has a primary carbon atom where R is bound with oxygen atom of R-O-; and x is number of moles of bonded ethyleneoxy groups and has integer values in range from 2 to 5

where R^b1 represents a chain hydrocarbon group containing from 12 to 18 carbon atoms, and may include group -(A′O)_s-, where A′O represents ethyleneoxy group or propyleneoxy-group, and s is average number of moles A′O, located in range from 0 to 10; group R^b2, R^b3 and R^b4 each independently represents a methyl group, ethyl group, benzyl group or a hydroxyalkyl group containing 1-3 carbon atoms; and X^- is CH₃SO₄ ^-, CH₃CH₂SO₄ ^- or halogen-ion, and where component (A) contains at least one nonionic surfactant selected from surfactants of formulae (a1) and/or (a2), in amount of 10 to 60 wt%: R^1a-O-[(C₂H₄O)_p/(AO)_q]H (a1), where R^1a represents an alkyl or alkenyl group containing 8 to 22 carbon atoms, AO denotes alkyleneoxy-group containing 3-5 carbon atoms; p denotes average number of moles of bonded C₂H₄O-groups, located in range of 8-40; q denotes average number of moles of bonded AO groups located in range from 0 to 5; and “/” means that C₂H₄O-groups and AO group can be distributed or statistical connection, or block connection; R^2a(CO)₁O-[(C₂H₄O)_m/(AO)_n]R^21a (a2), where R^2a represents an alkyl or alkenyl group containing 8 to 22 carbon atoms; R^21a represents an alkyl group containing 1-3 carbon atoms; 1 denotes a number equal to 0 or 1; AO denotes alkyleneoxy-group containing 3-5 carbon atoms; m denotes average number of moles of bonded C₂H₄O-groups, located in range of 5-30; n is average number of moles of bonded AO groups located in range from 0 to 5; and “/” means that C₂H₄O-groups and AO groups can be distributed or statistical connection, or block connection.

EFFECT: providing detergent power, which suppresses onset of specific smell, due to wet-dry state textile articles.

13 cl, 4 tbl

Description

Technical field

The present invention relates to a liquid detergent composition for textiles, and, moreover, for clothing.

State of the art

The trend towards the creation of nuclear families is expanding the population with two working spouses. In a growing number of households, therefore, they are generally washed at night or on weekends, and laundry items are dried indoors. In addition, the growing awareness of energy saving recently creates a moment for the development of washing and drying machines with reduced energy losses. As a result, a new technology of drying at low temperature using the moisture absorption function of an air conditioner is proposed. However, drying indoors or at low temperatures tends to lead to the appearance of a musty odor such as the smell of a moist and dirty floor cloth.

There is also a change in approaches to washing. More precisely, there is an increasing tendency to use the presence of smell as a criterion for washing even in the absence of dirt or stains. The presence of a cigarette smell or body odor on a textile product after training is a common factor sufficient to create a feeling of a need for washing. Recently, even the presence or occurrence of a small odor has become a factor in the appearance of such a sensation. The appearance of a smell on a textile product due to a prolonged wet-dry (semi-dry) state during drying after washing is thus an undesirable condition. The mass awareness of an unpleasant odor due to a wet-dry state further increases with the dissemination of information about the relationship between bacterial growth and odor due to a wet-dry state. As used in this case, the definition of "wet-dry state" refers to the wet state of a textile product, in addition with a small amount of moisture. Specifically, the “wet-dry state” includes a wet state when a textile product is washed and hung under wet conditions without a dryer until the product is dry, and a wet state when a dry textile product is used to wipe wet hands or body, or which has been exposed to rain, or wet after swimming.

Various substances have been identified and identified as responsible for odor due to the wet-dry state. Specific examples of the substance include decomposition products from sebum secretion stains, such as metabolites formed by the growth of bacteria. Hanihara and Sonoda report that the smell due to the wet-dry state (the smell that appeared during drying in the room) is a complex odor, including the “musty smell of mold” of medium chain aldehydes, medium chain alcohols and ketones, the “smell of rotten eggs” of short chain fatty acids and medium chain fatty acids, the “fishy smell” of nitrogen compounds and the smell of sulfur compounds, in which medium chain fatty acids (Heyaboshi shuu wo yokusei suru senzai nituite (Detergents to control special odor arising from drying indoors), Koryo (fragrance), 2004, September, No. 223, p. 109-116). Takeuchi et al. Reports that a specific odor due to a wet-dry state on clothing includes a persistent odor of 4-methyl-3-hexenoic acid, which is one of the medium chain fatty acids (Irui no namagawaki shuu no kaiseki (Odor analysis due to a wet-dry state on clothing), Japan Society for Bioscience, Biotechnology and Agrochemistry, 2010, annual meeting Abstracts, p. 149. Publication JP-A-2009-244094 proposes the use of a medium chain fatty acid having a defined structure as an indicator for a specific smell due to importantly dry condition.

The odor due to wet drying in accordance with the present invention includes the odor arising when the textile product is dried indoors, the odor arising when the textile product is left as it is after water is squeezed, and the odor arising when the dry textile product is again wetted by sweat or rain. Smells that appear during drying indoors and when the product is left as it is can be eliminated or reduced by complete drying. However, the odor that comes back from time to time when the textile product is wetted again is difficult to eliminate, and after the textile product has an unpleasant odor, this smell is easily returned when the product is used, although the smell can be temporarily removed by washing and drying completely. The odor that comes back from time to time resembles the smell of accessories for cleaning the floor and furniture, such as a widely used rag and mop. Once arising, easily returning from time to time, the smell can occur even when drying in the open air and is difficult to eliminate.

A smell that comes back from time to time differs in that it appears slightly or does not appear on a textile product washed and completely dried, but occurs to a large extent when the product becomes wet. The odor that comes back from time to time due to the wet-dry state also easily appears during storage for a long time in a cabinet or similar place. After an odor that comes back from time to time, textiles that often come in contact with human skin and are often used for a short wash and use cycle, including underwear, handkerchiefs and towels, often emit a smell that comes back from time to time when used, and also tend to the appearance of a stronger odor with an increase in the number of washings.

To eliminate a specific smell or similar phenomena from a textile product, there are traditionally known methods, including masking the fragrance component and eliminating bacteria responsible for the odor by destroying or inhibiting the development of bacteria using a bactericide or antibacterial agent. For example, the publications JP-A2010-31285 and JP-A2007-314693 describe a masking method using a tissue treatment agent containing an alicyclic ketone compound as a perfume component or stabilizer for a perfume component. To eliminate odor by destroying or inhibiting the development of odor-causing bacteria with a bactericide or antibacterial agent, treatment with a diketone compound, a cationic organic antibacterial agent or a treatment agent containing a bactericide such as triclosan and dichlorosan is known. For example, JP-A2009-263812 discloses a method for controlling odor due to a wet-dry state using a bactericide. In addition, JP-A2008-173441 discloses the production of an inhibitor of a volatile sulfur compound containing a specific fragrance component and acting through the suppression of enzymes by the fragrance component.

Liquid bleaching agents comprising hydrogen peroxide, a cationic surfactant and a nonionic surfactant are also known. JP-A09-59675 discloses a liquid whitening composition comprising hydrogen peroxide, a nonionic surfactant having an HLB of 5 to 12, an anionic or cationic surfactant and perfume. Publications JP-A09-188895 and JP-A09-217090 also describe a liquid whitening composition comprising a nonionic surfactant and a cationic surfactant. Publications JP-A2007-169530 and JP-A2007-177145 disclose a liquid detergent composition containing hydrogen peroxide, a boron compound and a polyhydric alcohol, in which a boron compound and a polyhydric alcohol act to bring the pH of the aqueous dilution of the composition to alkalinity when diluted with water when applied, increasing the washing ability as a result.

JP-A2006-169515 discloses a liquid detergent composition comprising hydrogen peroxide, a boron compound, a hydroxy compound, a bleaching activator, a surfactant, and water. JP-A2007-106903 discloses a liquid whitening detergent composition comprising hydrogen peroxide, a boron compound, a hydroxy compound, a bleaching activator, a nonionic surfactant, and a quaternary ammonium salt. JP-A2010-059296 discloses a liquid detergent composition comprising hydrogen peroxide, acid and a surfactant. JP-A2011-063784 discloses a liquid detergent composition comprising a nonionic surfactant, an anionic surfactant, and a water miscible organic solvent. JP-A2010-265445 discloses a liquid detergent composition comprising a nonionic surfactant, an anionic surfactant, a cationic surfactant, and a water miscible organic solvent.

Publication JP-A2011-116932, published June 18, 2011, discloses a detergent composition for textiles containing a non-ionic surfactant and a cationic surfactant. Publication JP-A2011-168730, published September 1, 2011, discloses a surfactant composition comprising a nonionic surfactant and a nonionic compound. Publication JP-A2011-168731, published September 1, 2011, discloses a liquid detergent composition containing a nonionic surfactant, a hydrophobic organic solvent, and water. Publication JP-A2011-168732, published September 1, 2011, discloses a liquid detergent composition comprising a nonionic surfactant, a nonionic compound, a water soluble salt, and water. Publication JP-A2011-168733, published September 1, 2011, discloses a liquid detergent composition containing a nonionic surfactant, a cationic compound, a nonionic compound and water. Publication JP-A2011-168734, published September 1, 2911, discloses a liquid detergent composition containing a nonionic surfactant, hydrogen peroxide, hydrocarbon, organic acid and water. Publication JP-A2011-246585, published December 8, 2011, discloses a liquid detergent composition containing a surfactant, a hydrotropic agent, hydrogen peroxide, a water-miscible solvent and water.

SUMMARY OF THE INVENTION

The present invention relates to a liquid detergent composition comprising:

(A) a nonionic surfactant [hereinafter referred to as component (A)] in an amount of from 15 to 70% by weight,

(B) a cationic surfactant represented by the formula (B1) [hereinafter referred to as component (B)] in an amount of from 0.3 to 5% by weight,

(D) hydrogen peroxide [hereinafter referred to as component (D)] in an amount of from 0.3 to 10% by weight, and

water

where component (A) contains, at least in part, (A1) a non-ionic compound represented by formula (A1), in an amount of from 0.5 to 10% of the mass. composition

the mass ratio (c1) of an anionic surfactant other than a fatty acid or its salt to component (B), (C1) / (B) is from 0 to 1, and

the composition has a pH of from 3.0 to 7.0 at 20 ° C. as measured in accordance with JIS K3362: 1998, Section 8.3:

RO- (C ₂ H ₄ O) _x -H (A1),

where R is a linear alkyl group containing 12 carbon atoms and has a primary carbon atom in which R binds to the oxygen atom R-O-; and x represents the number of moles of attached ethyleneoxy groups and has integer values in the range from 2 to 5:

,

,

where R ^b1 represents a chain hydrocarbon group containing from 12 to 18 carbon atoms, and may have a group - (A′O) _s - in it, where A′O represents an ethyleneoxy group or a propyleneoxy group, and s means average the number of moles A′O, in the range from 0 to 10; the groups R ^b2 , R ^b3 and R ^b4 each independently represents a methyl group, an ethyl group, a benzyl group or a hydroxyalkyl group containing from 1 to 3 carbon atoms; and X ^- represents CH ₃ SO ₄ ^- or CH ₃ CH ₂ SO ₄ ^- or a halogen ion.

The present invention also relates to a method for washing a textile product using an aqueous solution of a liquid detergent composition of the present invention.

The present invention also relates to a method for cleaning a textile product, comprising the step of applying a liquid detergent composition to a textile product and preparing a soap foam using a detergent composition, wherein the detergent composition comprises:

(A) a nonionic surfactant [hereinafter referred to as component (A)] in an amount of from 15 to 70% by weight,

(B) a cationic surfactant represented by the formula (B1) [hereinafter referred to as component (B)], in an amount of from 0.3 to 5% by weight,

(D) hydrogen peroxide [hereinafter referred to as component (D)] in an amount of from 0.3 to 10% by weight, and

water

where component (A) contains (A1) a nonionic compound represented by the formula (A1) in an amount of from 0.5 to 10% by weight. composition

the mass ratio (c1) of an anionic surfactant other than a fatty acid or its salt to component (B), (C1) / (B) is from 0 to 1, and

the composition has a pH of from 3.0 to 7.0 at 20 ° C. as measured in accordance with JIS K3362: 1998, Section 8.3:

RO- (C ₂ H ₄ O) _x -H (A1),

where R is a linear alkyl group containing 12 carbon atoms and has a primary carbon atom in which R binds to the oxygen atom R-O-; and x means the attached number of moles of ethyleneoxy group and has an integer value in the range from 2 to 5:

,

,

where R ^b1 represents a chain hydrocarbon group containing from 12 to 18 carbon atoms, and may have a group - (A′O) _s - in it, where A′O represents an ethyleneoxy group or a propyleneoxy group, and s means average the number of moles attached A'O, in the range from 0 to 10; the groups R ^b2 , R ^b3 and R ^b4 each independently represents a methyl group, an ethyl group, a benzyl group or a hydroxyalkyl group containing from 1 to 3 carbon atoms; and X ^- represents CH ₃ SO ₄ ^- or CH ₃ CH ₂ SO ₄ ^- or a halogen ion.

The present invention also relates to the use of a liquid detergent composition for cleaning a textile product.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a liquid detergent composition that suppresses a specific odor due to the wet-dry state of a textile product, and then to a liquid detergent composition that has a high controlling effect against a musty odor such as the smell of a wet and dirty floor cloth, including a smell that comes back from time to time, when the product becomes wet from sweat, which is more difficult to eliminate than other odors due to the wet-damp state.

The present invention also provides a liquid detergent composition that is capable of visually assessing the presence of bacteria by forming a soap foam without deteriorating detergency, and a method of cleaning a textile article with a visual assessment.

Considering these problems, the applicants of the present invention studied specific odors due to the wet-dry state in terms of substances and bacteria causing the smell, and the mechanism of its occurrence, taking into account the method of washing and use of a textile product, and focused not only on the smell due to moisture a dry state that occurs when a textile product is left wet for a long time until it dries, and also returns from time to time and odor due to the wet-dry state that occurs when a laundered and fully dried textile product becomes wet. As a result, the applicants of the present invention unexpectedly found that the odor that comes back from time to time due to the wet-dry state of the textile product is caused by microorganisms, especially bacteria, that bacteria can survive or multiply on the textile product even after the textile product has been washed and dried until completely eliminating a musty odor such as the smell of a wet and dirty floor cloth and that a trace amount of the odor due to the wet-dry state is captured by the fibers by shki and released when the fabric article becomes wet or wet-dry, thus unnoticed after drying this smell is easily felt due to its low perception threshold. Applicants of the present invention have found that the main unpleasant odor of a recurring odor from time to time arises from the presence of branched medium chain fatty acids, including mainly 4-methyl-3-hexenoic acid, described above (hereinafter referred to as 4M3H). Applicants of the present invention have identified the causing bacteria generating 4M3H, which are Moraxella bacteria (Moraxella sp.), And found that this bacterium is insensitive to dehydration. From consideration of such facts, it is obvious that reliable, conventional elimination of odors after washing and drying does not directly mean that the odor that comes back from time to time due to the wet-dry state can also be effectively suppressed. For an accurate assessment of the effect on the odor that comes back from time to time due to the wet-dry state, it is necessary to consider the liquid detergent composition and evaluate from the point of view of establishing the cause of such results.

Based on the obtained data, the applicants of the present invention have developed a liquid detergent composition that is effective not only as a regular deodorant for odor due to a wet-dry state, but also as a deodorant of an odor that returns from time to time due to a wet-dry state, especially 4-methyl-3 odor -hexenoic acid.

The liquid detergent composition of the present invention has a deodorizing effect for odors due to the wet-dry state of the textile product, including the occasional smell arising when the dry textile product becomes wet again, and in particular 4M3H odor.

The liquid detergent composition of the present invention can make eye-catching the formation of soap foam in the presence of bacteria in a textile product when applied to a textile product, and therefore the use of the composition can be carried out to confirm the presence of bacteria.

Below, the liquid detergent composition of the present invention is described in more detail.

<Component (A)>

The liquid detergent composition of the present invention contains a component of non-ionic surfactant (A), which is the main surfactant.

Examples of the component of the nonionic surfactant (A) are surfactants containing a chain hydrocarbon group having from 8 to 22 carbon atoms in the molecule and a hydrophilic group such as an ethyleneoxy group and a hydroxy group. Specific examples include polyalkylene alkyl or alkenyl ethers containing an ethyleneoxy group as an alkyleneoxy group, polyoxyalkylene alkyl (more preferably 1 to 3 carbon atoms) fatty acid esters containing an ethyleneoxy group as an alkyleneoxy group, alkyl polyglycosides, alkyl glycosides, fatty acid sorbitan esters, fatty acid polyoxyethylene sorbitan esters, other polysaccharide surfactants, fatty acid monoglycerides, fatty alkanolamides acid, polyhydroxy fatty acid amides, polyglyceryl fatty acid esters and polyglycerol alkyl esters.

Particularly in terms of detergency and deodorizing effect, component (A) preferably contains at least one non-ionic surfactant selected from the following components (a1) to (a5), and more preferably a combination of non-ionic surfactant from (a1) or (a2) or non-ionic surfactants selected from (a1) and (a2), with a non-ionic surfactant selected from (a3). In terms of detergency, deodorizing effect and visual assessment of the presence of bacteria on a textile product through the formation of soap foam of the applied composition on a textile product (hereinafter referred to as visual assessment of the formation of soap foam), component (A) preferably contains a combination of non-ionic surfactants, selected from (a1) and (a3). The ability to form a soap foam through application can be attributed to a surfactant selected from (a1). A surfactant selected from (A1) more preferably has a PO group. Preferred conditions for surfactants (a1), (a2) and (a3) are described below.

(a1) Non-ionic surfactants based on polyoxyalkylene (alkyl or alkenyl) ether [hereinafter referred to as component (a1)], represented by formula (a1):

R ^1a —O [(C ₂ H ₄ O) _p / (AO) _q ] H (a1),

where R ^1a represents an alkyl or alkenyl group containing from 8 to 22 carbon atoms; AO means alkyleneoxy group containing from 3 to 5 carbon atoms; p means the average number of moles of attached C ₂ H ₄ O groups, ranging from 8 to 40; q means the average number of moles of attached AO groups, ranging from 0 to 5; and “/” means that C ₂ H ₄ O-groups and AO groups can be distributed either by statistical or block addition.

(a2) Non-ionic surfactants based on polyoxyalkylene (short chain fatty acid alkyl ester or aliphatic alkyl ester) [hereinafter referred to as component (a2)] represented by the formula (a2):

R ^2a (CO) _l O - [(C ₂ H ₄ O) _m / (AO) _n ] R ^21a (a2),

where R ^2a represents an alkyl or alkenyl group containing from 8 to 22 carbon atoms; R ^21a represents an alkyl group containing from 1 to 3 carbon atoms; l is the number 0 or 1; AO means alkyleneoxy group containing from 3 to 5 carbon atoms; m means the average number of moles of attached C ₂ H ₄ O groups, ranging from 5 to 30; n means the average number of moles of attached AO groups, ranging from 0 to 5; and “/” means that C ₂ H ₄ O-groups and AO groups can be distributed either statistically or in a block manner.

(a3) Non-ionic surfactants based on polyoxyethylene alkyl ether [hereinafter referred to as component (a3)] represented by the formula (a3):

R ^3a —O— (C ₂ H ₄ O) _r —H (a3),

where R ^3a represents an alkyl or alkenyl group containing from 8 to 22 carbon atoms and has a primary and / or secondary carbon atom in which R ^3a binds to the oxygen atom R ^3a —O—; and r means the average number of moles of attached C ₂ H ₄ O groups ranging from 2 to less than 8.

(a4) Nonionic surfactants based on the (alkyl or alkenyl) ether of polyglycerol [hereinafter referred to as component (a4)].

(a5) Polysaccharide surfactants [hereinafter referred to as component (a5)].

Preferred options for component (a1) are described below.

Component (A1) can be produced from a primary or secondary alcohol having an alkyl or alkenyl group, more preferably an alkyl group containing an alkyl group containing from 8 to 22 carbon atoms, more preferably from 10 to 18 carbon atoms, and even more preferably from 12 to 16 carbon atoms, by attaching ethylene oxide [hereinafter referred to as EO (EO)] and alkylene oxide containing from 3 to 5 carbon atoms for random or block addition. In formula (a1), R ^1a preferably has a primary and / or secondary carbon atom, more preferably a primary carbon atom in which R ^{1a is} attached to the oxygen atom R ^1a —O—, and preferably represents a linear alkyl group.

In the formula (a1), p is the average number of moles of attached ethyleneoxy groups (C ₂ H ₄ O, hereinafter also referred to as EO groups (EO)). From the point of view of water solubility and cleansing characteristics (washing ability), p ranges from 8 to 40, preferably from 10 to 40, more preferably from 14 to 35, and even more preferably from 16 to 30. The q value means the average number of moles affiliated AO groups. From the point of view of cleaning characteristics, q is in the range from 0 to 5, preferably from 1 to 5, more preferably from 1 to 4, and even more preferably from 1 to 3. In the case of q taking the value 0, p is preferably in the range from 18 up to 35 and more preferably in the range from 20 to 30.

In formula (A1), each AO group is introduced by the addition of an alkylene oxide containing from 3 to 5 carbon atoms, and preferably has a branched methyl, ethyl or propyl group at the junction. Each AO group is preferably an alkyleneoxy group containing 3 or 4 carbon atoms, and the AO groups may be the same or different. Specific examples of the AO group include a trimethyleneoxy group, an oxypropane-2,2-diyl, oxybutane-1,2-diyl, oxybutane-1,3-diyl, oxybutane-2,3-diyl and oxytetramethylene group. An oxypropane-1,2-diyl group (hereinafter also referred to as a propyleneoxy group or PO (PO) group) is more preferred.

From the point of view of storage stability at low temperature, cleaning characteristics and visual assessment of the formation of soap suds when used, the present invention preferably uses a non-ionic surfactant having the formula (a1) in which R ^1a is a linear alkyl group containing from 10 to 18 carbon atoms, more preferably from 12 to 16 carbon atoms, and having a primary carbon atom in which the group R ^1a joins the oxygen atom R ^1a -O-; p denotes the average number of moles of attached EO groups, ranging from 14 to 35, and more preferably from 16 to 30; AO group is a propyleneoxy group; and q is an average number of moles of attached AO groups ranging from 1 to 4, more preferably from 1 to 3, and even more preferably from 2 to 3 [hereinafter referred to as non-ionic surfactant (a1 ′)]. The nonionic compound represented by formula (A1) is highly hydrophobic. However, by combining a nonionic surfactant that has many ethyleneoxy groups and is hydrophilic, the nonionic compound represented by formula (A1) can be stably incorporated into the composition, providing the effects of the present invention. In addition, the presence of a propyleneoxy group in the non-ionic surfactant contributes to greater stabilization and higher detergency of the liquid detergent composition, and the composition easily makes foam more visible in the presence of bacteria, while quickly eliminating the foam, and additionally has good penetration into fibers. For these reasons, the present invention in component (A) preferably contains a non-ionic surfactant (A1 ′).

In the formula (a1), “/” means that component (a1) of the present invention has EO groups and AO groups distributed either by statistical or block addition. AO groups can be distributed in a large number of divided blocks.

Examples of a nonionic surfactant represented by the formula (a1) are surfactants represented by the formulas (a1-1) to (a1-6):

R ^1a O- (AO) _q - (C ₂ H ₄ O) _p H (a1-1) R ^1a O- (C ₂ H ₄ O) _p - (AO) _q H (a1-2) R ^1a O - [(C ₂ H ₄ O) _p11 ● (AO) _q ] - (C ₂ H ₄ O) _p12 H (a1-3) R ^1a O- (C ₂ H ₄ O) _p11 - [(AO) _q ● (C ₂ H ₄ O) _p12 ] N (a1-4) R ^1a O- (C ₂ H ₄ O) _p11 - (AO) _q - (C ₂ H ₄ O) _p12 H (a1-5) R ^1a O- (C ₂ H ₄ O) _p11 - [(AO) _q ● (C ₂ H ₄ O) _p13 ] - (C ₂ H ₄ O) _p12 N (a1-6),

where R ^1a , p, q and AO take the same values as defined above; p11, p12 and p13 each represents the average number of moles of attached C ₂ H ₄ O groups, excluding 0, provided that p = p11 + p12 + p13 or p = p11 + p12; and “●” means that the groups are distributed in a statistical join.

Non-ionic surfactants represented by formulas (a1-1) to (a1-6) can be obtained from R ^1a OH by reactions with alkylene oxides taking into account the proportions of the reactants and the reaction order. In formulas (a1-1) to (a1-6), the average number of moles of each alkyleneoxy group attached may be the number of moles of each alkylene oxide used per mole of R ^1a OH in the reaction, or the average number of moles of each of the alkylene oxide groups in the resulting compound. Independently of each other, p11 and p12 are preferably equal to from 1 to 20. More preferably p11 has values from 3 to 20 and even more preferably from 4 to 15. More preferably p12 takes values from 1 to 15 and even more preferably from 3 to 15. Preferably p13 is a number from 0.1 to 10. The corresponding intervals p11, p12 and p13 will depend on the intervals or preferred intervals p and q in the formula (a1). Formulas (a1-1) to (a1-6) are more preferably defined as being subordinate to nonionic surfactants (a1 ′).

As described above, the group R ^1a in the formula (a1) can be obtained from alcohol made from natural fats and oils. From the point of view of storage stability, a nonionic surfactant represented by the formula (a1-2), (a1-4), (a1-5) or (a1-6), more preferably the formula (a1-5) or ( A1-6) and even more preferably the formula (A1-5).

Component (a1) of the present invention can be produced, for example, by reacting R ^1a OH with an alkylene oxide containing from 3 to 5 carbon atoms and ethylene oxide so as to obtain the intended structure represented by formulas (a1-1) to (a1-6) . The reaction conditions and the order of addition can be planned as preferred for the intended structure, including statistical location or block location. The reaction proportions of alkylene oxide containing from 3 to 5 carbon atoms and ethylene oxide per mole of R ^1a OH can be in the ranges p and q described for formula (1), or p = from 8 to 40 and q = from 0 to 5, respectively or as satisfying p = p11 + p12 + p13 or p = p11 + p12, or within the preferred ranges described above. In other words, alkylene oxide having from 3 to 5 carbon atoms and ethylene oxide can be reacted with an aliphatic alcohol in any proportions within the ranges of p and q, p11, p12 and p13.

In general, the corresponding proportions of ethylene oxide and propylene oxide introduced into the reaction per mole of R ^1a OH are substantially equal to the average number of moles of the corresponding alkylene oxide groups in the corresponding formulas described above. However, in the present invention, they may be different depending on the production method.

Component (A1) of the present invention is more preferably a non-ionic surfactant represented by the formula (A1-5) or (A1-6), more preferably the formula (A1-5) and even more preferably the formula (A1-5), which p11 / (p11 + p12) is in the range from 0.2 to 0.8.

Component (a1) having p11, p12, p13 and q within narrower ranges can be produced under more preferred manufacturing conditions using a method comprising the following steps A to D:

stage A: the addition of ethylene oxide to R ^1a OH in a proportion of 4 to 14 moles and preferably from 8 to 12 moles (the range of moles can be used as designation p11 in the formula) per mole of R ^1a OH;

stage B: then the addition of propylene oxide in a proportion of 1 to 3 moles and preferably from 2 to 3 moles (the mole range can be used as q in the formula) and ethylene oxide in a proportion of 0 to 4 moles (the mole range can be used as p13 in the formula) for statistical or block addition, it is more preferable to attach only propylene oxide in a proportion of 2 to 3 moles (the interval of moles can be used as the designation n in the formula);

stage C: again the addition of ethylene oxide in a proportion of from 4 to 14 moles and preferably from 8 to 12 moles (the range of moles can be used as the designation p12 in the formula);

and

stage D: processing of the catalyst used in the reaction. Examples of the treatment include neutralizing the alkaline catalyst with an acid and filtering the solid catalyst.

The p, q values and similar values in component (a1) can be determined by NMR, liquid chromatography, or similar methods. In the case of compounds having a short chain of alkyleneoxy groups, such as the reaction product between 1 mole of a linear linear alcohol having an alkyl group and less than 8 moles of ethylene oxide, gas chromatography can be used. In the present invention, p and q and similar values can also be proportions of alkylene oxide containing from 3 to 5 carbon atoms and ethylene oxide reacted with 1 mole of R ^1a OH.

A preferred embodiment of component (a2) is described below.

In formula (a2), component (a2) R ^2a represents an alkyl or alkenyl group containing from 2 to 22 carbon atoms, preferably from 10 to 18 carbon atoms, more preferably from 12 to 14 carbon atoms and even more preferably a linear alkyl group, containing from 12 to 14 carbon atoms. The group R ^21a represents an alkyl group containing from 1 to 3 carbon atoms, and preferably a methyl group. The exponent l represents the number 0 or 1, more preferably 1. AO represents an alkyleneoxy group containing from 3 to 5 carbon atoms. Each AO group is introduced by the addition of an alkylene oxide containing from 3 to 5 carbon atoms, and preferably has a branched methyl, ethyl or propyl group at the binding site. Each AO group is preferably an alkyleneoxy group containing 3 or 4 carbon atoms, and the AO groups may be the same or different from each other. Specific examples of the AO group are a trimethyleneoxy group, an oxypropane-1,2-diyl group, an oxybutane-1,2-diyl group, an oxybutane-1,3-diyl group, an oxybutane-2,3-diyl group and an oxytetramethylene group. Of these, an oxypropane-1,2-diyl group (hereinafter also referred to as a propyleneoxy group or a PO (PO) group) is more preferred as an AO group. The indicator m means the average number of moles of attached C ₂ H ₄ O-groups, ranging from 5 to 30, more preferably from 8 to 25, and even more preferably from 10 to 20. The indicator n means the average number of moles of attached AO groups, located in the range from 0 to 5, and more preferably from 0 to 3.

In cases of n satisfying the condition 0 <n≤3, and more preferably n in the range from 0.5 to 3, the nonionic surfactant represented by the formula (a2) is preferably represented by the formula (a2-1), (a2 -2) or (A2-3), and more preferably formula (A2-2), from the point of view of stability during storage of the liquid. Preferably, the AO is an oxypropane-1,2-diyl group (hereinafter also referred to as a propyleneoxy group or a PO (PO) group). Preferably m is in the range from 5 to 30, more preferably from 8 to 25, and even more preferably from 10 to 20. In cases of formula (a2-3), m is preferably in the range from 10 to 30.

R ^2a (CO) O- (AO) _n - (C ₂ H ₄ O) _m -CH ₃ (a2-1) R ^2a (CO) O- (C ₂ H ₄ O) _n - (AO) _m -CH ₃ (a2-2) R ^2a (CO) O- (C ₂ H ₄ O) _m -CH ₃ (a2-3).

A preferred embodiment of component (a3) is described below.

In formula (a3), component (a3) R ^3a represents an alkyl or alkenyl group containing from 8 to 22 carbon atoms, preferably from 10 to 18 carbon atoms, more preferably from 12 to 14 carbon atoms, and even more preferably a linear alkyl group, containing from 12 to 14 carbon atoms. The R ^3a group has a primary and / or secondary carbon atom in which R ^3a binds to the oxygen atom R ^3a —O—. In the present invention, certain alkyl or alkenyl groups having a secondary carbon atom may also be called a linear group that is different from a branched hydrocarbon group. Index r represents the average number of moles of attached ethyleneoxy groups ranging from 2 or more and less than 8, preferably from 2.5 to 7.5, and more preferably from 3 to 7.

In a method for producing a non-ionic surfactant having a primary carbon atom in which R ^3a binds to an oxygen atom, ethylene oxide is attached to the primary alcohol. A non-ionic surfactant having a secondary carbon atom in which R ^3a binds to an oxygen atom can be produced by any known method, for example, by attaching ethylene oxide to a secondary alcohol, reacting a 1-olefin or internal olefin with ethylene oxide, reacting an olefin with polyethylene glycol or by introducing a hydroxy group into n-paraffin and adding ethylene oxide.

A preferred embodiment of component (a4) is described below.

Component (a4) preferably contains a compound represented by formula (a4):

R ^4a —O - [(AO) _s / (Gly) _t ] -H (a4),

where R ^4a represents an alkyl or alkenyl group containing from 8 to 22 carbon atoms; AO is an ethyleneoxy group or a propyleneoxy group; Gly is a residual group derived from glycerol; s means the average number of moles of attached AO groups, ranging from 0 to 5; t means the average number of moles of attached Gly groups, ranging from 2 to 10; and “/” means that AO groups and Gly groups can be distributed by statistical or block joining.

In the formula (a4), the number of carbon atoms in R ^4a is preferably from 12 to 16 or more, preferably 12 or 14. The group R ^{4a is} preferably a linear alkyl group and more preferably a linear alkyl group having a primary carbon atom in which R ^4a binds with an oxygen atom R ^4a —O—. Preferably, s is 0, and t is the average number of moles and is preferably in the range of 2 to 5.

The compound represented by formula (a4) may be a mixture of compounds having s having the value 0 and different values of t ′ representing the number of moles of attached Gly groups (integer). In this case, the mixture preferably contains at least one, more preferably two or more compounds having t ′ taking the value 3, 4 or 5. In the mixture, the total proportion of compounds having t ′ taking the value 3, 4 or 5, preferably is not less than 40% of the mass., more preferably not less than 60% of the mass. and even more preferably not less than 80% of the mass. From the point of view of cleaning characteristics at low temperature, the total fraction is preferably not more than 99% by mass, more preferably not more than 90% by mass. and even more preferably not more than 85% of the mass. In the mixture, the proportion of compounds having t ′ having a value of 1 or 2 is preferably less than 50% of the mass. and more preferably less than 35% of the mass.

A preferred embodiment of compound (a5) is described below.

Compound (a5) includes a polysaccharide surfactant represented by formula (a5):

R ^5a - (OR ^51a ) _x Z _y (a5),

where R ^5a represents an alkyl or alkenyl group containing from 8 to 18 carbon atoms; R ^51a represents an alkylene group containing from 2 to 4 carbon atoms; Z represents a residual group formed from a reducing sugar containing 5 or 6 carbon atoms; x is the number of moles of attached OR ^51a groups, ranging from 0 to 6; and y means an average degree of condensation in the range of 1 to 10.

In the formula (a5), the number of carbon atoms in R ^{5a is} preferably from 12 to 16 and more preferably 12 or 14. Preferably R ^5a is a linear alkyl group and more preferably a linear alkyl group containing a primary carbon atom in which R ^5a binds to an oxygen atom R ^5a —O—. Preferably x is 0. Preferably z is a glucose residue. Preferably, y is an average degree of condensation ranging from 1.2 to 3. The compound represented by formula (a5) may be a mixture of compounds having different y values representing an integer of the degree of condensation Z. In this case, the mixture preferably contains, by at least one, more preferably two or more compounds having x taking the value 0, and y ′ taking the value 1, 2 or 3. In the mixture, the total proportion of compounds having y ′ taking the value 1, 2 or 3, preferably is less than 60% of the mass. and more preferably not less than 80% of the mass.

The liquid detergent composition of the present invention contains a non-ionic compound represented by the formula (A1) [hereinafter also referred to as component (A1)] in component (A):

RO- (C ₂ H ₄ O) _x -H (A1)

where R is a linear alkyl group containing 12 carbon atoms and has a primary carbon atom in which R binds to the oxygen atom R-O-; and x is the number of moles of attached ethyleneoxy groups and is an integer ranging from 2 to 5.

In order to achieve the present invention, it is important that in formula (A1) the R group is represented by a linear alkyl group containing 12 carbon atoms and has a primary carbon atom in which the hydrocarbon group of the alkyl group binds to an oxygen atom. The component of the nonionic compound (A1) can exhibit, together with the component of the cationic surfactant (B), a deodorizing effect on odors due to the wet-dry state, consisting mainly of 4M3H odor, on a textile product, which are difficult to eliminate in the usual area, and further inhibits the occurrence of a recurring odor from time to time due to the wet-dry state. Component (A1) is preferably represented by formula (A1), in which x is 3, 4 or 5, since the compound containing 3, 4 and 5 EO groups exhibits a more reliable deodorizing effect on odors due to the wet-dry state, especially returning occasionally odor due to wet-dry condition. In component (A1), the total proportion of compounds represented by formula (A1), in which x is 3, 4 or 5, is preferably from 70 to 100% by weight. and more preferably from 80 to 100% of the mass.

A compound having one mole of ethyleneoxy group may be mixed as component (A1). A mixture of polyoxyethylene alkyl esters having a different number of moles of ethyleneoxy groups, produced or commercially available, can be mixed as a non-ionic surfactant. From an economic point of view, in the production of component (A1) can be obtained from component (A1) or (A3). In cases where component (a3) is prepared, component (a3) has the formula (a3) in which R ^3a is a linear alkyl group containing 12 carbon atoms and has a primary carbon atom in which R ^3a binds to the oxygen atom R ^3a - ABOUT-. In this case, as a non-ionic surfactant containing component (A1), the composition of the present invention preferably contains a non-ionic surfactant represented by formula (a3), for example, produced by the addition of ethylene oxide with an average amount of not less than 2 mol to less than 8 moles to lauryl alcohol in the presence of an alkaline or acidic catalyst. In this case, component (a3) is a mixed product containing polyoxyethylene lauryl ethers having a different number of moles of ethyleneoxy groups, including component (A1). The content of the compound corresponding to the component (A1) in the component (a3) must be confirmed, and the component (a3) must be mixed in a correction amount in accordance with the contents of the component (A) and (A1) in the composition.

Depending on the production methods, in some production methods, component (A1) may be present in a small amount in component (A1) in which q is 0 and the group R ^{1a is} derived from lauryl alcohol (representing a lauryl group). Therefore, the content of the compound corresponding to component (A1) in component (A1) should be confirmed taking into account the structure and method of production of component (A1), and component (A1) should be mixed in an appropriate amount in accordance with the contents of component (A) and component ( A1) in the composition. In the cases of component (a1) in which q has a value of not less than 1, and in addition, AO contains a propyleneoxy group, the composition contains almost no component (A1) obtained from component (a1).

Component (A1) may be component (a3). For example, in the case of component (a3), the content of compounds in which R ^3a is a linear alkyl group containing 12 carbon atoms and contains a primary carbon atom on which R ^3a binds to the oxygen atom R ^a3 -O- and has one number moles of non-distributed ethyleneoxy groups, the average number of moles of added ethyleneoxy groups may be 2, 3, 4 or 5. Accordingly, component (a3) can also serve as component (A1). Component (a3) thus may contain component (A1). Component (A1) may contain two or more different compounds together.

In cases of mixing component (A1) as a component in component (a3), such component (a3) is produced by adding ethylene oxide in a small molar ratio, and therefore it is available as a mixture with unreacted alcohol. If unreacted alcohol causes an odor or affects the storage stability of the product, the alcohol can be removed by distillation or the like.

In the present invention, the proportion of unreacted alcohol and a compound having one mole of EO groups, or an aliphatic alcohol having a hydrocarbon group containing from 8 to 12 carbon atoms, and a compound produced from alcohol by the addition of one mole of EO groups, in the nonionic surfactant component substance (A) is preferably not more than 10 wt. -%, more preferably not more than 5% of the mass. and even more preferably not more than 3% of the mass. The lower limit is determined taking into account the energy required for distillation, and environmental load.

For a deodorizing effect on odors due to the wet-dry state, especially 4M3H odor, on a textile product, the liquid detergent composition of the present invention contains a nonionic compound component (A1) in an amount of from 0.5 to 10% by weight, preferably from 1 to 8% by weight. and more preferably from 2 to 5% of the mass. Component (A1) forms part of the non-ionic surfactant component (A).

From the point of view of detergency, the liquid detergent composition of the present invention contains a component of non-ionic surfactant (A) in an amount of from 15 to 70% by weight, preferably from 20 to 65% by weight, more preferably from 25 to 60% by weight. and even more preferably from 30 to 55% of the mass. This amount of component (A) contains a certain amount of component (A1) in component (A).

For components (a1) to (a5) and more preferably components (a1) to (a3), presented as an example of a non-ionic surfactant, the total proportion of these components in component (A) is preferably from 50 to 100% of the mass ., more preferably from 60 to 100% of the mass. and even more preferably from 80 to 100% of the mass. Of these components, component (A1) and / or component (A2), more preferably component (A1), preferably serve as the main non-ionic surfactant. From the point of view of washing ability and from the point of view of visual assessment of the formation of soap suds when used, the liquid detergent composition of the present invention preferably contains component (a1) and / or component (a2), more preferably component (a1) in an amount of from 10 to 60% of the mass. , more preferably from 15 to 55% of the mass. and even more preferably from 20 to 50% of the mass. From the point of view of the deodorizing effect and stability of the liquid, the liquid detergent composition of the present invention preferably contains component (a3) in an amount of from 0.5 to 20% by weight, more preferably from 1 to 18% by weight. and even more preferably from 2 to 15% of the mass.

In order to reliably incorporate components (A1) and (B) and fully achieve a detergency and deodorizing effect on odors due to a wet-wet state, the liquid detergent composition of the present invention contains components (A) and (A) satisfying at least one of the following conditions from (1) to (8).

Condition (1): The content of component (A) is from 20 to 65% of the mass. and preferably from 25 to 60% of the mass. liquid detergent composition.

Condition (2): The content of component (A1) is from 1 to 8% of the mass. and preferably from 2 to 5% of the mass. liquid detergent composition.

Condition (3): Component (A) contains component (a1).

Condition (4): Component (A) contains component (A1) represented by formula (A1), more preferably formula (A1-5), in which R ^1a represents an alkyl group containing from 12 to 16 carbon atoms and has a primary a carbon atom in which R ^1a binds to an oxygen atom R ^1a —O—; AO is a propyleneoxy group; and p = from 14 to 35 (in cases of the formula (a1-5), in addition, p11 = from 1 to 20 and p12 = from 1 to 20); q = 1 to 3.

Condition (5): The content of component (a1) is from 15 to 55% of the mass. and preferably from 20 to 50% of the mass. liquid detergent composition.

Condition (6): Component (A) contains component (a3).

Condition (7): Component (A) contains component (a3) represented by formula (a3), in which R ^a3 is a linear alkyl group containing from 12 to 14 carbon atoms and has a primary carbon atom in which R ^3a combines with an oxygen atom R ^a3 —O—; and r is a number from 3 to 7.

Condition (8): The content of component (a3) is from 1 to 18% of the mass. and preferably from 2 to 15% of the mass. liquid detergent composition.

Given these conditions, the liquid detergent composition of the present invention preferably contains component (A) in an amount of from 20 to 60% by weight, more preferably from 25 to 55% by weight, component (A1) in an amount of from 1 to 8% by weight, more preferably from 2 to 5 wt. -%, component (A1) as component (A), which is represented by formula (A1), more preferably formula (A1-5), in which R ^1a represents an alkyl group containing from 12 to 16 carbon atoms and has a primary carbon atom, in which R ^1a is bound to an oxygen atom -O-, R ^1a, AO meaning is a propyleneoxy group, and p = from 14 to 35 (in cases of formula (a1-5), in addition, p11 = from 1 to 20 and p12 = from 1 to 20), and q = from 1 to 3, in the amount from 15 to 55 wt. -%, more preferably from 20 to 50 wt. -%, and component (a3) in component (A), which is represented by formula (a3), in which R ^a3 represents a linear alkyl group containing from 12 to 14 carbon atoms, and has a primary carbon atom in which R ^3a binds to an oxygen atom R ^a3 —O—, and r is a number from 3 to 7, in an amount of from 1 to 18% by weight, more preferably from 2 to 15 % of the mass.

Component (A1) can be obtained from component (a1), as well as from component (a3). The respective components satisfy the structural conditions described above in their preferred embodiments. The intervals of each concentration and the total concentration of nonionic surfactants in the subordinate category, as required, should only be in the concentration range of component (A) of the higher order category. Preferred concentration ranges may be combined.

The conditions (1) to (8) and the preferred conditions described above are also preferable from the point of view of visual assessment of the formation of soap suds when applied.

<Component B>

The liquid detergent composition of the present invention contains a cationic surfactant component (B) represented by the formula (B1):

,

,

where R ^b1 represents a chain hydrocarbon group containing from 12 to 18 carbon atoms, and may have a group - (A′O) _s - in it, where A′O represents an ethyleneoxy or propyleneoxy group, and s means the average number moles of attached A'O groups, ranging from 0 to 10; R ^b2 , R ^b3 and R ^b4 each independently represents a methyl group, an ethyl group, a benzyl group or a hydroxyalkyl group containing from 1 to 3 carbon atoms; and X ^- represents CH ₃ SO ₄ ^- or CH ₃ CH ₂ SO ₄ ^- , or a halogen ion.

In the formula (B1), the group R ^b1 preferably contains from 14 to 18 carbon atoms and more preferably from 14 to 16 carbon atoms. The chain hydrocarbon group R ^b1 represents a hydrocarbon group, with the exception of a benzene ring or a cyclic group. The chain hydrocarbon group is preferably a linear alkyl or alkenyl group and, moreover, is preferably derived from natural fats and oils. Preferably s is 0.

In the formula (B1), X ^- represents the counterion of component (B) and preferably represents CH ₃ SO ₄ ^- or CH ₃ CH ₂ SO ₄ ^- in order to fully achieve the deodorizing effect on odors.

Component (B) may contain a non-ionic surfactant selected from the following compounds (b1) to (b4) and more preferably from compounds (b1) and (b3). The proportion of compound (b1) is preferably not less than 50 wt%, more preferably not less than 60 wt%. and even more preferably not less than 80% of the mass. component (B). Compounds (b1) to (b4) preferably have an R ^b1 group containing from 12 to 16 carbon atoms, and more preferably from 14 to 16 carbon atoms. The hydrocarbon chain group R ^{b1 is} preferably a linear alkyl group, and, in addition, is preferably derived from natural fats and oils. The counterion is preferably CH ₃ SO ₄ ^- or CH ₃ CH ₂ SO ₄ ^- .

(b1) Quaternary ammonium salts represented by the formula (B1), in which R ^b1 represents a linear alkyl group containing from 12 to 18 carbon atoms, and the groups R ^b2 -R ^b4 each represent a methyl group or ethyl group.

(b2) Quaternary ammonium salts represented by the formula (B1), in which R ^b1 represents a branched alkyl group containing from 12 to 18 carbon atoms, and R ^b2 —R ^b4 groups each represent a methyl group or ethyl group.

(b3) Quaternary ammonium salts represented by the formula (B1), in which R ^b1 represents a linear alkyl group containing from 12 to 18 carbon atoms, and the groups R ^b3 and R ^b4 each represent a methyl group or an ethyl group.

(b4) Quaternary ammonium salts represented by the formula (B1), in which R ^b1 is a linear alkyl group containing from 12 to 18 carbon atoms, s is in the range from 1 to 5, and the groups R ^b2 , R ^b3 and R ^b4 each represents a methyl group or an ethyl group.

The cationic surfactant component (B) can work together with the non-ionic compound (A1) to inhibit the reproduction of the resistant to drying which causes the smell of bacteria on the textile product. In other words, the combination exhibits a remarkable suppressive effect with respect to, along with odors due to the wet-dry state, the odor returning from time to time due to the wet-dry state on the textile product, when the product is completely dried and then becomes wet again. The combination effectively suppresses the odor of medium chain fatty acids, consisting predominantly of 4-methyl-3-hexenoic acid.

From the point of view of the deodorizing effect on odors due to the wet-dry state, especially on the smell of 4M3H, and the washing ability, the liquid washing composition of the present invention contains component (B) in an amount of from 0.3 to 5% by weight, preferably from 0.3 to 4 % wt., more preferably from 0.5 to 3% of the mass. and even more preferably from 0.8 to 3% of the mass.

<Component C>

A nonionic surfactant (A) containing a nonionic compound (A1) and a cationic surfactant (B) are essential components in the liquid detergent composition of the present invention. However, the composition additionally, under certain conditions, may contain (C) another surfactant, such as an anionic surfactant or amphoteric surfactant [hereinafter referred to as component (C)].

Anionic surfactants other than fatty acid based surfactants or their salts can reduce the deodorizing effect of the liquid detergent composition of the present invention. Therefore, surfactants based on fatty acids and their salts are described separately from other anionic surfactants. In cases of a liquid detergent composition of the present invention having an acidic pH, some surfactants may be present in the form of an acid in the composition. Such acidic compounds should also be included in surfactants.

(c1) Anionic surfactants other than surfactants based on fatty acids or their salts

Specific examples of another anionic surfactant include:

(c1-1) alkylbenzenesulfonates which have an alkyl group containing on average 10 to 20 carbon atoms;

(c1-2) polyoxyalkylene alkyl ether sulfate ester salts which have an alkyl group derived from a linear primary or secondary alcohol or from a branched alcohol, and this group contains an average of 10 to 20 carbon atoms, and an average alkyleneoxy group of 1 to 5 moles in which alkyleneoxy groups include ethyleneoxy groups and may contain propyleneoxy groups in an average amount of 0.2 to 2 moles;

(c1-3) salts of alkyl or alkenyl sulfate esters which have an alkyl or alkenyl group containing on average 10 to 20 carbon atoms; and

(c1-4) carboxylates of polyoxyacylene alkyl ethers which have an alkyl group derived from a linear primary or secondary alcohol or from a branched alcohol, and this group contains on average 10 to 20 carbon atoms, and alkyleneoxy groups on average 1 to 5 moles in which alkyleneoxy groups include an ethyleneoxy group and may contain a propyleneoxy group in an average amount of 0.2 to 2 moles.

From the point of view of the deodorizing effect on odors due to the wet-dry state, the salt is preferably selected from alkali metal salts such as sodium and potassium salts.

In the present description, whitening activators containing an anionic group, more preferably alkanoyloxybenzenesulfonic acid, alkanoyloxybenzoic acid or an alkali metal salt thereof having a linear or branched alkyl group containing from 8 to 22 carbon atoms, are included in another anionic surfactant (c1).

(c2) Surfactants based on fatty acids and their salts

Surfactants based on fatty acids and their salts contain from 10 to 18 carbon atoms and can be obtained from natural fats and oils with a fatty acid distribution. Fatty acid surfactants and their salts in the liquid detergent composition of the present invention can be mixed as a foam suppressant. The salt is preferably selected from alkali metal salts such as sodium salt or potassium salt.

(c3) Amphoteric surfactants

Examples of amphoteric surfactants include sulfobetaine and carbobetaine having an alkyl group containing from 8 to 22 carbon atoms, amidopropyl (or hydroxypropyl) betaine fatty acids and amidopropyl (or hydroxypropyl) carbobetaine fatty acids having an alkyl group containing from 7 to 21 carbon atom.

(c4) Cationic surfactants other than component (B)

Examples of a cationic surfactant other than component (B) include quaternary ammonium compounds and amine compounds other than component (B), such as amidopropyl dimethyl amines of fatty acids containing from 7 to 21 carbon atoms.

Another anionic surfactant (C1) reduces the bactericidal effect of the combination of components (A1) and (B), and therefore, it is added in a limited amount to fully achieve the deodorizing effect on odors due to the wet-dry state on the textile product. More specifically, the weight ratio of the other anionic surfactant (c1) to the cationic surfactant (B), (c1) / (B) is from 0 to 1, preferably from 0 to 0.8, more preferably from 0 up to 0.5 and even more preferably from 0 to 0.1. As described above, whitening activators having an anionic group are included in another anionic surfactant (C1). Thus, the proportion of the whitening activator is preferably low. The mass of another anionic surfactant (C1) is calculated based on its acid form. Within the mass ratio (s1) / (B), the content of the anionic surfactant (s1) other than fatty acids and their salts is preferably not more than 5% by weight, more preferably not more than 3% by weight, even more preferably not more than 2% of the mass. and even more preferably not more than 0.4% of the mass. liquid detergent composition.

An amphoteric surfactant can be added within a range that does not affect the present invention, but preferably within a range such that the mass ratio [(c1) + (c3)] / (B) falls within the range of the mass ratio ( c1) / (B). In accordance with the mass ratio [(c1) + (c3)] / (B), the content of component (c3) is preferably not more than 5% by mass, more preferably not more than 3% by mass. and even more preferably not more than 1% of the mass.

The content of component (c2) selected from fatty acids and their salts is from 0.05 to 5 wt., Preferably from 0.1 to 4% of the mass. and more preferably from 0.1 to 3% of the mass. compositions calculated on the basis of a fatty acid form (acid form). In the composition, some salts of the fatty acid may be present in the form of acid t in accordance with the pH. From the point of view of the deodorizing effect on odors due to the wet-dry state, alkali metal salts such as sodium salt or potassium salt are preferred.

<Component D>

The liquid detergent composition of the present invention contains hydrogen peroxide as component (D) to suppress odors due to a wet-dry state. The present invention uses a non-ionic compound (A1), a cationic surfactant (B) and hydrogen peroxide (D) under certain conditions to obtain a deodorizing effect on the entire textile product, including the occasional smell due to the wet-dry state, which is usually not being solved sufficiently.

From the point of view of the deodorizing effect on odors due to the wet-dry state and stability of hydrogen peroxide, the liquid detergent composition of the present invention contains component (D) in an amount of from 0.3 to 10% by weight, preferably from 0.5 to 8% by weight. and more preferably from 1 to 6% of the mass. The concentration of hydrogen peroxide in the composition can be determined by back titration with a solution of potassium iodide.

<Other components>

Other components that may be used in the present invention are described below.

[Component (E)]

The liquid detergent composition of the present invention preferably contains a water miscible organic solvent as component (E). As used in this case, a water-miscible organic solvent refers to a solvent that dissolves in an amount of not less than 50 g in 1 liter of ion-exchanged water at 25 ° C. or has a solubility in water of not less than 50 g / l.

Component (E) is preferably selected from water-miscible organic solvents having a hydroxyl group and / or an ether group.

Examples of a water miscible organic solvent include:

(e1) alkanols such as ethanol, 1-propanol, 2-propanol and 1-butanol;

(e2) glycols such as propylene glycol, butylene glycol and hexylene glycol;

(e3) glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and tripropylene glycol;

(e4) alkyl ethers, such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, monomethyl ether-dipropylene glycol, mono-1-methylethyl ether-1-monoethyl ether-1-monomethyl ether ethoxy-2-propanol, 1-methyl glycerol ether, 2-methyl glycerol ether, 1,3-dimethyl glycerol ether, 1-ethyl glycerol ether, 1,3-glycerol diethyl ether, glycerol triethyl ether, 1-pentyl th glycerol ether, 2-pentyl ester of glycerol, 1-octyl glyceryl ether, 2-ethylhexyl glyceryl ether and diethylene glycol monobutyl ether.

(e5) aromatic ethers such as 2-phenoxy-ethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, phenoxypropylene glycol, 2-benzyloxyethanol and diethylene monobenzyl ether.

Component (E) in the composition may serve as a viscosity adjusting agent and / or gelatinization preventing agent. Component (E) is preferably at least one compound selected from (e1) alkanols, (e2) glycols, (e4) alkyl ethers and (e5) aromatic ethers, and more preferably (e2) glycols, ( e4) alkyl ethers and (e5) aromatic ethers, to effectively control the viscosity and / or suppress gelation of the composition.

For reliable introduction of hydrogen peroxide in the liquid detergent composition of the present invention in order to suppress odors due to the wet-dry state, component (E) is preferably at least one compound selected from (e4) alkyl ethers and (e5) aromatic ethers, more preferably from diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether and phenoxypropylene glycol, and even more preferably from monobutyl ether diethyleneglycol and triethylene glycol monophenyl ether.

The liquid detergent composition of the present invention preferably contains compound (E) in an amount of from 1 to 40% by weight, more preferably from 4 to 20% by weight. and even more preferably from 5 to 10% of the mass.

[Component (F)]

The liquid detergent composition of the present invention preferably contains a hydrotropic agent as component (F) to stabilize the composition. The hydrotropic agent used in the present invention is an organic compound containing an anionic group and, in addition, one or two alkyl groups selected from a methyl group, an ethyl group and a propyl group, and a sulfate or carboxylate group. Examples of the hydrotropic agent include alkylbenzenecarboxylic and alkylbenzenesulfonic acids and their salts. Specific examples of the hydrotropic agent include p-toluenesulfonic acid, cumensulfonic acid, m-xylene sulfonic acid and benzoic acid. The salt is preferably selected from alkali metal salts. In the present invention, p-toluene-sulfonic acid and its alkali metal salts are preferred. The hydrotropic agent can be added in acid form and neutralized in the composition with an alkaline agent. Component (F) can confer stability to the composition without attenuating the deodorizing effect on odors due to the wet-dry state.

Component (F) is preferably added in the form of an alkali metal salt. The content of component (F) is preferably from 0.1 to 5% by mass., More preferably from 0.5 to 4% by mass. and even more preferably from 1 to 3% of the mass. liquid detergent composition of the present invention, calculated on the basis of its acid form.

[Component (G)]

For reliable administration of hydrogen peroxide and similar components, the liquid detergent composition of the present invention preferably contains an alkaline agent [hereinafter referred to as component (G)] to neutralize the anionic surfactant, hydrotropic agent and / or chelating agent in the form of an acid to adjust the pH . As described below, in a liquid detergent composition of the present invention having a pH of not more than 7.0, an alkaline agent may be substantially absent. The alkaline agent used to neutralize is preferably selected from alkali metal hydroxides and more preferably selected from potassium hydroxide and / or sodium hydroxide.

In the case of using water-miscible organoamine compounds, more preferably alkanolamines having a total number of carbon atoms of 6 or less, such as monoethanolamine, diethanolamine and triethanolamine [hereinafter also referred to as component (G ′)], as a neutralizing agent from the point of view of deodorizing the effect on odors due to the wet-dry state, the content of the neutralizing agent is preferably less than 1% by mass, more preferably not more than 0.5% by mass. and even more preferably not more than 0.08% of the mass. composition. The amount of component (G ′) includes the amount of alkaline agent (a neutralizing agent for adjusting the pH), as well as the amount of anionic compound added in salt form.

[Component (H)]

The liquid detergent composition of the present invention preferably contains an organic chelating agent that can form a polyvalent metal ion chelate [hereinafter referred to as component (H)] in order to maintain the effects of the present invention for an extended period. Examples of the component of the organic chelating agent (H) include aminopolyacetic acid, such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylene triamine pentaacetic acid, glycol ether diaminetetraacetic acid, hydroxyethyliminodiacetic diacetic acid; other polycarboxylic acids, including aminopolyacetic acids, such as diglycolic acid, hydroxyhydroxy succinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, hydroxy succinic acid, gluconic acid, carboxymethyl succinic acid and their carboxyme; and organophosphoric acids such as aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and their salts. Examples of salts include alkali metal salts. Component (H) can be added in its acid form and neutralized with an alkaline agent in the composition to form a salt. Of the organic chelating agents, organophosphonic acids and their salts are preferred, and 1-hydroxyethylidene-1,1-diphosphonic acid is more preferred. The counterion is preferably selected from alkali metal salts.

To suppress the reduction of the effects of the present invention during storage, the composition of the present invention preferably contains an organic chelating agent. The inhibitory effect of the organic chelating agent is mainly realized due to the function of the agent to suppress the decomposition of hydrogen peroxide by probable heavy metal ions in the composition. However, many compounds used as an organic chelating agent have the property of attenuating pH changes upon dilution. To achieve good detergency, an organic chelating agent that is effective with a small amount is preferable in order to facilitate a pH change with water to close to neutral. Such an organic chelating agent is preferably organophosphonic acid or its salts. Preferably, the salt is a potassium salt or a sodium salt.

In the composition, the content of component (H) is preferably from 0.01 to 0.5% by weight, more preferably from 0.03 to 0.3% by weight. and even more preferably from 0.05 to 0.2 wt.%, calculated on the basis of its acid form. The composition more preferably contains 1-hydroxyethylidene-1,1-diphosphonic acid as component (H) within a limited content range.

[Component (I)]

The liquid detergent composition of the present invention preferably contains a water-soluble polymer as component (I) to enhance the deodorizing effect on odors due to the wet-dry state. The water soluble polymer preferably has a structural unit containing a carboxylate group. Examples of a water soluble polymer include polyacrylic acids, copolymers (acrylic acid) - (maleic acid) and copolymers of acrylic acid or maleic acid and an olefin containing from 2 to 5 carbon atoms. In a concentrated system containing a significant amount of surfactant, it is preferable to use polymers having a structural unit containing a carboxylate group and a structural unit containing a polyoxyethylene chain. Examples of the polymer include the polymers described in JP-A10-60476 and JP-A2004-155937. The content of component (I) is preferably from 0.1 to 5% of the mass. and more preferably from 0.5 to 4% of the mass.

[Components other than those described above]

The liquid detergent composition of the present invention may optionally contain one or more components selected from the following components (i) to (vii) within an interval that does not attenuate the effects of the present invention:

(i) enzymes such as cellulase, amylase, pectinase, protease and lipase;

(ii) enzyme stabilizers, such as sources of calcium ions (giving calcium ion compounds), dihydroxy compounds and formic acid;

(iii) fluorescent dyes, such as industrial dyes, including Tinopal CBS (trade name, Ciba specialty Chemicals Inc.) and Whitex SA (trade name, Sumitomo Chemical Co., Ltd.);

(iv) antioxidants such as butylhydroxytoluene, distirol-modified cresol, sodium sulfite and sodium hydrosulfite;

(v) the gelatinization inhibiting polymer described in JP 11-513067 W, and more preferably polypropylene glycol and polyethylene glycol having a weight average molecular weight of 600 to 5000 and more preferably 1000 to 4000 when measured using a light scattering method using a dynamic scattering spectrophotometer light (e.g., DLS-8000 series, Otsuka Electronics Co., Ltd.);

(vi) water-immiscible organic solvents such as paraffins (e.g. octane, decane, dodecane and tridecane), olefins (e.g. decen and dodecene), alkyl halides (e.g. methylene chloride and 1,1,1-trichloroethane) and terpenes ( for example, D-limonene); and

(vii) other agents, such as pigment, perfume, antiseptic and foaming suppressing agent (e.g. silicones).

The following concentrations of such optional components are indicative of the addition of the present invention to a liquid detergent composition. Such concentrations can be suitably adjusted so as not to impair the effect of the present invention, or even be zero if the component is unsuitable for the composition.

The content of the enzyme (i) is preferably from 0.001 to 2% of the mass. The content of the stabilizer of the enzyme (ii) is preferably from 0.001 to 2% of the mass. The content of the fluorescent dye (iii) is preferably from 0.001 to 1% of the mass. The content of antioxidant (iv) is preferably from 0.01 to 2% of the mass. The content of polyalkylene glycol anti-gelatinization polymer (v) is preferably from 0.01 to 2% of the mass. The content of water-immiscible organic solvent (vi) is preferably from 0.001 to 2% of the mass. The content of the other agent (vii) may be any known concentration.

From the point of view of fluid stability and suppressing decomposition of hydrogen peroxide, the liquid detergent composition of the present invention preferably contains a bleaching activator, for example, a bleaching activator having an anionic group, in an amount of less than 1 wt.%, More preferably not more than 0.4 wt. and even more preferably does not contain a bleaching activator. As used herein, a “whitening activator” refers to a compound that reacts with hydrogen peroxide in water under mild conditions, such as for domestic use, to form an organic acid. Examples of the bleaching activator include TAED (tetraacetylethylenediamine) and alkanoyloxybenzenesulfonic and alkanoyloxybenzenecarboxylic acids containing a linear or branched alkyl group containing from 8 to 22 carbon atoms, and their salts with alkali metals, which are known to be mixed in a liquid bleaching composition. Of these, alkanoyloxybenzenesulfonic and alkanoyloxybenzenecarboxylic acids containing a linear or branched alkyl group containing from 8 to 22 carbon atoms, and their salts with alkali metals, as is known, are reliably mixed with hydrogen peroxide. However, in the present invention, such acids and their salts are also whitening activators having an anionic group and anionic surfactants (C1) other than fatty acids or their salts, and are therefore subject to the limitation of the weight ratio (C1) / ( AT). The whitening activator may be present in such an amount that the mass ratio (c1) / (B) falls within a certain range, but in such an amount it will not be enough to fully manifest its effect in the liquid detergent composition of the present invention. In addition, the whitening activator imposes a restriction on the composition as necessary reliable mixing in the composition and causes a decrease in the deodorizing effect of the present invention.

In general, a washing solution and a bleaching liquid containing hydrogen peroxide increase their bleaching effects at a higher pH when the liquid is used. However, the liquid detergent composition of the present invention is preferably substantially free of the boron compound that is used to alkalize the aqueous dilution of the composition. In the present invention, boron compounds reduce detergency. As used herein, a “boron compound” includes boric acid, borax, and borates. Specific examples of borate are sodium borate, potassium borate, ammonium borate, sodium tetraborate, potassium tetraborate and ammonium tetraborate. In the present invention, the expression “substantially free of boron compound” includes trace contamination with a boron compound, for example, from an enzyme preparation containing a boron compound as an enzyme stabilizer. Specifically, the composition contains a boron compound in an amount of less than 0.1 wt.%, And more preferably less than 0.01 wt.%, Calculated on the basis of boric acid, provided that borax is calculated based on its weight. The lower limit is 0% of the mass.

The remainder of the liquid detergent composition of the present invention is water. The water used is preferably sterilized deionized water.

In terms of detergency and deodorizing effect, the liquid detergent composition of the present invention preferably has a pH of from 3.0 to 7.0, more preferably from 3.5 to 7.0, and even more preferably from 4.0 to 6.0 at 20 ° C in accordance with JIS K3362: 1998, Section 8.3.

More preferably, the liquid detergent composition of the present invention preferably has a pH of from 4.0 to 8.5, and more preferably from 6.0 to 8.0 at 20 ° C. in the form of a solution of 2 ml of the composition in 3 l of soft water having a hardness of 4 ° DH and a pH of 6.0 to 8.0 at 20 ° C., prepared by adding calcium carbonate to deionized water.

From the point of view of ease of handling, the liquid detergent composition of the present invention preferably has a viscosity of from 10 to 1000 mPa · s, more preferably from 50 to 600 mPa · s and even more preferably from 100 to 300 mPa · s at 20 ° C. Viscosity can be controlled by changing the proportions of the components (a1), (a2) and (E) and water, etc. To reduce the viscosity of the composition, the nonionic surfactant (a1 ′) of component (a1) is used appropriately.

In the present invention, viscosity is measured using a B-type viscometer. The rotor is selected depending on the viscosity. The liquid detergent composition is rotated at a speed of 60 rpm, and the measured value after 60 seconds of rotation is considered as the viscosity of the composition.

The liquid detergent composition of the present invention can be used for textiles, preferably household textiles, such as clothing, a towel, sanitary cover and bedding, and more preferably for clothing. The liquid detergent composition of the present invention can also be suitably used for washable textiles.

In the present invention, the liquid detergent composition of the present invention gives good detergency and good deodorizing effect when used in a cleaning liquid containing water, for example, in an aqueous solution of a composition for washing a textile product. A cleaning liquid is preferably prepared by dissolving from 0.3 to 1.0 g of the composition in 1 liter of water. Such a cleaning liquid, for example, an aqueous solution, is usually called a washing solution. The washing liquid may be at any temperature during washing. In accordance with the present invention, a liquid detergent composition can provide a washing ability and a deodorizing effect, provided that the temperature of the washing solution is not limited, within a wide range of water temperature from 5 to 40 ° C. The step of immersion in the soaking liquid can be introduced before washing. In this case, the concentration of the liquid detergent composition in the soaking liquid is preferably 3-6 times higher than the concentration in the cleaning liquid.

The liquid detergent composition of the present invention can produce a conspicuous soapy foam in the presence of bacteria in a used textile product, especially a worn textile product, when applied (in a non-soap condition) to a textile product. Soap foam is produced by the dismutation of bacterial catalase. It is noteworthy that soap foam does not appear on a new textile product or textile product after one day of use or wearing. Soap foam appears when the liquid detergent composition of the present invention is applied to a textile product that has been used or worn repeatedly and cleaned several times, and in some cases, to a durable textile product even immediately after cleaning and drying.

Thus, the present invention also provides a method for cleaning a textile product, comprising the step of applying a liquid detergent composition of the present invention to a textile product to obtain a soap foam. In this method, part or all of the liquid detergent composition can be applied to a textile product to confirm the presence of bacteria due to the formation of soap foam.

A method comprising such an application of the present invention makes it possible not only to confirm the state of the presence of bacteria, but also pays attention to the use of a liquid detergent composition in the area showing the presence of bacteria. Such a methodology is disclosed in JP-A2010-59296 regarding detergent for hard surfaces. Some common liquid textile whitening compositions containing hydrogen peroxide also produce soap suds in the presence of bacteria. Such a soapy foam, however, may not be noticeable enough for visual assessment due to the low concentration of surfactant in such a conventional liquid hydrogen peroxide bleaching composition. In addition, conventional bleaches for textiles are aimed at bleaching and are intended for concentrated application on a visually dirty place, such as a stain, collar and cuffs. On the contrary, the composition of the present invention is supposed to suppress odors caused by bacteria, and, therefore, creates an advantage from the conspicuous soap foam, which allows visual assessment due to the formation of soap foam.

The liquid detergent composition of the present invention provides a soap foam by contact with bacteria. A composition having good characteristics for visually assessing the presence of bacteria by foaming has a structure that follows the preferred conditions for the liquid detergent composition described above, for example, in which, as a nonionic surfactant (A), compounds of formulas (a1) and (a2 ) use preferably, and more preferably, compounds having PO groups in an amount of from not less than 1 mol to not more than 3 mol on average. A composition having such a structure readily gives an eye-catching soap foam in the presence of bacteria, and there is an acceptable period of time from the formation to the disappearance of soap foam.

The present invention also relates to a method for cleaning a textile product, including the steps of applying a liquid detergent composition of the present invention to a textile product to obtain a soap foam, and washing the textile product with a washing solution containing water. A textile product with the liquid detergent composition of the present invention applied thereto may be washed with another textile product in a washing machine using any detergent. Any detergent does not exclude the remainder of the applied liquid detergent composition of the present invention or other detergent. More specifically, the textile product can be cleaned by applying part or all of the liquid detergent composition of the present invention, which should be used to clean the textile product, and contacting the treated textile product with a washing solution containing the remainder of the composition and water. In even more detail, a method of washing a textile product includes applying a portion of the liquid detergent composition of the present invention, placing the textile product and, optionally, optionally any textile product, and the remainder of the composition and water in a washing tank, and washing the textile products in an aqueous solution, and can provide good deodorizing effect also on parts of the textile product without the applied composition and any other textile product washed together. All liquid detergent composition of the present invention, which should be used, can be applied to a textile product, which must be washed. If the application step is included, the liquid detergent composition of the present invention is used in such an amount that the concentration of the composition in the detergent solution is in the range from 0.3 to 1.0 g / l, as described above (the concentration may be a calculated value based on the applied amount ) to fully achieve the effects of the present invention.

As used in this case, the definition of “washing” or “leaving by washing” includes mechanical stirring with a washing machine and manual leaving when washing manually, for example, by friction, beating or trampling.

The method of cleaning a textile product of the present invention when used can undoubtedly be distinguished from the traditional task by the orientation of the invention to a method for deodorizing or to a method for deodorizing and cleaning.

EXAMPLES

The following examples demonstrate the present invention. The examples are intended to illustrate the present invention and do not limit it.

<Test examples (determination of the substance causing the odor due to the wet-dry state>

Cotton towels with a strong smell of dampness after washing and drying are collected at home and a piece weighing 50 g is cut out. The piece is treated with 500 ml of dichloromethane to extract the odor generating component. The extracting solution was concentrated under reduced pressure. 200 ml of an aqueous solution of 1 M sodium hydroxide was added to the residue. The aqueous layer is collected. 200 ml of hydrochloric acid was added to the organic layer to acidify the mixture. 200 ml of dichloromethane are added to the mixture. The organic layer was concentrated under reduced pressure to obtain 1 ml of an acid component concentrate.

Then, using an Agilent gas chromatograph and a Gerstel preparative fraction collector (PCF) attached to the instrument, the exact dilutions are fractionated depending on the retention time in the GC under the following conditions. Thirty GC fractions near the target component were each captured with 200 ml of vehicle (trade name: TENAX TA, GL Sciences Inc.) in a glass tube having an inner diameter of 6 mm and a length of 117 mm.

(GC-PCF Terms)

GC: Agilent 6890N (product name, Agilent Technologies Inc.)

Column: DB-1 (product name, Agilent Technologies Inc.), length: 30 m, internal diameter: 0.53 mm, thickness: 1 μm

40 ° С for 1 min, retention → 6 ° С / min to 60 ° С → 4 ° С / min to 300 ° С

Injection Volume: 2 μl

PCF (PFC, Gerstel K.K. Japan): capture time: from the 18th minute to 24 minutes, 30 fractions

Trap: TENAX TA (product name, GL Sciences Inc.) 200 mg

Finally, the target component captured using TENAX TA is analyzed in a Gerstel thermal desorption system (STD) attached to an Agilent GC-MS system under the following conditions.

(Terms STD-GC-MS)

GC: Agilent 6890N (product name, Agilent Technologies Inc.)

MS: Agilent 5973 (product name, Agilent Technologies Inc.)

STD desorption (TDS): 250 ° С, purge flow rate: 50 ml / min, purge time: 3 min.

Column: DB-FFAP (product name, Agilent Technologies Inc.), length: 30 m, internal diameter: 250 μm, thickness: 0.25 μm

40 ° С for 1 min, retention → 6 ° С / min to 60 ° С → 2 ° С / min to 240 ° С

In the analysis, branched medium chain fatty acids, including 4M3H, are determined in the component that causes odor due to the wet-dry state.

<Examples and comparative examples>

(1) Assessment of washing ability

(1-1) Preparation of the cut-off collar blank

The collars of polyester / cotton shirts that were worn for three days are cut from the shirts and sorted to select dirty collars with the same degree of contamination that are used as the dirty collar fabrics to be tested. The selected fabrics for testing are cut in half and individually sewn onto a cotton fabric measuring 30 × 30 cm (hereinafter referred to as a cut blank). Six pairs of cut blanks (a total of twelve blanks) are prepared for each of the liquid detergent compositions shown in tables 1-3. Six sheets of one of the half blanks are washed with each composition of examples and comparative examples, and the other half is washed with a standard detergent to determine the washing ability.

(1-2) Preparation of washing water

Hard water is prepared by dissolving 25.14 g of calcium chloride dihydrate and 8.70 g of magnesium chloride hexahydrate in 2966.13 g of ion-exchanged water to obtain a hardness of 400 ° DH and a calcium / magnesium ratio of 8: 2 as components of hardness. The prepared hard water is diluted with ion-exchange water to a hardness of 4 ° DH and is used as washing water in the washing test.

(1-3) Rating

The washing test uses a washing machine (NA-FV8001; Panasonic Corporation) and washing water, which is obtained as described above. Ten participants in the experiment (men over thirty) make a conclusion about the washing ability. Visually evaluate six halves of cut preforms washed with a liquid detergent composition from liquid detergent compositions (test detergents) shown in Tables 1-3, and other halves washed in the same way, except that they use the standard detergent described in JIS K3362: 1998, instead of liquid detergent compositions. It is concluded that detergents are better in terms of their washing ability. A washed pair of cut preforms is assigned a “+1” score if the cut preform washed with the test detergent is cleaner than that washed with a standard detergent, or “-1” if less clean than that washed with a standard detergent facilities. The point assigned in the aggregate by the participants in the experiment is in the range from +6 to -6. For each detergent, ten participants in the experiment give a conclusion and evaluate it in accordance with all ten points. A test detergent that receives a total score within the range of +5 to -5 is considered to have the same detergent ability with a standard detergent. At a total score of +6 or higher, the test detergent is considered to be better in its washing ability than a standard detergent, and at -6 or lower, it is considered to be bad. A test detergent that receives a higher total score is considered to have a better detergency.

(2) Odor assessment of the type of musty odor of a dirty and damp floor cloth

From underwear (100% cotton), repeatedly worn by adult men from twenty to forty years old and washed, linen is selected that emits the usual smell due to the wet-dry state when it becomes wet, but does not emit odor after washing and complete drying. The selected laundry is cut into pieces measuring 5 × 5 cm and sorted using special experimental participants to select pieces that emit odors to the same extent when they become wet. The usual odor due to the wet-dry state is quantitatively analyzed and the presence of the smell of branched medium chain fatty acids, mainly consisting of the smell of 4M3H and sulfur, is confirmed.

In order to evaluate the cut blanks assembled and sorted as test blanks of real clothes for study, if possible in the same initial state to each other, these cut blanks are washed in a washing solution containing 0.67 g / l of standard detergent using the following fragrance-free compositions using a washing tester with stirring (tergotometer, Terg-O-tometer) under conditions: water temperature 25 ° C, stirring speed 85 rpm, stirring time 10 minutes and the ratio in the tank 15. Postir These cut blanks are thoroughly rinsed with tap water and immediately placed in an environment with a temperature of 25 ° C and a relative humidity of 35% and left for 24 hours until completely dry. From the dried cut preforms, preforms are additionally selected having an odor intensity indicated by “1” (no odor) according to the rating scale described below, agreed by five special controllers. Such selected blanks are used as test blanks of real test clothing. Such test pieces processed using a standard detergent have been shown to emit an odor including 4M3H odor when they become wet.

Standard detergent contains:

(1) alkyl (12 carbon atoms, linear) sodium benzenesulfonate in an amount of 10 wt%, (2) alkyl (12 carbon atoms) sodium sulfate in an amount of 2 wt%, (3) sodium fatty acid salt derived from palm oil , in an amount of 2% wt., (4) simple polyoxyethylene (average number of attached moles: 10) alkyl (12-14 carbon atoms) ether in an amount of 10% wt., (5) sodium carbonate in an amount of 15% wt., ( 6) zeolite in an amount of 10 wt.%, (7) copolymer (acrylic acid) - (maleic acid) (weight average molecular weight: 70,000, molar ratio: (acrylic slots) / (maleic acid) = 6: 4) in an amount of 5% by weight, (8) sodium silicate No. 2 in an amount of 1% by weight, and (9) sodium sulfate in the residue (total 100% by weight).

Then the test blanks are washed using liquid detergent compositions shown in tables 1-3, and evaluated in accordance with the above tests of odor intensity (estimates of odor intensity A and B).

- Assessment of odor intensity A (assessment of odor released from a raw textile product in a short time)

For each of the liquid detergent compositions shown in Tables 1-3, a detergent solution containing 0.67 g / L of the liquid detergent composition is prepared and used to wash a set of five test pieces of real fabrics using a stirred washing tester (Tergot-o -Meter) under the conditions: water temperature 25 ° C, stirring speed 85 rpm, stirring time 10 minutes, and the ratio in the tank 15. The washed test pieces are thoroughly rinsed with tap water and stored in a climatic chamber for 3 hours under conditions of temperature uroy 30 ° C and relative humidity of 90%, which, apparently, causes the development of odor due to the wet-dry state. The stored test pieces are organoleptically evaluated for odor due to a wet-dry state (a complex odor including odors of S, N, aldehydes, short chain fatty acids and branched chain medium fatty acids such as 4M3H) by five special controllers.

- Evaluation of the intensity of the smell B (evaluation of the returning from time to time the smell released from the dry textile product)

For each of the liquid detergent compositions shown in Tables 1-3, a detergent solution containing 0.67 g / L of the liquid detergent composition is prepared and used to wash a set of five test pieces of real fabrics using a stirred washing tester (Tergot-o -Meter) under the conditions: water temperature 25 ° C, stirring speed 85 rpm, mixing time 10 minutes, and the ratio in the tank 15. The washed test pieces are thoroughly rinsed with tap water and stored in a climatic chamber for 12 hours at 30 ° C and rel relativity humidity of 90%, which, apparently, causes the development of odor due to the wet-dry state. Then the test blanks are given the opportunity to stay all night and all day in an environment with a temperature of 25 ° C and a relative humidity of 35% until completely dry. The dried test pieces are odorless due to the wet-dry state.

The test pieces are again moistened with 0.1 g of tap water sprayed through a spray bottle. Wet test blanks are organoleptically evaluated for odor returning from time to time due to the wet-dry state (the smell of branched medium chain fatty acids, consisting mainly of 4M3H) by the same five special controllers.

The scoring of the estimates of odor intensity A and B is carried out in accordance with the rating scale given below using special controllers as agreed.

Rating scale:

1: no smell

2: almost no smell

3: faint smell

4: odor recognized by careful sniffing

5: easily recognizable odor.

The results of the estimates of the intensity of odor A and B are presented in tables 1-3. A point classification of 3 to 5 means that at least four controllers paid attention to the smell.

Examples of the composition of the liquid detergent composition of the present invention are shown below in table 4.

Table 4 Mixing Examples one 2 3 four 5 Liquid detergent composition Components (% wt.) (BUT) (a1) A1-1 40,0 40,0 40,0 35.0 A1-2 30,0 (a3) a3-6 5,0 10.0 a3-7 5,0 10.0 15.0 (AT) b1-1 5,0 b1-2 2.0 2.0 1,5 b1-3 1,5 (FROM) (c1) Las 1,0 0.5 (D) Hydrogen peroxide 3.0 3.0 3.0 3.0 3.0 (E) e-1 10.0 10.0 5,0 10.0 e-2 5,0 10.0 (F) f-1 2.0 2.0 2.0 2.0 2.0 (H) h-1 0.1 0.1 0.1 0.1 0.1 (I) i-1 2.0 2.0 1,5 2.0 2.0 Perfume 0.5 0.5 0.8 - 0.8 Sterile water Balance Balance Balance Balance Balance Total one hundred one hundred one hundred one hundred one hundred pH (20 ° C) 4.0 3,5 5,0 5.5 4.0 The content of component (A),% mass. 45.0 45.0 50,0 45.0 45.0 The content of component (A1),% mass. 2.5 1.7 5,0 3.4 5.1 (c1) / (B) (mass ratio) 0.5 0,0 0,0 0,0 0.3

The ingredients shown in the tables are the following components.

<Ingredients>

In the description below, ethylene oxide and propylene oxide are reduced to EO and PO, respectively. The concentration of the anionic organic compound in its salt form is converted to the concentration of its acid form. The converted concentration is indicated in the tables. The pH values of the compositions are adjusted using an aqueous solution of sodium hydroxide or an aqueous solution of hydrochloric acid.

Component (A)

Component (A1)

- a1-1:

Polyoxyethylene (9) polyoxypropylene (2) polyoxyethylene (9) -alkyl ether (numbers in parentheses indicate the average number of moles attached) [obtained by addition of 9 moles of ethylene oxide, 2 moles of propylene oxide and 9 moles of ethylene oxide in the indicated order with block addition per mole of saturated linear primary alcohol containing from 10 to 14 carbon atoms, that is, the compound represented by formula (a1-5), in which p11 = 9, q = 2 and p12 = 9. Component (A1) is not present].

- a1-2:

Polyoxyethylene (8) polyoxypropylene (2) polyoxyethylene (8) -alkyl ether (numbers in parentheses indicate the average number of moles attached) [obtained by attaching 8 moles of ethylene oxide, 2 moles of propylene oxide and 8 moles of ethylene oxide in this order with block addition per mole of saturated linear primary alcohol containing from 10 to 14 carbon atoms, that is, a compound represented by the formula (a1-5) in which p11 = 8, q = 2 and p12 = 8. Component (A1) is not present].

- a1-3:

Polyoxyethylene (15) polyoxypropylene (2) polyoxyethylene (15) -alkyl ether (numbers in parentheses indicate the average number of moles attached) [obtained by adding 15 moles of ethylene oxide, 2 moles of propylene oxide and 15 moles of ethylene oxide in the indicated order when block moiety per mole of saturated linear primary alcohol containing from 10 to 14 carbon atoms, that is, a compound represented by the formula (a1-5) in which p11 = 15, q = 2 and p12 = 15. Component (A1) is not present].

- a1-4:

Polyoxyethylene (20) polyoxypropylene (2) alkyl ether (numbers in parentheses indicate the average number of moles attached) [obtained by adding 20 moles of ethylene oxide and 2 moles of propylene oxide in this order with block addition per mole of saturated linear primary alcohol containing from 10 to 14 carbon atoms, i.e. a compound represented by the formula (a1-2) in which p = 20 and q = 2. Component (A1) is not present].

- a1-5:

Polyoxyethylene (14) polyoxypropylene (2) polyoxyethylene (4) -alkyl ether (numbers in parentheses indicate the average number of moles attached) [obtained by adding 14 moles of ethylene oxide, 2 moles of propylene oxide and 4 moles of ethylene oxide in the indicated order with block addition per mole of saturated linear primary alcohol containing from 10 to 14 carbon atoms, that is, a compound represented by the formula (a1-5) in which p11 = 14, q = 2 and p12 = 4. Component (A1) is not present].

Component (A2)

- a2-1: a nonionic surfactant represented by the formula (a2) in which R ^2a is a linear primary alkyl group containing 11 carbon atoms, l is 1, m is 15, n is 0 and R ^21a represents a methyl group.

- a2-2: a non-ionic surfactant represented by the formula (a2) in which R ^2a is a linear primary alkyl group containing 11 carbon atoms, l is 1, m is 10, n is 0 and R ^21a represents a methyl group.

Component (a3)

- a3-1: a non-ionic surfactant represented by the formula (a3) in which R ^3a is a linear alkyl group containing from 12 to 14 carbon atoms and has a secondary carbon atom in which the R ^3a group binds to an oxygen atom R ^3a —O—, and r = 7 [obtained by addition of 7 moles of EO per mole of saturated linear secondary alcohol containing 12 to 14 carbon atoms, and separation of the unreacted alcohol by distillation. The content of R ^a2 OH is less than 0.1% by mass.].

- a3-2: a non-ionic surfactant represented by the formula (a3) in which R ^3a is a linear alkyl group containing 12 carbon atoms and has a primary carbon atom in which the R ^3a group binds to the oxygen atom R ^3a - O-, and r = 3 (with simple distribution), approximately 100% a3-2 is a component (A1), which is a compound represented by the formula (A1), in which x = 3.

- a3-3: a nonionic surfactant represented by the formula (a3) in which R ^3a is a linear alkyl group containing 12 carbon atoms and has a primary carbon atom in which the R ^3a group binds to the oxygen atom R ^3a - O-, and r = 5 (with a simple distribution), approximately 100% a3-2 is a component (A1), which is a compound represented by the formula (A1) in which x = 5.

- a3-4: a nonionic surfactant represented by the formula (a3) in which R ^3a is a linear alkyl group containing 14 carbon atoms and has a primary carbon atom in which the R ^3a group binds to the oxygen atom R ^3a - O-, and r = 5 (with a simple distribution) that does not contain component (A1).

- a3-5: a nonionic surfactant represented by the formula (a3) in which R ^3a is a linear alkyl group containing 10 carbon atoms and has a primary carbon atom in which the R ^3a group binds to the oxygen atom R ^3a - O-, and r = 5 (with a simple distribution).

- a3-6: a nonionic surfactant having 3 moles of EA on average produced by attaching ethylene oxide to lauryl alcohol, or a nonionic surfactant represented by formula (a3) in which R ^3a is a linear alkyl group containing 12 carbon atoms, and has a primary carbon atom in which the R ^3a group binds to the oxygen atom R ^3a -O-, and r = 3, containing component (A1), of which non-ionic compounds represented by formula (A1), in which x = 2, 3, 4 or 5, make up 50% of the mass. a3-6 in total, and non-ionic compounds in which x = 3, 4 or 5, make up 32% of the mass. A3-6 in total. In a3-6 are non-ionic compounds that can be represented by formula (A1), in which x = 0 or 1 for convenience, and have the same R groups as described in formula (A1), in a total amount of 33% of the mass.

- a3-7: a nonionic surfactant having 6 moles of EA on average produced by attaching ethylene oxide to lauryl alcohol, or a nonionic surfactant represented by formula (a3) in which R ^3a is a linear alkyl group containing 12 carbon atoms, and has a primary carbon atom in which the R ^3a group binds to the oxygen atom R ^3a -O-, and r = 6, containing component (A1), of which non-ionic compounds represented by the formula (A1), in which x = 2, 3, 4 or 5, make up 34% of the mass. a3-7 in total, and non-ionic compounds in which x = 3, 4 or 5, make up 27% of the mass. A3-7 in total. A3-7 also contains non-ionic compounds, which can be represented by formula (A1), in which x = 0 or 1 for convenience, and have the same R groups as described in formula (A1), in a total amount of 10% of the mass.

- a3-8: a nonionic surfactant represented by the formula (a3) in which R ^3a is a linear alkyl group containing 12 carbon atoms and has a primary carbon atom in which the R ^3a group binds to the oxygen atom R ^3a - O-, and r = 8 (with a simple distribution), not containing component (A1), but containing a compound that can be represented by formula (A1) for convenience, and contains approximately 100% of compounds with x = 8.

Component (B)

- b1-1: N- (1-dodecyl) -N, N, N-trimethylammonium ethyl sulfate.

- b1-2: N- (1-tetradecyl) -N, N-dimethyl-N-ethylammonium ethyl sulfate.

- b1-3: N- (1-octadecyl) -N, N, N-trimethylammonium methyl sulfate.

Component (C)

- LAS: alkylbenzenesulfonic acid having a linear alkyl group containing from 10 to 14 carbon atoms (average carbon number: 11.7)

- palm oil fatty acid: Lunac L-55 (product name), Kao corporation

- di (long chain alkyl (C14)) cation: di (linear alkyl (14 carbon atoms)) dimethylammonium ethyl sulfate, in which two C14 alkyl groups bonded to the nitrogen atom have a primary carbon atom.

Component (E)

- e-1: diethylene glycol monobutyl ether (also called butoxydiglycol).

- e-2: triethylene glycol monophenyl ether (PHG-30, Nippon Nyukazai Co., Ltd.).

- e-3: ethanol.

Component (F)

- f-1: sodium p-toluenesulfonate (the concentration shown in the tables is calculated based on its acid form).

Component (N)

h-1: 1-hydroxyethylidene-1,1-diphosphonic acid.

Component (I)

- i-1: a polymer compound produced by the method of Synthesis Example 1 described in JP-A10-60476 p. 4, paragraph 0020.

- fluorescent dye: Tinopal CBS-X (product name) (BASF Japan).

- enzyme: Everlase 16.0L-EX (product name) (protease, Novozymes).

<Formation of soapy foam when applied>

The liquid detergent compositions of Examples 7-20 in Table 2 and Comparative Example 11 in Table 3 are prepared. Black cotton socks any adult male from twenty to forty years old wears 12 hours, wash the socks using a standard detergent described in the evaluation method for odor due to wet -dry condition and dried indoors at a temperature of 20 ° C and a relative humidity of 60%. This cycle of socks, washing and drying is repeated ten times. The black cotton socks prepared in this way are used for evaluation.

A liquid detergent composition is applied to the lower part of the sock, worn and washed repeatedly. Each of the liquid detergent compositions of the examples gives a significant soapy foam, although the formation of foam varies from one owner to another. Soap foam forms within 15 seconds of application and disappears within 60 seconds of application. The liquid detergent composition of comparative example 11 without hydrogen peroxide does not give a soap foam.

Claims (13)

1. A liquid detergent composition containing:
(A) a non-ionic surfactant [hereinafter referred to as component (A)] in an amount of from 15 to 70% by weight,
(B) a cationic surfactant represented by the formula (B1) [hereinafter referred to as component (B)] in an amount of from 0.3 to 5% by weight,
(D) hydrogen peroxide [hereinafter referred to as component (D)] in an amount of from 0.3 to 10% by weight, and
water
where component (A) contains (A1) a nonionic compound represented by the formula (A1) in an amount of from 0.5 to 10% by weight. composition
the mass ratio (c1) of an anionic surfactant other than a fatty acid or its salt to component (B), (c1) / (B) is from 0 to 1, and
the composition has a pH of from 3.0 to 7.0 at 20 ° C when measured in accordance with JIS K3362: 1998, Section 8.3:

where R is a linear alkyl group containing 12 carbon atoms, and has a primary carbon atom in which R binds to the oxygen atom RO-; and x represents the number of moles of attached ethyleneoxy groups and has integer values ranging from 2 to 5:

where R ^b1 represents a chain hydrocarbon group containing from 12 to 18 carbon atoms, and may have a group - (A′O) _s - in it, where A′O represents an ethyleneoxy group or a propyleneoxy group, and s means average the number of moles A′O, in the range from 0 to 10; the groups R ^b2 , R ^b3 and R ^b4 each independently represents a methyl group, an ethyl group, a benzyl group or a hydroxyalkyl group containing from 1 to 3 carbon atoms; and X ^- represents CH ₃ SO ₄ ^- , CH ₃ CH ₂ SO ₄ ^- or a halogen ion, and
where component (A) contains at least one non-ionic surfactant selected from surfactants represented by formulas (a1) and / or (a2), in an amount of from 10 to 60% of the mass .:

where R ^1a represents an alkyl or alkenyl group containing from 8 to 22 carbon atoms; AO means alkyleneoxy group containing from 3 to 5 carbon atoms; p denotes the average number of moles of attached C ₂ H ₄ O groups ranging from 8 to 40; q means the average number of moles of attached AO groups, ranging from 0 to 5; and “/” means that C ₂ H ₄ O-groups and AO groups can be distributed either by statistical accession or by block accession;

where R ^2a represents an alkyl or alkenyl group containing from 8 to 22 carbon atoms; R ^21a represents an alkyl group containing from 1 to 3 carbon atoms; 1 means the number 0 or 1; AO means alkyleneoxy group containing from 3 to 5 carbon atoms; m means the average number of moles of attached C ₂ H ₄ O groups, ranging from 5 to 30; n means the average number of moles of attached AO groups, ranging from 0 to 5; and “/” means that C ₂ H ₄ O-groups and AO groups can be distributed either by statistical accession or by block accession. 2. The liquid detergent composition according to claim 1, where in component (A1) the total proportion of compounds in which x is 3, 4 or 5 is from 70 to 100% of the mass. 3. Liquid detergent composition according to claim 1 or 2, where the composition contains component (A1) in an amount of from 1 to 8% of the mass. 4. The liquid detergent composition according to claim 1, wherein component (A) contains a non-ionic surfactant represented by formula (a3) in an amount of from 0.5 to 20% by mass:

where R ^3a represents an alkyl or alkenyl group containing from 8 to 22 carbon atoms, and has a primary and / or secondary carbon atom in which R ^3a binds to the oxygen atom R ^3a —O—; and r means the average number of moles of attached C ₂ H ₄ O groups ranging from 2 to less than 8. 5. The liquid detergent composition according to claim 1, additionally containing (c2) fatty acid and its salt in an amount of from 0.05 to 5% by weight, calculated on the basis of its acid form. 6. The liquid detergent composition according to claim 1, additionally containing (E) miscible with water, an organic solvent in an amount of from 1 to 40% of the mass. 7. The liquid detergent composition according to claim 1, additionally containing (H) an organic chelating agent in an amount of from 0.01 to 0.5% of the mass. 8. The liquid detergent composition according to claim 1, wherein the content of the water-miscible organoamine compound is less than 1% by weight. 9. A liquid detergent composition according to claim 1, not containing a whitening activator. 10. The method of cleaning a textile product using an aqueous solution of a liquid detergent composition according to any one of paragraphs. 1-8. 11. A method of cleaning a textile product, comprising the step of applying a liquid detergent composition to a textile product and obtaining soap foam using a detergent composition, where the detergent composition contains:
(A) a non-ionic surfactant [hereinafter referred to as component (A)] in an amount of from 15 to 70% by weight,
(B) a cationic surfactant represented by the formula (B1) [hereinafter referred to as component (B)], in an amount of from 0.3 to 5% by weight,
(D) hydrogen peroxide [hereinafter referred to as component (D)] in an amount of from 0.3 to 10% by weight, and
water
where component (A) contains (A1) a nonionic compound represented by the formula (A1) in an amount of from 0.5 to 10% by weight. composition
the mass ratio of anionic surfactant other than a fatty acid or its salt to component (B), (c1) / (B) is from 0 to 1, and
the composition has a pH of from 3.0 to 7.0 at 20 ° C. as measured in accordance with JIS K3362: 1998, Section 8.3:

where R is a linear alkyl group containing 12 carbon atoms, and has a primary carbon atom in which R binds to the oxygen atom RO-; and x means the number of moles of attached ethyleneoxy groups and has an integer value in the range from 2 to 5:

where R ^b1 represents a chain hydrocarbon group containing from 12 to 18 carbon atoms, and may have a group - (A′O) _s - in it, where A′O represents an ethyleneoxy group or a propyleneoxy group, and s means average the number of moles of attached A′O ranging from 0 to 10; the groups R ^b2 , R ^b3 and R ^b4 each independently represents a methyl group, an ethyl group, a benzyl group or a hydroxyalkyl group containing from 1 to 3 carbon atoms; and X ^- represents CH ₃ SO ₄ ^- , CH ₃ CH ₂ SO ₄ ^- or a halogen ion, and
where component (A) of the liquid detergent composition contains at least one non-ionic surfactant selected from surfactants represented by formulas (a1) and / or (a2) in an amount of from 10 to 60% by weight:

where R ^1a represents an alkyl or alkenyl group containing from 8 to 22 carbon atoms; AO means alkyleneoxy group containing from 3 to 5 carbon atoms; p means the average number of moles of attached C ₂ H ₄ O groups, ranging from 8 to 40; q means the average number of moles of attached AO groups, ranging from 0 to 5; and “/” means that C ₂ H ₄ O-groups and AO groups can be distributed either by statistical accession or by block accession;

where R ^2a represents an alkyl or alkenyl group containing from 8 to 22 carbon atoms; R ^21a represents an alkyl group containing from 1 to 3 carbon atoms; 1 means the number 0 or 1; AO means alkyleneoxy group containing from 3 to 5 carbon atoms; m means the average number of moles of attached C ₂ H ₄ O groups ranging from 5 to 30; n means the average number of moles of attached AO groups, ranging from 0 to 5; and “/” means that C ₂ H ₄ O-groups and AO groups can be distributed either by statistical addition or by block addition. 12. The method of cleaning a textile product according to claim 11, comprising applying a portion of the liquid detergent composition to be used on the textile product and contacting the treated textile product with a detergent solution containing the remainder of the liquid detergent composition and water to wash the textile product. 13. The use of a liquid detergent composition according to any one of paragraphs. 1-9 for cleaning a textile product.