JP2012233144A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition that inhibits the generation of the half-dry smell of a fiber product and has a high inhibiting effect on the recurrent half-dry smell.SOLUTION: The liquid detergent composition includes (A) a nonionic surfactant, (B) a specific cationic surfactant and (D) hydrogen peroxide each in a specific range and contains water. As component (A), a nonionic compound (A1) represented by formula (A1) as given below is contained in an amount of 0.5 to 10 mass% in the composition. The ratio of (c1) an anionic surfactant other than a fatty acid and a salt thereof to component (B), i.e. the mass ratio of (c1)/(B) is 0 to 1. The pH at 20°C as described in Paragraph 8.3 of JIS K3362:1998 is 3.0 to 7.0. Formula (A1) is R-O-(CHO)-H (wherein R is a 12C straight-chain alkyl group and the carbon atom of R which bonds to the oxygen atom of R-O- is a primary carbon atom; and x is an addition mole number of ethyleneoxy groups and is an integer of 2 to 5).

Description

  The present invention relates to a liquid detergent composition for textile products. Furthermore, it is related with the liquid detergent composition for textiles, especially for clothes.

  In recent years, with the increase in the number of nuclear families, the number of co-working generations has increased, and the number of households that wash and dry indoors at night and on holidays has increased. With the recent increase in energy conservation awareness, a new drying technology called low temperature drying that applies the dehumidifying function of air conditioners has been proposed as a washing dryer with low energy loss. However, laundry drying and low temperature drying make it easier to produce a fresh odor.

  On the other hand, the awareness of washing has changed. Specifically, there is an increasing tendency to use odor adhesion as a criterion for washing without being contaminated. The attachment of tobacco odors and body odors after exercise to textiles has long been a sufficient factor to remind you of washing, but recently, even if a minute amount of unpleasant odor is attached or generated It has become. Therefore, the generation of odor due to the continuous half-dry state of the textile product during drying after washing is not desirable, and it is also accompanied by the dissemination of information that links the odor and the growth of bacteria. People's interest is growing. Here, “freshly dried” means a state in which the fiber product is wet, in particular, a state in which the fiber product is wet with a small amount of moisture. Specifically, in relation to the washing and use of textile products, it means that the textile products after washing are moistened until they are dried in a humid environment without using a dryer. In some cases, the dry textile product may mean a wet state by wiping wet hands or body, rain or sweat.

  Various causes of raw dry odor are known, but decomposition products of sebum soil, specifically, metabolites due to the growth of microorganisms have been pointed out as causative substances. In Non-Patent Document 1, raw dry odor (room-dried odor) includes “smell-like odor” such as medium chain aldehyde, medium chain alcohol and ketone, “sour odor” such as short chain fatty acid and medium chain fatty acid, nitrogen compounds It has been reported that the contribution of medium-chain fatty acids is particularly large, which is a complex odor composed of “smelly odor” and sulfur compounds. Non-Patent Document 2 describes that 4-methyl-3-hexenoic acid has a strong odor as a raw dry odor of clothing, particularly as a medium chain fatty acid odor. Patent Document 1 proposes to use a medium-chain fatty acid having a specific structure as an indicator substance for a raw dry odor.

  The raw dry odor that is the subject of the present invention includes the odor that is generated when the laundry is dried, the odor that is generated when the laundry is left after being dehydrated, and the odor that is generated when the laundry is wetted with sweat or rain. The odor generated when drying indoors and the odor generated when left in the washing tub can be removed or reduced by sufficiently drying. However, it is difficult to remove the recurring odor that returns to the same odor when dried and rewet. Once the fiber product generates this raw dry odor, the odor is temporarily removed by sufficient drying after washing. However, it tends to recur during use. The recurring odor is reminiscent of the odor of cleaning tools used on floors and tables such as worn rags and mops. Such a freshly dried odor that is likely to recur is generated even in the case of outdoor drying, once the odor is generated, and cannot be easily removed.

  A characteristic feature of this recurrent dry odor is that it is odorless or almost odorless after being washed and sufficiently dried, but odor is generated when it is wet. In addition, this freshly dried odor is likely to occur when stored in a chase for a long time. In addition, textile products that are frequently used with human skin, such as underwear, handkerchiefs, or towels, and that are frequently used for a short period of the cleaning-use cycle, are in use once this recurrent dry-dry odor occurs. In addition, the odor often recurs, and as the number of washings increases, the odor intensity of a recurrent dry odor tends to increase.

  Conventionally, as a method for removing off-flavors and the like generated from textile products, masking using a fragrance component, and antibacterial or antibacterial sterilization of microorganisms that cause off-flavor using an antibacterial agent are known. A masking method using a fabric treatment agent containing an alicyclic ketone compound as a fragrance component or a fragrance component stabilizer is known (see, for example, Patent Documents 2 and 3). Known methods of deodorization by antibacterial and sterilization of microorganisms that cause off-flavors include methods using diketone compounds, cationic organic antibacterial agents, treatment agents containing fungicides such as triclosan and dichlorosan, etc. Yes. For example, Patent Literature 4 discloses a technique for suppressing a raw dry odor using a bactericide. In addition, Patent Document 5 discloses a volatile sulfur compound production inhibitor by enzyme inhibition using a specific fragrance component.

  A liquid bleaching agent containing hydrogen peroxide, a cationic surfactant and a nonionic surfactant is also known. Patent Document 6 discloses a liquid bleach composition in which a perfume is blended with hydrogen peroxide, a nonionic surfactant having an HLB of 5 to 12, and an anionic surfactant or a cationic surfactant. Other examples of liquid bleaching compositions containing such nonionic and cationic surfactants include Patent Documents 7 and 8. Also known is a liquid detergent composition containing hydrogen peroxide, which increases the detergency by changing the pH to alkaline when diluting water during use by blending a boron compound and a polyhydric alcohol. Patent Document 9 and Patent Document 10 can be cited.

JP 2009-244094 A JP 2010-31285 A JP 2007-314693 A JP 2009-263812 A JP 2008-173441 A Japanese Patent Laid-Open No. 9-59675 JP-A-9-188895 JP-A-9-217090 JP 2007-169530 A JP 2007-177145 A

Sugawara, Sonoda, “Detergents that Control Room Drying Odors”, Fragrance, September 2004, No.223, p.109-116 Takeuchi et al., “Analysis of Raw Dry Odor of Clothing”, 2010 Agricultural Chemical Society Abstracts p.149

  An object of the present invention is to provide a liquid detergent composition that suppresses the production of a raw dry odor of a textile product, and further a liquid that has a high inhibitory effect on a recurrent raw dry odor that has been difficult to remove among the raw dry odors. It is to provide a cleaning composition.

  Another object of the present invention is to provide a liquid detergent composition that is excellent in the visibility of the presence of bacteria due to bubbles without reducing the detergency, and a method for cleaning a textile product by the visual recognition.

In view of the above problems, the present inventors have conducted intensive studies from the viewpoints of causative substances, causative bacteria, and generation mechanisms of raw dry odors based on the washing and use of textile products. As a result, the present inventors have not only a fresh dry odor as a fresh dry odor but also a wet state until the drying after washing, as well as a recurrent property that is reappeared when the textile is sufficiently dried and then wetted. Focusing on the raw dry odor, new knowledge was obtained. That is, the fiber product is surprisingly odor produced by microorganisms, especially bacteria living or growing in the fiber product, even after the raw odor has been sufficiently removed by drying after washing. In addition, we found that a small amount of odor was trapped by the fiber due to drying and became undetectable after drying, but it was released again by wetting of the fiber product, that is, by dry drying, and it was easy to feel because it was a low threshold. . And the compound which controls the recurrent odor was found to be a branched medium chain fatty acid odor mainly composed of the 4-methyl-3-hexenoic acid (hereinafter sometimes referred to as 4M3H). And it identified that it was Moraxella sp . ( Moraxella sp .) As a causative bacterium of 4M3H, and discovered that this bacterium was resistant under a dry condition. From such a background, it has been clarified that even if the deodorizing effect after washing and drying is excellent, it does not immediately mean that it is effective in suppressing recurrent dry odor. In order to correctly evaluate the effect on the recurrent dry odor, it is necessary to newly design and evaluate a liquid detergent composition from the viewpoint of recognizing this problem.

  In addition, the present inventors not only suppress the production of conventional raw dry odor but also an effective liquid for suppressing the generation of recurrent raw dry odor, particularly 4-methyl-3-hexenoic acid odor. A detergent composition was developed.

In the present invention, the nonionic surfactant (A) [hereinafter referred to as component (A)] is 15 to 70% by mass, the cationic surfactant (B) represented by the following general formula (B1) [hereinafter, (B ) Component] is 0.3 to 5% by mass, hydrogen peroxide (D) [hereinafter referred to as (D) component] is 0.3 to 10% by mass, and a liquid detergent composition containing water. ,
(A) 0.5-10 mass% of nonionic compounds (A1) shown by the following general formula (A1) are contained in the composition as at least a part of the component,
The ratio of the anionic surfactant (c1) other than the fatty acid and its salt to the component (B) is 0 to 1 in a mass ratio of (c1) / (B),
The pH at 20 ° C. described in 8.3 of JIS K3362: 1998 is 3.0 to 7.0.
The present invention relates to a liquid detergent composition.
R—O— (C ₂ H ₄ O) _x —H (A1)
[Wherein, R is a linear alkyl group having 12 carbon atoms, and the carbon atom of R bonded to the oxygen atom of R—O— is a primary carbon atom. x is an added mole number of ethyleneoxy group and is an integer of 2 to 5. ]

Wherein, R ^b1 is a chain hydrocarbon group having 12 to 18 carbon atoms, in R ^b1 - (A'O) _s - may contain. A′O is an ethyleneoxy group or a propyleneoxy group, s represents an average added mole number of A′O and is 0 to 10, and R ^b2 , R ^b3 and R ^b4 are each independently a methyl group, ethyl Group, a benzyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and X ⁻ is CH ₃ SO ₄ ^— or CH ₃ CH ₂ SO ₄ ⁻ , a halogen ion. ]

  Moreover, this invention relates to the method of wash | cleaning textiles with the aqueous solution which dissolved the liquid cleaning composition of this invention in the said water.

Further, the present invention provides a nonionic surfactant (A) [hereinafter referred to as component (A)] of 15 to 70% by mass, a cationic surfactant (B) represented by the following general formula (B1) [hereinafter, A liquid detergent composition containing 0.3 to 5% by mass of (B) component, 0.3 to 10% by mass of hydrogen peroxide (D) [hereinafter referred to as (D) component], and water. There,
(A) 0.5-10 mass% of nonionic compounds (A1) shown by the following general formula (A1) as a component are contained in the composition,
The ratio of the anionic surfactant (c1) other than the fatty acid and its salt to the component (B) is 0 to 1 in a mass ratio of (c1) / (B),
The pH at 20 ° C. described in 8.3 of JIS K3362: 1998 is 3.0 to 7.0.
The present invention relates to a method for cleaning a textile product, which includes a step of applying a liquid detergent composition to the textile product to generate bubbles.
R—O— (C ₂ H ₄ O) _x —H (A1)
[Wherein, R is a linear alkyl group having 12 carbon atoms, and the carbon atom of R bonded to the oxygen atom of R—O— is a primary carbon atom. x is an added mole number of ethyleneoxy group and is an integer of 2 to 5. ]

Wherein, R ^b1 is a chain hydrocarbon group having 12 to 18 carbon atoms, in R ^b1 - (A'O) _s - may contain. A′O is an ethyleneoxy group or a propyleneoxy group, s represents an average added mole number of A′O and is 0 to 10, and R ^b2 , R ^b3 and R ^b4 are each independently a methyl group, ethyl Group, a benzyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and X ⁻ is CH ₃ SO ₄ ^— or CH ₃ CH ₂ SO ₄ ⁻ , a halogen ion. ]

  The liquid detergent composition of the present invention has an excellent inhibitory effect on raw dry odors generated from textile products, recurrent raw dry odors generated by wetting after drying, and in particular, 4M3H odors.

  In addition, in the case of using the liquid detergent composition of the present invention applied to a textile product, the presence of bacteria in the textile product forms a bubble that is easy to visually recognize. Can be performed.

  Hereinafter, the liquid detergent composition of the present invention will be described in detail.

<(A) component>
The liquid detergent composition of this invention contains the nonionic surfactant of (A) component as main surfactant.

  As the nonionic surfactant of component (A), a nonionic surfactant having a chain hydrocarbon group having 8 to 22 carbon atoms and a hydrophilic group such as an ethyleneoxy group or a hydroxy group in the molecule is used. Can be mentioned. Furthermore, polyoxyalkylene alkyl or alkenyl ether having an ethyleneoxy group as an alkyleneoxy group, polyoxyalkylene alkyl having an ethyleneoxy group as an alkyleneoxy group (further alkyl having 1 to 3 carbon atoms) ether fatty acid ester, alkyl polyglycoside , Alkyl glycosides, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, other polysaccharide surfactants, fatty acid monoglycerides, fatty acid alkanolamides, polyhydroxy fatty acid amides, polyglycerin fatty acid esters, polyglycerin alkyl ethers, and the like.

  Among these, from the viewpoint of detergency and deodorizing effect, the component (A) is preferably at least one nonionic surfactant selected from the following (a1) to (a5). More preferably, the following (a1) and / or (a2) and (a3) are used in combination, and the detergency, deodorizing effect, and visibility due to foaming in contact with a textile product containing bacteria ( Hereinafter, from the viewpoint of foaming visibility), it is even more preferable to use (a1) and (a3) in combination. In particular, the foaming property by coating is preferably the surfactant (a1) having a PO group. The preferred requirements of (a1), (a2) and (a3) were also described subsequently.

(A1): Polyoxyalkylene alkyl or alkenyl ether type nonionic surfactant represented by the following general formula (a1) [hereinafter referred to as component (a1)]
R ^1a —O [(C ₂ H ₄ O) _p / (AO) _q ] H (a1)
[Wherein, R ^1a represents an alkyl group or alkenyl group having 8 to 22 carbon atoms. AO is an alkyleneoxy group having 3 to 5 carbon atoms. p and q are average addition mole numbers, p is a number of 8-40, and q is a number of 0-5. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded randomly or in blocks. ]
(A2): Polyoxyalkylene short chain alkyl ether fatty acid ester or aliphatic alkyl ether type nonionic surfactant represented by the following general formula (a2) [hereinafter referred to as component (a2)]
_{^{R 2a (CO) l O -}} [(C 2 H 4 O) m / (AO) n] R 21a (a2)
[Wherein, R ^2a is an alkyl group or alkenyl group having 8 to 22 carbon atoms. R ^21a is an alkyl group having 1 to 3 carbon atoms. l is a number of 0 or 1, and AO is an alkyleneoxy group having 3 to 5 carbon atoms. m and n are average addition mole numbers, m is a number of 5-30, n is a number of 0-5. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded randomly or in blocks. ]
(A3): Polyoxyethylene alkyl ether type nonionic surfactant represented by the following general formula (a3) [hereinafter referred to as component (a3)]
R ^3a —O— (C ₂ H ₄ O) _r —H (a3)
[Wherein, R ^3a is an alkyl group or alkenyl group having 8 to 22 carbon atoms. The carbon atom of R ^3a bonded to the oxygen atom of R ^3a —O— is a primary carbon atom and / or a secondary carbon atom. r is an average added mole number, and is a number of 2 or more and less than 8. ]
(A4): Polyglycerin alkyl or alkenyl ether type nonionic surfactant (hereinafter referred to as component (a4))
(A5) polysaccharide type surfactant (hereinafter referred to as component (a5))

  A preferred embodiment of the component (a1) is as follows.

The component (a1) is a C8 to C22, preferably C10 to C18, more preferably C12 to C16 alkyl group or alkenyl group, preferably a primary or secondary alcohol having an alkyl group, ethylene oxide [below And EO in some cases] and an alkylene oxide having 3 to 5 carbon atoms can be obtained by addition reaction in a random or block manner. R ^1a in formula (a1) is such that the carbon atom of R ^1a bonded to the oxygen atom of R ^1a —O— is a first carbon atom and / or a secondary carbon atom, and further a first carbon atom. And a straight-chain alkyl group is preferred.

Further, p in the general formula (a1) is an average added mole number of ethyleneoxy group (C ₂ H ₄ O, hereinafter also referred to as EO group), and is 8 to 8 in terms of solubility in water and washing performance. 40, preferably 10-40, more preferably 14-35, and even more preferably 16-30. q is the average number of moles of AO group added, and is 0 to 5, preferably 1 to 5, more preferably 1 to 4 and even more preferably 1 to 3 from the viewpoint of cleaning performance. Moreover, when q = 0, p is preferably 18 to 35, and more preferably 20 to 30.

  The AO group in the general formula (a1) is obtained by addition reaction of an alkylene oxide having 3 to 5 carbon atoms, and the portion bonded by the addition reaction has a structure of methyl branch, ethyl branch or propyl branch. Those are preferred. Furthermore, the AO group is preferably an alkyleneoxy group having 3 carbon atoms and / or an alkyleneoxy group having 4 carbon atoms. Specifically, a trimethyleneoxy group, an oxypropane-1,2-diyl group, an oxybutane-1,2 -A diyl group, an oxybutane-1,3-diyl group, an oxybutane-2,3-diyl group, and an oxytetramethylene group can be mentioned. The AO group is more preferably an oxypropane-1,2-diyl group (hereinafter, in the present invention, the oxypropane-1,2-diyl group may be a propyleneoxy group or a PO group).

In the present invention, in general formula (a1), R ^1a has 10 to 18 carbon atoms, more preferably 12 to 16, and the carbon atom of R ^1a bonded to the oxygen atom of R ^1a —O— is the first carbon atom. A linear alkyl group having an average addition mole number p of EO group of 14 to 35, more preferably 16 to 30, an AO group being a propyleneoxy group, and an average addition mole number q of 1 to 4, more preferably 1-3, and even more preferably 2-3 non-ionic surfactant (hereinafter referred to as non-ionic surfactant (a1 ′)), low-temperature storage stability, cleaning performance, and It is preferable from the viewpoint of foaming visibility at the time of coating use. Since the nonionic compound of the general formula (A1) has strong hydrophobicity, the nonionic compound represented by the general formula (A1) includes a large number of added moles of ethyleneoxy group and a highly hydrophilic surfactant. An ionic compound can be stably contained in the composition, and this effect can be exhibited. In addition, by having a propyleneoxy group, not only can the liquid detergent composition be further stabilized and detergency can be obtained, but in the case of application, it is easy to foam and easily visible in the presence of bacteria, but immediately thereafter. Bubbles are easy to disappear and the liquid detergent composition has excellent permeability into the fiber. From this viewpoint, in the present invention, it is preferable to use a nonionic surfactant (a1 ′) as the component (A).

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

Examples of the nonionic surfactant represented by the general formula (a1) include nonionic surfactants represented by the following general 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 ] H (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 H (a1-6)
[Wherein, R ^1a , p, q, and AO have the above-mentioned meanings, and p11, p12, and p13 are average added mole numbers, respectively, and are non-zero numbers, and p = p11 + p12 + p13. “·” Indicates a random bond. ]

The nonionic surfactants represented by the general formulas (a1-1) to (a1-6) can be prepared by taking into consideration the reaction ratio and reaction sequence of alkylene oxide with respect to R ^1a OH. In the general formulas (a1-1) to (a1-6), the average number of added moles of each alkyleneoxy group may be the number of moles of each alkylene oxide used for R ^1a OH during the reaction, or Any of the average addition mole number of the alkyleneoxy group of the obtained compound may be sufficient. In addition, p11 and p12 are independently preferably 1 to 20, p11 is preferably 3 to 20, and p12 is more preferably 1 to 15, p11 is preferably 4 to 15, and p12 is more preferably 3 to 15. Further, p13 is preferably from 0.1 to 10. The range of p11, p12, and p13 shall depend on each range condition of p and q thru | or general preferred range conditions of general formula (a1). Furthermore, the general formulas (a1-1) to (a1-6) are more preferably defined as subordinate concepts of the nonionic surfactant (a1 ′).

As described above, R ^1a in the general formula (a1) may be an alcohol derived from natural fats and oils. From the viewpoint of storage stability, the nonionic surfactant of the general formula (a1-2), (a1-4), (a1-5) or (a1-6) is preferable, and among these, the general formula (a1- The nonionic surfactant of 5) or (a1-6) is more preferred, and the nonionic surfactant of general formula (a1-5) is more preferred.

The component (a1) of the present invention reacts, for example, an alkylene oxide having 3 to 5 carbon atoms and ethylene oxide according to the structure of the general formulas (a1-1) to (a1-6) with respect to R ^1a OH. It is obtained by. From the target structure, the blending order and conditions may be examined, and the addition reaction may be performed in a block or random manner. Further, the reaction ratio of the alkylene oxide having 3 to 5 carbon atoms and ethylene oxide per mole of R ^1a OH is within the range of p and q in the general formula (1), that is, p = 8 to 40, q = 0 to 0. 5, p = p11 + p12 + p13, or the preferred range described above. In other words, the reaction ratio of the alkylene oxide having 3 to 5 carbon atoms to be added to the aliphatic alcohol and ethylene oxide may be in the numerical range of p and q, p11, p12, and p13.

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

  As the component (a1) of the present invention, a more preferable nonionic surfactant has a structure of the general formula (a1-5) or (a1-6), and more preferably a structure of the general formula (a1-5). . In the general formula (a1-5), p11 / (p11 + p12) is preferably 0.2 to 0.8.

As the optimum production conditions further narrowing down the ranges of p11, p12, p13 and q, a production method having the following steps A to D can be mentioned.
Step A: With respect to ¹ mol of R ^1a OH, ethylene oxide is subjected to addition reaction at a ratio of 4 to 14 mol, preferably 8 to 12 mol (the numerical range may be defined as p11 in the above formula). .
Step B: Next, 1 to 3 mol of propylene oxide, preferably 2 to 3 mol (the numerical range may be defined as q in the above formula) and 0 to 4 mol of ethylene oxide (the numerical range is the above formula) (Which may be defined as p13 of the above) is subjected to a random or block addition reaction. More preferably, only propylene oxide is subjected to an addition reaction of 2 to 3 moles (the numerical range may be defined as n in the above formula).
Step C: Thereafter, ethylene oxide is again subjected to an addition reaction of 4 to 14 mol, preferably 8 to 12 mol (the numerical range may be defined as p12 in the above formula).
Process D: The process for the catalyst used for reaction is performed. For example, when an alkali catalyst is used, it is neutralized with an acid, and when it is a solid catalyst, filtration is performed.

P and q, etc. for the component (a1) can be determined by NMR or liquid chromatographic analysis. The alkyleneoxy group is short, for example, the alkyl group is less than 8 moles of ethylene oxide per mole of linear primary alcohol. In the case of a compound obtained by an addition reaction at a ratio of, gas chromatographic analysis may be used. Or in this invention, p, q, etc. may be the ratio of the C3-C5 alkylene oxide and ethylene oxide reacted per mol of R <^1a> O-H.

  Moreover, the preferable aspect of (a2) component is as follows.

In the general formula (a2) of the component (a2), R ^2a is an alkyl group or alkenyl group having 8 to 22 carbon atoms, preferably an alkyl group or alkenyl group having 10 to 18 carbon atoms, more preferably 12 to 14 carbon atoms, More preferably, it is a linear alkyl group having 12 to 14 carbon atoms. R ^21a is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group. l is a number of 0 or 1, more preferably a number of 1. AO is an alkyleneoxy group having 3 to 5 carbon atoms, and is obtained by addition reaction of alkylene oxide having 3 to 5 carbon atoms, and the portion bonded by the addition reaction is methyl-branched, ethyl-branched or propyl-branched. Those having a structure are preferred. Further, the AO group is preferably an alkyleneoxy group having 3 carbon atoms and / or an alkyleneoxy group having 4 carbon atoms, specifically, a trimethyleneoxy group, an oxypropane-1,2-diyl group, an oxybutane-1,2- Examples thereof include a diyl group, an oxybutane-1,3-diyl group, an oxybutane-2,3-diyl group, and an oxytetramethylene group. Among these, the AO group is preferably an oxypropane-1,2-diyl group (hereinafter, in the present invention, the oxypropane-1,2-diyl group may be a propyleneoxy group or a PO group). m and n are average addition mole numbers, m is 5-30, Furthermore, 8-25, More preferably, 10-20 are preferable, n is the number of 0-5, Furthermore, the number of 0-3 is preferable.

  When n is 0 <n ≦ 3, and further when n is 0.5 to 3, as the nonionic surfactant represented by the general formula (a2), the following general formula (a2-1), ( The nonionic surfactant represented by a2-2) or (a2-3) is preferable, and general formula (a2-2) is more preferable from the viewpoint of storage stability of the liquid. AO is preferably an oxypropane-1,2-diyl group (hereinafter, in the present invention, the oxypropane-1,2-diyl group may be a propyleneoxy group or a PO group), m is 5 to 30, and Is preferably 8 to 25, more preferably 10 to 20. In the case of general formula (a2-3), m is preferably 10-30.

^{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) m - (AO) n -CH 3 (a2-2)
^{R 2a (CO) O- (C} 2 H 4 O) m -CH 3 (a2-3)

  Moreover, the preferable aspect of (a3) component is as follows.

In the general formula (a3) of the component (a3), R ^3a is an alkyl group or alkenyl group having 8 to 22 carbon atoms, preferably an alkyl group or alkenyl group having 10 to 18 carbon atoms, more preferably 12 to 14 carbon atoms, More preferably, it is a linear alkyl group having 12 to 14 carbon atoms. The carbon atom of R ^3a bonded to the oxygen atom of R ^a3 —O— is a primary carbon atom and / or a secondary carbon atom. In the present invention, an alkyl group or an alkenyl group having a secondary carbon atom may be expressed as a straight chain in order to be separated from a branched hydrocarbon group. The average added mole number r of the ethyleneoxy group is 2 or more and less than 8, preferably 2.5 to 7.5, more preferably 3 to 7.

As for the production of the nonionic surfactant in which the carbon atom of R ^3a bonded to the oxygen atom is the first carbon atom, a method of adding ethylene oxide to the primary alcohol can be mentioned. For the production of a nonionic surfactant in which the carbon atom of R ^3a bonded to the oxygen atom is a secondary carbon atom, a method of adding ethylene oxide to a secondary alcohol or reacting ethylene oxide with a 1-olefin or an internal olefin Well-known production methods such as a method of reacting polyethylene glycol with olefin and a method of adding ethylene oxide by introducing a hydroxyl group into n-paraffin can be used.

  Moreover, the preferable aspect of (a4) component is as follows.

The component (a4) is preferably a compound represented by the following general formula (a4).
^R4a- O-[(AO) _s / (Gly) _t ] -H (a4)
[Wherein, R ^4a represents an alkyl group or an alkenyl group having 8 to 22 carbon atoms. AO is an ethyleneoxy group or propyleneoxy group, Gly is a residue derived from glycerin, s is an average addition mole number of AO, t is an average addition mole number of Gly, s is 0 to 5, and t is 2 to 10 It is. / Indicates that AO and Gly may be random or block. ]

R ^4a in general formula (a4) preferably has 12 to 16 carbon atoms, more preferably 12 or 14 carbon atoms, and R ^4a bonded to a linear alkyl group, particularly an oxygen atom of R ^4a —O—. Straight chain alkyl groups in which the carbon atom is the first carbon atom are preferred. s is preferably 0. t represents the average number of moles added and is preferably 2-5.

  The compound represented by the general formula (a4) may be a mixture containing s = 0 and compounds having different addition mole numbers t ′ (integer values) of Gly. In this case, a mixture containing one or more, more preferably two or more compounds having t ′ of 3, 4 or 5 is preferred. In the mixture, the total ratio of the compounds whose t ′ is 3, 4 or 5 is preferably 40% by mass or more, more preferably 60% by mass or more, still more preferably 80% by mass or more, From the viewpoint of low-temperature cleaning performance, it is preferably 99% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less. Further, the proportion of the compound having t 'of 1 or 2 in the mixture is preferably less than 50% by mass, and more preferably less than 35% by mass.

  Moreover, the preferable aspect of (a5) component is as follows.

Examples of the component (a5) include polysaccharide-type surfactants represented by the following general formula (a5).
R ^5a- (OR ^51a ) _x Z _y (a5)
[Wherein R ^5a is an alkyl or alkenyl group having 8 to 18 carbon atoms, R ^51a is an alkylene group having 2 to 4 carbon atoms, Z is a residue derived from a reducing sugar having 5 or 6 carbon atoms, x is an average The number of added moles is shown, x is a number from 0 to 6, y is an average degree of condensation, and y is a number from 1 to 10. ]

In the general formula (a5), R ^5a is preferably 12 to 16 carbon atoms, more preferably having 12 or 14 carbon atoms, also straight-chain alkyl group, the R ^5a to bind to inter alia R ^5a -O- oxygen atom carbon A straight-chain alkyl group in which the atom is the first carbon atom is preferred. x is preferably 0. Z is preferably a glucose residue. The average degree of condensation of y is preferably 1.2-3. The compound represented by the general formula (a5) may be a mixture including compounds having different condensation degrees y ′ (integer values) of Z. In this case, a mixture containing one or more, more preferably two or more compounds where x = 0 and y ′ is 1, 2 or 3 is preferred. In the mixture, the total ratio of compounds in which y ′ is 1, 2 or 3 is preferably 60% by mass or more, and more preferably 80% by mass or more.

The liquid detergent composition of the present invention contains, as component (A), a nonionic compound represented by the following general formula (A1) [hereinafter sometimes referred to as component (A1)].
R—O— (C ₂ H ₄ O) _x —H (A1)
[Wherein, R is a linear alkyl group having 12 carbon atoms, and the carbon atom of R bonded to the oxygen atom of R—O— is a primary carbon atom. x is an added mole number of ethyleneoxy group and is an integer of 2 to 5. ]

  From the viewpoint of achieving the object of the present invention, R in the general formula (A1) is straight-chain alkyl having 12 carbon atoms, and the hydrocarbon group of the alkyl group bonded to oxygen is the first carbon atom. is important. The nonionic compound (A1) is used in combination with the cationic surfactant (B), which suppresses the generation of odors in textile products caused by fresh drying, mainly 4M3H, which has been difficult to remove. As well as being able to control recurrent, dry odors. In addition, as for the component (A1), x in the general formula (A1) is 3, 4 because a compound having 3, 4 and 5 moles of EO group is excellent in the effect of suppressing a raw dry odor, particularly a recurring raw dry odor. Or 5 is preferable. Furthermore, in the component (A1), it is preferable that the total of the compounds in which x in the general formula (A1) is 3, 4 or 5 occupy 70 to 100% by mass, more preferably 80 to 100% by mass.

The component (A1) may be a compound having a single number of added moles of polyethyleneoxy groups synthesized in the composition of the present invention, or a polyoxyethylene alkyl ether having a different number of added moles of ethyleneoxy groups. It can mix | blend as a component in the nonionic surfactant manufactured and obtained as a mixture. From an economical viewpoint in production, the component (A1) may be, for example, a component derived from the component (a1) or the component (a3), and when derived from the component (a3), R ^{3a in the} general formula (a3) is A straight-chain alkyl group having 12 carbon atoms, and the carbon atom of R ^3a bonded to the oxygen atom of R ^3a —O— is the first carbon atom. In the case of the nonionic surfactant of the general formula (a3), for example, a nonionic surfactant obtained by adding an average of 2 to less than 8 mol of ethylene oxide to lauryl alcohol under an alkali catalyst or an acid catalyst (A1 ) It is preferable to contain as a nonionic surfactant containing a component. In this case, the component (a3) is produced as a mixture of polyoxyethylene lauryl ethers in which the number of added moles of ethyleneoxy groups is distributed, and the component (A1) is contained in the mixture. It is necessary to confirm the content of the compound corresponding to the component (A1) in the component (a3) and adjust the content in the composition of the component (A) or the component (A1).

Although the component (A1) varies depending on the production method, it may be contained in a small amount even when the component (a1) is q = 0 and R ^1a is derived from lauryl alcohol (when it is a lauryl group). . Therefore, also about (a1) component, based on a structure, a manufacturing method, etc., content of the compound corresponded to (A1) component is confirmed suitably, and inclusion in the composition of (A) component or (A1) component It can mix | blend by adjusting quantity etc. In addition, when (a1) component is q> = 1 or more, and also when propyleneoxy group is contained as AO, (A1) component derived from (a1) component is hardly contained.

The component (A1) may be the same as the component (a3). For example, as the component (a3), R ^3a is a linear alkyl group having 12 carbon atoms, the carbon atom of R ^3a bonded to the oxygen atom of R ^a3 —O— is the first carbon atom, and an ethyleneoxy group When the number of added moles is a single added mole number having no distribution, the average added mole number r can be 2, 3, 4 or 5, and therefore such a compound is used as the component (A1). be able to. That is, the component (a3) may include the component (A1). In addition, (A1) component may be used in combination of two or more.

  Moreover, when mix | blending (A1) component as a component in (a3) component, since there are few addition moles of ethylene oxide used for reaction, it is normally obtained as a mixture containing unreacted alcohol. If the unreacted alcohol affects the odor problem or the storage stability of the composition, it may be reduced by distillation or the like.

  In the present invention, the proportion of the unreacted alcohol and the compound having 1 mol of EO group, that is, the aliphatic alcohol having a hydrocarbon group having 8 to 22 carbon atoms and the compound having 1 mol of EO group added to the alcohol is (A) In the component nonionic surfactant, the content is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. However, the lower limit is considered after considering the energy and environment required for the distillation process.

  The liquid detergent composition of the present invention contains 0.5 to 10% by mass, preferably 1 to 8% by mass, of the nonionic compound of component (A1) from the viewpoint of suppressing the dry odor of textiles, particularly 4M3H odor. %, More preferably 2 to 5% by mass. In addition, (A1) component comprises a part of nonionic surfactant which is (A) component.

  From the viewpoint of detergency, the liquid detergent composition of the present invention contains 15 to 70% by mass, preferably 20 to 65% by mass, more preferably 25 to 60% by mass of the nonionic surfactant as component (A). Even more preferably, 30 to 55% by mass is contained. This amount includes the content of the component (A1).

  In addition, the total concentration of the (a1) component to the (a5) component mentioned as specific examples of the nonionic surfactant, and further the (a1) to (a3) component nonionic surfactants occupy the component (A). The proportion is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 80 to 100% by mass. Of these, the nonionic surfactant of the component (a1) and / or the component (a2), and the nonionic surfactant of the component (a1) are preferably used as the main nonionic surfactant, and the liquid cleaning of the present invention In the case of use of the cleaning agent and coating, the agent composition is preferably (a1) component and / or (a2) component, more preferably (a1) component, more preferably 10 to 60% by mass, more preferably from the viewpoint of foaming visibility. 15-55 mass%, More preferably, it contains 20-50 mass%. Moreover, the liquid detergent composition of the present invention is preferably 0.5 to 20% by mass, more preferably 1 to 18% by mass, and still more preferably 2 from the viewpoint of deodorizing effect and liquid stability. Contains ~ 15% by mass.

  The liquid cleaning composition of the present invention contains the component (A1) and the component (B) stably in the composition, and in order to sufficiently exert the cleaning power and the effect of suppressing the dry odor, the components (A) and ( It is preferable that the component A) satisfies at least one of the following conditions (1) to (8).

Condition (1): The component (A) is contained in the liquid detergent composition in an amount of 20 to 65% by mass, preferably 25 to 60% by mass.
Condition (2): The component (A1) is contained in the liquid detergent composition in an amount of 1 to 8% by mass, preferably 2 to 5% by mass.
Condition (3): The component (a1) is contained as the component (A).
Condition (4): The component (A1) is contained as the component (A), and the component (a1) is represented by the general formula (a1), and further, in the general formula (a1-5), R ^1a has 12 to 16 carbon atoms. R ^1a bonded to the oxygen atom of R ^1a —O— is an alkyl group in which the carbon atom of R ^1a is the first carbon atom, the AO group is a propyleneoxy group, and p = 14 to 35 [general formula (a1- In the case of 5), p11 = 1 to 20 and p12 = 1 to 20. ], Q = 1-3.
Condition (5): The component (a1) is contained in the liquid detergent composition in an amount of 15 to 55% by mass, preferably 20 to 50% by mass.
Condition (6): The component (a3) is contained as the component (A).
Condition (7): The component (A3) is contained as the component (A), and the component (a3) is a linear alkyl group having 12 to 14 carbon atoms in R ^a3 in the general formula (a3). The carbon atom of R ^3a bonded to the oxygen atom of R ^a3 —O— is the first carbon atom, and r is 3-7.
Condition (8): The component (a3) is contained in the liquid detergent composition in an amount of 1 to 18% by mass, preferably 2 to 15% by mass.

Based on the above conditions, the liquid detergent composition of the present invention is
The component (A) is contained in the liquid detergent composition at 20 to 60% by mass, preferably 25 to 55% by mass,
The component (A1) is contained in the liquid detergent composition in an amount of 1 to 8% by mass, preferably 2 to 5% by mass,
As the component (A), in the general formula (a1) and further in the general formula (a1-5), R ^1a has 12 to 16 carbon atoms, and the carbon atom of R ^1a bonded to the oxygen atom of R ^1a —O— It is an alkyl group having the first carbon atom, the AO group is a propyleneoxy group, and p = 14 to 35 [in the case of the general formula (a1-5), p11 = 1 to 20 and p12 = 1 to 20 . ] The component (a1) where q = 1 to 3 is contained in the liquid detergent composition in an amount of 15 to 55% by mass, preferably 20 to 50% by mass,
As the component (A), in general formula (a3), R ^a3 is a linear alkyl group having 12 to 14 carbon atoms, and the carbon atom of R ^3a bonded to the oxygen atom of R ^a3 —O— is the first carbon. It is preferable to contain 1 to 18% by mass, preferably 2 to 15% by mass of the component (a3) which is an atom and r is 3 to 7.

  However, the component (A1) may be derived from the component (a1) as well as the component (a3). In addition, the preferable aspect on the structure of each component follows the above-mentioned requirements. Further, the concentration range of each non-ionic surfactant compound in the subordinate concept and the total concentration range thereof may be within the range included in the concentration range of the component (A), which is the superordinate concept. Ranges may be combined.

  Moreover, said conditions (1)-(8) description and a preferable requirement are also a preferable requirement also from a viewpoint of the foaming visibility at the time of application | coating use.

<(B) component>
The liquid detergent composition of the present invention contains a cationic surfactant represented by the general formula (B1) as the component (B).

Wherein, R ^b1 is a chain hydrocarbon group having 12 to 18 carbon atoms, in R ^b1 - (A'O) _s - may contain. A′O is an ethyleneoxy group or a propyleneoxy group, s represents an average added mole number of A′O and is 0 to 10, and R ^b2 , R ^b3 and R ^b4 are each independently a methyl group, ethyl Group, a benzyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and X ⁻ is CH ₃ SO ₄ ^— or CH ₃ CH ₂ SO ₄ ⁻ , a halogen ion. ]

Formula (B1) the number of carbon atoms of R ^b1 in is preferably from 14 to 18, 14 to 16 is more preferable. In addition, the chain hydrocarbon group of R ^b1 excludes a benzene ring or a cyclic structure group. The chain hydrocarbon group is preferably a linear alkyl group or a linear alkenyl group, and more preferably derived from natural fats and oils. S is preferably 0.

X ⁻ in the general formula (B1), which is the counter ion of the component (B), is preferably CH ₃ SO ₄ ^— or CH ₃ CH ₂ SO ₄ ^{— in} order to obtain a sufficient odor suppressing effect.

As the cationic surfactant of the component (B), for example, the following (b1) to (b4) can be used, but it is more preferable to contain a compound selected from (b1) and (b3). It is preferable that the compound of (b1) accounts for 50% by mass or more, further 60% by mass or more, and more preferably 80% by mass or more in the component (B). In the compounds (b1) to (b4), the carbon number of R ^b1 is preferably 12 to 16, more preferably 14 to 16, and the chain hydrocarbon group is preferably a linear alkyl group, Those derived from natural fats and oils are preferred. The counter ion is preferably CH ₃ SO ₄ ^— or CH ₃ CH ₂ SO ₄ ^— .

(B1) A quaternary ammonium salt in which R ^b1 in the general formula (B1) is a linear alkyl group having 12 to 18 carbon atoms, and R ^{b2 to} R ^b4 are each an alkyl group having 1 to 3 carbon atoms.
(B2) A quaternary ammonium salt in which R ^b1 in the general formula (B1) is a branched alkyl group having 12 to 18 carbon atoms, and R ^{b2 to} R ^b4 are each an alkyl group having 1 to 3 carbon atoms.
(B3) A quaternary ammonium salt in which R ^b1 in the general formula (B1) is a linear alkyl group having 12 to 18 carbon atoms, and R ^b3 and R ^b4 are each an alkyl group having 1 to 3 carbon atoms.
(B4) R ^b1 in formula (B1) is a linear alkyl group having 12 to 18 carbon atoms, s is ^{1~5, R b2, R b3,} R b4 is 1 to 3 carbon atoms, respectively A quaternary ammonium salt which is an alkyl group.

  Component (B), a cationic surfactant, can be combined with the nonionic compound (A1) to suppress the growth of odor-causing bacteria in textile products having excellent drying resistance. That is, among the freshly dried odors, the fiber product is sufficiently dried, and then exhibits a remarkable inhibitory effect on the recurrent freshly dried odors that turn back by being dampened. That is, it works effectively in suppressing the generation of the medium chain fatty acid odor mainly composed of the aforementioned 4-methyl-3-hexenoic acid.

  In the liquid detergent composition of the present invention, the component (B) is 0.3 to 5% by mass, preferably 0.3 to 4% by mass, from the viewpoints of suppression of raw dry odor, particularly suppression of 4M3H odor and detergency. More preferably, the content is 0.5 to 3% by mass, and still more preferably 0.8 to 3% by mass.

<(C) component>
By the way, the liquid cleaning composition of this invention contains the nonionic surfactant (A) containing a nonionic compound (A1) and a cationic surfactant (B) as an essential component as surfactant. However, you may contain other surfactant (C) [henceforth (C) component], such as anionic surfactant and an amphoteric surfactant, with a restriction | limiting.

  Among the anionic surfactants, anionic surfactants other than fatty acids and salts thereof are feared to reduce the odor suppressing effect of the liquid detergent composition of the present invention, and are therefore described separately from fatty acids and salts thereof. To do. In addition, when pH of the liquid cleaning composition of this invention is acidic, depending on surfactant, it may exist as an acid type compound, and an acid type compound is also considered as surfactant.

(C1) Anionic surfactants other than fatty acids and salts thereof As specific examples of anionic surfactants other than fatty acids and salts thereof,
(C1-1) alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 20,
(C1-2) It has an alkyl group derived from a linear primary alcohol or linear secondary alcohol having 10 to 20 carbon atoms or an alkyl group derived from a branched alcohol, and the average number of added moles of an alkyleneoxy group is 1 to 5 A polyoxyalkylene alkyl ether sulfate ester salt that contains an ethyleneoxy group as an alkyleneoxy group and may contain a propyleneoxy group in an average addition mole number range of 0.2 to 2 mol,
(C1-3) alkyl or alkenyl sulfate ester salt having an alkyl group or alkenyl group having an average carbon number of 10 to 20, and (c1-4) a linear primary alcohol or linear secondary alcohol having an average carbon number of 10 to 20 Having an alkyl group derived from a branched alcohol or an alkyl group derived from a branched alcohol, having an alkyleneoxy group having an average addition mole number of 1 to 5, containing an ethyleneoxy group as the alkyleneoxy group, and having an average addition mole number of 0.2 to 2 mol A polyoxyalkylene alkyl ether carboxylate which may contain a propyleneoxy group in the range of
And so on. The salt is preferably an alkali metal salt such as sodium or potassium from the viewpoint of suppressing a dry odor.

  In the present specification, a bleach activator having an anionic group, in particular, an alkanoyloxybenzenesulfonic acid or alkanoyloxybenzenecarboxylic acid having a linear or branched alkyl group having 8 to 22 carbon atoms or an alkali thereof. The metal salt is an anionic surfactant (c1) other than fatty acid and its salt.

(C2) Fatty acid and its salt The fatty acid and its salt are preferably fatty acids having 10 to 18 carbon atoms and their salts, and those having a fatty acid distribution obtained from natural fats and oils may be used. A fatty acid and its salt can be mix | blended with the liquid detergent composition of this invention as an antifoamer. The salt is preferably an alkali metal salt such as sodium or potassium.

(C3) Amphoteric surfactant As an amphoteric surfactant, sulfobetaine or carbobetaine having an alkyl group having 8 to 22 carbon atoms, or fatty acid amidopropyl (or hydroxypropyl) having an alkyl group having 7 to 21 carbon atoms Examples include betaine and carbobetaine.

(C4) Cationic surfactants other than component (B) As cationic surfactants other than component (B), quaternary ammonium compounds other than component (B), amine compounds such as fatty acids having 7 to 21 carbon atoms Mention may be made of amine compounds such as amidopropyldimethylamine.

  Anionic surfactants (c1) other than fatty acids and salts thereof reduce the bactericidal effect of the (A1) component and the (B) component. Content is limited. Specifically, the ratio of the anionic surfactant (c1) other than the fatty acid and its salt to the cationic surfactant (B), that is, the mass ratio of (c1) / (B) is 0 to 1, preferably. Is 0 to 0.8, more preferably 0 to 0.5, more preferably 0 to 0.1. As described above, in the present invention, a bleaching activator having an anionic group is also considered as an anionic surfactant (c1) other than fatty acids and salts thereof, but the blending ratio is preferably low. Let the mass of an anionic surfactant (c1) be a numerical value at the time of assuming an acid type. After satisfying such a (c1) / (B) mass ratio, the content of the anionic surfactant (c1) other than the fatty acid and its salt is 5% by mass or less in the liquid detergent composition, It is preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 0.4% by mass or less.

  The amphoteric surfactant can be blended to such an extent that the effects of the present invention are not impaired, but the mass ratio of [(c1) + (c3)] / (B) is in the range of (c1) / (B). It is preferable to use in such an amount. The component (c3) is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less, in the composition after satisfying the mass ratio.

  The content of the fatty acid and its salt (c2) in the composition is 0.05 to 5% by mass, more preferably 0.1 to 4% by mass, still more preferably in terms of fatty acid (in terms of acid type compound). Is 0.1-3 mass%. In the composition, the fatty acid salt may exist in an acid form due to pH. The salt is preferably an alkali metal salt such as sodium or potassium from the viewpoint of suppressing a dry odor.

<(D) component>
The liquid detergent composition of the present invention contains hydrogen peroxide as the component (D) for the purpose of suppressing the raw dry odor. In the present invention, by using the nonionic compound (A1), the cationic surfactant (B) and the hydrogen peroxide (D) under specific conditions, it has not been possible to solve the problem sufficiently in the past. It shows the effect of suppressing the generation of odors in the entire textile product, including raw dry odors that tend to recur.

  In the liquid detergent composition of the present invention, the component (D) is 0.3 to 10% by mass, preferably 0.5 to 8% by mass, more preferably 1 from the viewpoints of suppression of raw dry odor and hydrogen peroxide stability. Contains ~ 6% by mass. The hydrogen peroxide concentration in the composition can be measured by a back titration method using a potassium iodide solution.

<Other ingredients>
Hereinafter, other components that can be used in the present invention will be described.

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

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

  Examples of water-miscible organic solvents include (e1) alkanols such as ethanol, 1-propanol, 2-propanol, 1-butanol, (e2) glycols such as propylene glycol, butylene glycol, hexylene glycol, and (e3) diethylene glycol. , Glycols such as triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, (e4) diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, tripropylene glycol Rumonomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methylglycerol ether, 2-methylglycerol ether, 1,3-dimethylglycerol ether, 1-ethylglycerol ether, 1,3- Alkyl ethers such as diethyl glycerin ether, triethyl glyceryl ether, 1-pentyl glyceryl ether, 2-pentyl glyceryl ether, 1-octyl glyceryl ether, 2-ethylhexyl glyceryl ether, diethylene glycol monobutyl ether, (e5) 2-phenoxyethanol, diethylene glycol mono Phenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, phenol Carboxymethyl propylene glycol, 2-benzyloxy ethanol, aromatic ethers such as diethylene glycol monobenzyl ether, and the like.

  The component (E) is effective as a viscosity modifier and a gelation inhibitor of the composition, and the above (e1) alkanols, (e2) glycols, (e4) alkyl ethers, (e5) aromatic ethers More preferably, the composition is more effective by containing at least one selected from (e2) glycols, (d4) alkyl ethers, and (e5) aromatic ethers. Viscosity adjustment and gelation can be suppressed.

  In addition, in the liquid detergent composition of the present invention, (e4) alkyl ethers and / or (e5) aromatic ethers are preferred in order to stabilize hydrogen peroxide and suppress a dry-dry odor, among which diethylene glycol monobutyl ether , Diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, or phenoxypropylene glycol. Furthermore, diethylene glycol monobutyl ether and / or triethylene glycol monophenyl ether are more preferred.

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

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

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

[(G) component]
In the liquid detergent composition of the present invention, from the viewpoint of the stability of hydrogen peroxide, etc., it is a medium for adjusting the pH when an anionic surfactant, hydrotrope, chelating agent, etc. are blended with an acid type compound. It is preferable to use an alkali agent (hereinafter referred to as the component (G)) as a compatibilizer or the like. When the pH of the liquid detergent composition of the present invention is 7.0 or less as described later, it is considered that there is almost no free alkaline agent. In addition, as an alkali agent used for neutralization, it is preferable to use an alkali metal hydroxide, and potassium hydroxide and / or sodium hydroxide are more preferable.

  In addition, water-miscible organic amine compounds, and further alkanolamine compounds having a total carbon number of 6 or less, such as monoethanolamine, diethanolamine, and triethanolamine [hereinafter sometimes referred to as (G ′) components]. ], When used as a neutralizing agent, the content in the composition is less than 1% by mass, more preferably not more than 0.5% by mass, and even more preferably not more than 0.08% by mass from the viewpoint of the effect of suppressing raw dry odor. Preferably there is. In addition to the alkali agent (neutralizing agent for pH adjustment), the component (G ′) is added to the amount of the component (G ′) in the form of a salt of an anionic compound.

[(H) component]
The liquid detergent composition of the present invention contains an organic chelating agent [hereinafter referred to as (H) component] capable of chelating polyvalent metal ions in that the effect of the present invention is maintained over time. preferable. Examples of the organic chelating agent of component (H) include nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid, and diencoric acid. Aminopolyacetic acid or salts thereof, diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid, carboxymethyltartaric acid, etc. Polycarboxylic acids other than acetic acid or salts thereof, aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic) Acid) and organic phosphonic acids or salts thereof may be mentioned of, salt and the like alkali metal salts. In the present invention, a salt blended with an acid and neutralized with an alkali agent in the system may be used. Among these, organic phosphonic acid or a salt thereof, particularly 1-hydroxyethylidene-1,1-diphosphonic acid is preferable. The counter ion is preferably an alkali metal salt.

  In the present invention, it is preferable to contain an organic chelating agent in order to suppress the deterioration of the present invention due to storage, but this is because the decomposition of hydrogen peroxide by heavy metal ions that may be contained in the composition is an organic chelating agent. There are many parts that contribute to being suppressed. On the other hand, since many organic chelating agents have the property of suppressing fluctuations in pH at the time of dilution, in order to obtain excellent detergency, the fluctuations in pH due to water can be easily changed to near neutral. The content is preferably a small amount and an effective agent. The organic phosphonic acid or a salt thereof is preferable as such an organic chelating agent, and the salt is preferably a potassium salt or a sodium salt.

  The content of the component (H) in the composition is preferably 0.01 to 0.5% by mass, more preferably 0.03 to 0.3% by mass, more preferably 0 when converted to an acid type compound. 0.05 to 0.2% by mass. Further, the component (H) is preferably contained as 1-hydroxyethylidene-1,1-diphosphonic acid in the limitation of the concentration range.

[Component (I)]
As the component (I), it is preferable to blend a water-soluble polymer for the purpose of improving the effect of inhibiting dryness. As the polymer, a polymer containing a structural unit having a carboxylic acid group is preferable, and polyacrylic acid, acrylic acid-maleic acid copolymer, acrylic acid or maleic acid and an olefin having 2 to 5 carbon atoms, Can be mentioned. In addition, a high-concentration surfactant system having a high surfactant content includes both a structural unit composed of a monomer having a carboxylic acid group and a structural unit composed of a monomer having a polyoxyethylene chain. It is preferable to use a high molecular polymer. Examples thereof include polymers described in JP-A-10-60476 and JP-A-2004-155937. The compounding ratio in the composition of (I) component becomes like this. Preferably it is 0.1-5 mass%, More preferably, it is 0.5-4 mass%.

[Ingredients other than the above]
Furthermore, the components shown in the following (i) to (vii) can be blended in the liquid detergent composition of the present invention to such an extent that the effects of the present invention are not impaired.
(I) Enzymes such as cellulase, amylase, pectinase, protease, lipase, etc. (ii) Enzyme stabilizers such as calcium ion source (calcium ion supply compound), bihydroxy compound, formic acid, etc. (iii) Fluorescent dyes such as Tinopearl CBS Fluorescent dyes (iv) butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium bisulfite, which are commercially available as name, manufactured by Ciba Specialty Chemicals) and Whitetex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.) v) Anti-gelling polymers described in JP-A-11-513067, and polypropylene glycol or polyethylene glycol having a weight average molecular weight of 600 to 5000, more preferably 1000 to 4000. The weight average molecular weight can be determined using a light scattering method, and can be measured with a dynamic light scattering photometer (DLS-8000 series, manufactured by Otsuka Electronics Co., Ltd.).
(Vi) Water such as paraffins such as octane, decane, dodecane and tridecane, olefins such as decene and dodecene, halogenated alkyls such as methylene chloride and 1,1,1-trichloroethane, and terpenes such as D-limonene. Immiscible organic solvents (vii) and other antifoaming agents such as pigments, fragrances, antibacterial preservatives, and silicone

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

  The liquid detergent composition of the present invention preferably contains less than 1% by weight of a bleach activator, for example, a bleach activator having an anionic group, from the viewpoint of liquid stability and suppression of hydrogen peroxide decomposition. 0.4 mass% or less, and more preferably no bleach activator is contained. The bleach activator referred to in the present invention refers to a compound that reacts with hydrogen peroxide in water and further reacts under mild conditions such as use in a domestic environment to produce an organic peracid. As a bleach activator, it is known to be blended in a liquid bleach composition in addition to TAED (tetraacelethylenediamine), and has a linear or branched alkyl group having 8 to 22 carbon atoms, Mention may be made of alkanoyloxybenzene sulfonic acids or alkanoyloxybenzene carboxylic acids or their alkali metal salts. Of these, alkanoyloxybenzenesulfonic acid or alkanoyloxybenzenecarboxylic acid or an alkali metal salt thereof having a linear or branched alkyl group having 8 to 22 carbon atoms can be stably mixed with hydrogen peroxide. However, in the present invention, these bleach activators are anionic surfactants (c1) other than fatty acids and salts thereof, and are limited by the mass ratio of (c1) / (B). It is possible to contain a bleach activator as long as the mass ratio is within a predetermined range. However, when these bleach activators are blended in the liquid detergent composition of the present invention, the effect of the bleach activators cannot be fully exhibited. Furthermore, in order to mix | blend a bleaching activator stably, there is not only a restriction on the composition, but also causes a decrease in the deodorizing effect of the present invention.

  In general, in the case of a cleaning solution or a bleaching solution containing hydrogen peroxide, the bleaching effect is improved by increasing the pH of the solution during processing. However, the liquid detergent composition of the present invention preferably contains substantially no boron compound, which is used to make the pH alkaline when diluted in water. Boron compounds reduce detergency in the present invention. Here, the boron compound is boric acid, borax, borate or the like. Specifically, as the borate, sodium borate, potassium borate, ammonium borate, sodium 4 borate, 4 Examples thereof include potassium borate and ammonium borate. Further, “substantially not containing” means excluding a case where an extremely small amount of enzyme preparation is mixed as an enzyme stabilizer, for example. Specifically, in terms of boric acid in the composition, borax, as its own mass, has a boron compound content of less than 0.1% by mass, and further less than 0.01% by mass. That means. The lower limit is 0% by mass.

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

  From the viewpoint of detergency and deodorizing effect, the liquid detergent composition of the present invention has a pH of 3.0 to 7.0 at 20 ° C. described in 8.3 of JIS K3362: 1998, and further 3.5. -7.0, and even more preferably 4.0-6.0.

  Furthermore, 2 ml of the liquid detergent composition of the present invention was dissolved in 3 L of soft water having a pH of 6.0 to 8.0 at 20 ° C. of 4 ° DH adjusted by adding calcium carbonate to deionized water. The pH of the aqueous solution at that time is preferably 4.0 to 8.5 at 20 ° C., more preferably 6.0 to 8.0.

  The viscosity at 20 ° C. of the liquid detergent composition of the present invention is preferably 10 to 1,000 mPa · s, more preferably 50 to 600 mPa · s, and still more preferably 100 to 300 mPa · s in terms of ease of handling. Viscosity can be adjusted by the ratio of (a1) component, (a2) component, (E) component, water, etc. in a compounding component. The nonionic surfactant (a1 ') described above can be easily used as the component (a1) for reducing the viscosity of the composition.

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

  The liquid cleaning composition of the present invention is used as a cleaning composition for textile products. Among them, it is suitable as a liquid detergent composition for textile products, such as clothing, towels, foot-wiping mats, bed sheet products, etc., for example, used in household life, and further as a liquid detergent composition for clothing. Furthermore, it is suitable as a liquid detergent composition for textiles that can be washed with water.

  In the present invention, a cleaning liquid containing the liquid detergent composition of the present invention and water, for example, a textile product is washed with an aqueous solution in which the liquid detergent composition of the present invention is dissolved in water. And the deodorizing effect can be obtained. Preferably, the cleaning liquid is a liquid cleaning composition used at a rate of 0.3 to 1.0 g / L with respect to 1 L of water. Such a cleaning solution such as an aqueous solution is generally called a washing solution. The temperature of the cleaning liquid at the time of cleaning is not particularly limited, but according to the liquid cleaning composition of the present invention, the cleaning power and deodorizing effect can be obtained even in a wide temperature range of 5 ° C. to 40 ° C. A soaking step may be provided before washing. When the soaking step is provided, the concentration of the liquid detergent composition is preferably 3 to 6 times the concentration at the time of cleaning.

  In addition, the liquid detergent composition of the present invention is applied to a used textile product, and further to a textile product such as worn clothing (applied in a non-foamed state), so that bacteria are present in the textile product. If it does, it will form a bubble that is easy to see. Foam is caused by a disproportionation reaction by catalase in bacteria. Interestingly, no foaming is observed in textiles used or worn for only one day from the new. Foaming due to the application of the present invention can be observed in textiles that have been used several times or worn and washed repeatedly. Furthermore, in some cases, the used fiber product can be confirmed to foam due to the application of the liquid detergent composition of the present invention even immediately after washing and drying.

  Therefore, in this invention, the washing | cleaning method of a textile product which has the process of apply | coating the liquid cleaning composition of this invention to a textile product and generating a foam is also provided. In this method, a part or all of the liquid detergent composition can be applied to the textile product while confirming the presence of bacteria due to the generation of bubbles.

  According to the textile product cleaning method of the present invention for performing such application, not only can the presence of bacteria in the textile product be confirmed, but also the liquid detergent composition is applied intensively around the presence of bacteria. be able to. Such a concept is disclosed in JP 2010-59296 A regarding hard surface cleaning agents. Moreover, the liquid bleach composition for textiles containing the conventional one part hydrogen peroxide may generate | occur | produce a bubble by presence of bacteria. However, the surfactant concentration of the conventional liquid bleach composition containing hydrogen peroxide is low, and sufficient foam visibility cannot be obtained. In addition, since the conventional bleaching agent for textile products has a bleaching effect as a main problem, it is intended to be intensively applied to places where stain stains and collar sleeve stains can be visually confirmed. On the other hand, when considering the problem of deodorization related to bacteria as in the present invention, visualization by foaming is very significant.

  The liquid detergent composition of the present invention foams upon contact with bacteria. The composition of the composition having excellent visibility of bacteria due to bubbles follows the preferable conditions of the liquid detergent composition described above. In particular, as the nonionic surfactant (A), compounds of the general formulas (a1) and (a2) are preferable, and those having a PO group in the molecule in an average of 1 mol or more and 3 mol or less are preferable. It is easy to generate bubbles that are easily visible due to the presence, and the time from foaming to defoaming is also appropriate.

  The present invention includes a step of applying the liquid detergent composition of the present invention to a fiber product and foaming the fiber product, and bringing the fiber product coated with the liquid detergent composition into contact with a cleaning liquid containing water for cleaning treatment. And a method for cleaning the textile product, including the step of performing. When the liquid detergent composition of the present invention is used for coating, the coated textile product and an optional cleaning agent can be put into a washing tub and washed together with other optional textile products. In addition, it does not deny that arbitrary cleaning liquid contains the liquid cleaning composition of this invention other than having used for application | coating, and another cleaning agent. Specifically, a part of the liquid detergent composition of the present invention used for washing (that is, the total amount of the liquid detergent composition of the present invention used for washing) is applied to a textile product, and the liquid detergent composition The textile product coated with can be brought into contact with the remaining cleaning solution containing the liquid detergent composition of the present invention and water for washing treatment. More specifically, for example, after a part of the liquid detergent composition of the present invention is applied to a fiber product, the applied fiber product, and optionally any fiber product and the remainder of the liquid detergent composition of the present invention. In addition to the part where the liquid detergent composition of the textile product is applied by the textile product washing method in which the water and the water are put in a washing tub and washed in an aqueous solution, also for any textile products, An excellent deodorizing effect can be provided. In addition, it can also wash | clean by apply | coating all the liquid cleaning composition of this invention used for washing | cleaning to a textiles. When the step of coating is included, the concentration of the liquid detergent composition of the present invention in the cleaning liquid is in the range of 0.3 to 1.0 g / L (this concentration may be a calculated value based on the coating amount). It is preferable to use it as described above in order to obtain a sufficient effect.

  In addition, the washing | cleaning or washing | cleaning process here also includes the process by hand washing in addition to the mechanical stirring by a washing machine, for example, rubbing, hitting, and stepping.

  In addition, the fiber product cleaning method of the present invention may be a fiber product deodorization method or a deodorization cleaning method, thereby clarifying the difference in purpose of use from the conventional method.

<Test example (specification of raw dry odor-causing substances)>
After washing and drying, a cotton towel that had a strong dry-dry odor was collected from the household, cut into 50 g, extracted from 500 mL of dichloromethane, and concentrated under reduced pressure. Furthermore, 200 mL of 1M sodium hydroxide aqueous solution was added to the extraction solution, and the aqueous layer was recovered, and 200 mL of 2M hydrochloric acid was added to make it acidic. To this solution, 200 mL of dichloromethane was added, the organic layer was concentrated under reduced pressure, and the acidic component concentrate was made up to 1 mL.

  Subsequently, using a gas chromatograph manufactured by Agilent with a Gestel Preparative Fraction Collector (PFC) device connected, the concentrate was fractionated by the GC retention time under the following conditions, and the GC around the target component was divided into 30 batches. It was collected in 200 mg of a filler (trade name: TENAX TA, manufactured by GL Sciences) filled in a glass tube having an inner diameter of 6 mm and a length of 117 mm.

(GC-PFC conditions)
GC: Agilent 6890N (trade name, manufactured by Agilent)
Column: DB-1 (trade name, manufactured by Agilent), length 30 m, inner diameter 0.53 mm, film thickness 1 μm
40 ° C. for 1 min. hold → 6 ° C / min. to 60 ° C. → 4 ° C./min. to 300 ℃
Injection volume: 2μL
PFC (manufactured by Gerstel): trap time 18 min. to 24 min. , 30times
trap: TENAX TA (trade name, manufactured by GL Sciences Inc.) 200mg

Finally, the target component collected in TENAX TA was analyzed under the following conditions with a device in which a Thermal Desorption system (TDS) manufactured by GUSTER Co. was connected to GC-MS manufactured by Agilent.
(TDS-GC-MS conditions)
GC: Agilent 6890N (trade name, manufactured by Agilent)
MS: Agilent 5973 (trade name, manufactured by Agilent)
TDS desorption conditions: 250 ° C., purge flow rate 50 mL / min, purge time 3 min.
Column: DB-FFAP (trade name, manufactured by Agilent), length 30 m, inner diameter 250 μm, film thickness 0.25 μm
40 ° C. for 1 min. hold → 6 ° C / min. to 60 ° C. → 2 ° C./min. to 240 ℃

  As a result of analysis, intermediate branched fatty acids such as 4M3H were detected as a raw dry odor.

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

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

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

(2) Evaluation of raw dry odor Of the underwear of adult males in their 20s to 40s who repeated washing and wearing multiple times, they do not smell when they are washed and dried sufficiently, but when damp, they have the same odor. Underwear (100% cotton) with a raw dry odor was collected. The underwear was cut into 5 cm × 5 cm, and cut fabrics that were confirmed by a professional evaluator to have the same odor level when the odor was moistened were selected. In addition, when qualitatively analyzing the raw odor of the same odor, it was confirmed that the intermediate branched fatty acid odor mainly containing 4M3H odor and sulfur odor were contained.

  In order to evaluate the collected and selected cut cloth as an actual clothing test cloth in the same initial state as possible, the above-mentioned selected cut cloth was prepared from a reference detergent having the following composition containing no fragrance and a concentration of 0.67 g. Washing was performed with a washing liquid of / L using a stirring-type cleaning tester (Target-o-Meter) under conditions of a water temperature of 25 ° C., a stirring speed of 85 rpm, a stirring time of 10 minutes, and a bath ratio of 15. The test cloth was thoroughly rinsed with tap water, and immediately left in an environment of 25 ° C. and a relative humidity of 35% for 24 hours to be sufficiently dried. The odor intensity of the dried real clothing test cloth was further selected according to the evaluation criteria 1 described later (“no odor at all”) by the agreement of five expert evaluators, and used as an actual clothing test cloth. In addition, it was confirmed that the garment test cloth processed with the reference | standard detergent produces the smell containing 4M3H by making it a raw dry state.

  The composition of the reference detergent is (1) alkyl (carbon number 12, straight chain) benzenesulfonic acid sodium salt 10% by mass, (2) alkyl (carbon number 12) sulfate ester sodium salt 2% by mass, (3) derived from coconut oil (4) polyoxyethylene (average number of moles added 10) alkyl (carbon number 12-14) ether 10% by weight, (5) sodium carbonate 15% by weight, (6) zeolite 10% by weight, (7) Acrylic acid-maleic acid copolymer (weight average molecular weight 70000, acrylic acid / maleic acid molar ratio = 6/4) 5% by mass, (8) No. 2 sodium silicate 1% by mass, (9) Residual sodium sulfate (100% by mass in total).

  Next, using the liquid detergent compositions shown in Tables 1 to 3, the actual clothing test cloths were washed, and the following odor strength evaluation tests (odor strength evaluations A and B) were performed.

・ Odor intensity evaluation A (Evaluation of odor generated in a short time from raw fiber products)
A washing liquid having a concentration of 0.67 g / L is prepared from the liquid detergent composition described in Tables 1 to 3, and the above-mentioned five actual clothing test cloths are used as one set, and a stirring type washing tester (Target-o-Meter). Was subjected to washing treatment under conditions of a water temperature of 25 ° C., a stirring speed of 85 rpm, a stirring time of 10 minutes, and a bath ratio of 15. After washing, the garment test cloth was sufficiently rinsed with tap water, and then stored for 3 hours in an incubator at 30 ° C. and a relative humidity of 90% under an environment in which a raw dry odor is likely to occur. The sensory evaluation of raw dry odors (complex odors including intermediate branched fatty acid odors such as S odor, N odor, aldehyde odor, lower fatty acid odor, 4M3H odor) was conducted by five expert evaluators on the actual clothing test cloth after storage. .

・ Odor intensity evaluation B (Evaluation of recurrent raw dry odor generated from dry textile products)
A washing liquid having a concentration of 0.67 g / L is prepared from the liquid detergent composition described in Tables 1 to 3, and the above-mentioned five actual clothing test cloths are used as one set, and a stirring type washing tester (Target-o-Meter). Was subjected to washing treatment under conditions of a water temperature of 25 ° C., a stirring speed of 85 rpm, a stirring time of 10 minutes, and a bath ratio of 15. After washing, the garment test cloth is sufficiently rinsed with tap water, stored for 12 hours in a 30 ° C. and 90% relative humidity incubator in an environment where odors are easily generated, and then at 25 ° C. It was left to stand in an environment with a humidity of 35% for a whole day and dried sufficiently. The dried garment test cloth did not smell fresh.

  Thereafter, 0.1 g of tap water was sprayed on the actual clothing test cloth using a spray container, and the actual clothing test cloth was wetted again. Sensory evaluation of the branched fatty acid odor was performed.

The evaluation results of the odor intensity evaluations A and B were determined by the agreement of professional evaluators based on the following evaluation criteria.
(Evaluation criteria)
1: No odor at all 2: Almost no odor 3: Somehow understandable odor 4: Smell understood when sniffing well 5: Clearly odor recognized The results of the odor intensity evaluations A and B are shown in Tables 1 to 3.
In the case of evaluation criteria 3 to 5, at least 4 people feel odor.

  Hereinafter, Table 4 shows formulation examples of the liquid detergent composition of the present invention.

The blending components in each table are shown below.
<Blending ingredients>
In the description of the following components, ethylene oxide is abbreviated as EO and propylene oxide is abbreviated as PO. Moreover, the anionic organic compound used as the salt showed the density | concentration converted into the acid type compound in the table | surface. The pH of the composition was adjusted with an aqueous sodium hydroxide solution or an aqueous hydrochloric acid solution.

(A) component (a1) component a1-1: polyoxyethylene (9) polyoxypropylene (2) polyoxyethylene (9) alkyl ether (numbers in parentheses are the average number of moles added) [carbon number 10-14 9 mol of ethylene oxide, 2 mol of propylene oxide, and 9 mol of ethylene oxide in the order of 9 mol per mol of the linear primary saturated alcohol of general formula (a1-5), p11 = 9, q = 2. It is a compound of p12 = 9. (A1) A component is not included. ]
A1-2: polyoxyethylene (8) polyoxypropylene (2) polyoxyethylene (8) alkyl ether (numbers in parentheses are average added moles) [linear primary saturated alcohol 1 having 10 to 14 carbon atoms] Eight moles of ethylene oxide, 2 moles of propylene oxide, and 8 moles of ethylene oxide are added in block order per mole. In general formula (a1-5), p11 = 8, q = 2, p12 = 8 is there. (A1) A component is not included. ]
A1-3: polyoxyethylene (15) polyoxypropylene (2) polyoxyethylene (15) alkyl ether (numbers in parentheses are the average number of moles added) [linear primary saturated alcohol 1 having 10 to 14 carbon atoms] A block addition of 15 moles of ethylene oxide, 2 moles of propylene oxide and 15 moles of ethylene oxide per mole, in general formula (a1-5), a compound of p11 = 15, q = 2, p12 = 15 is there. (A1) A component is not included. ]
A1-4: polyoxyethylene (20) polyoxypropylene (2) alkyl ether (numbers in parentheses are the average number of moles added) 20 ethylene oxide per mole of linear primary saturated alcohol having 10 to 14 carbon atoms In the general formula (a1-2), a compound in which p and 20 are added in the order of 2 moles and propylene oxide in a block order, p = 20 and q = 2. (A1) A component is not included. ]
A1-5: polyoxyethylene (14) polyoxypropylene (2) polyoxyethylene (4) alkyl ether (numbers in parentheses are average added moles) [linear primary saturated alcohol 1 having 10 to 14 carbon atoms] 14 mol of ethylene oxide, 2 mol of propylene oxide and 4 mol of ethylene oxide are added in block order per mol. In general formula (a1-5), p11 = 14, q = 2, p12 = 4 is there. (A1) A component is not included. ]

Component (a2): a2-1: R ^2a in the general formula (a2) is a linear primary alkyl group having 11 carbon atoms, l is 1, m is 15, n is 0, and R ^21a is a methyl group. Surfactant a2-2: Non-ionic, wherein R ^2a in formula (a2) is a linear primary alkyl group having 11 carbon atoms, l is 1, m is 10, n is 0, and R ^21a is a methyl group Surfactant

(A3) Component a3-1: In the general formula (a3), R ^3a is a linear alkyl group having 12 to 14 carbon atoms, and the carbon atom of R ^3a bonded to the oxygen atom of R ^3a —O— Nonionic surfactant with r = 7, which is the second carbon atom (7 mol of EO is added per 1 mol of secondary linear saturated alcohol having 12 to 14 carbon atoms, and unreacted alcohol is removed by distillation. R ^a2 OH content is less than 0.1% by mass.)
A3-2: In general formula (a3), R ^3a is a linear alkyl group having 12 carbon atoms, and the carbon atom of R ^3a bonded to the oxygen atom of R ^3a —O— is the first carbon atom. And is a nonionic surfactant in which r = 3 (however, it is a single distribution), and as the component (A1), in general formula (A1), x = 3 compounds occupy about 100% .
· A3-3: In the general formula (a3), R ^3a is a linear alkyl group of 12 carbon atoms, the carbon atoms of R ^3a to bind to R ^3a -O- oxygen atom of the first carbon atom In the general formula (A1), the compound of x = 5 occupies about 100% as a nonionic surfactant having r = 5 (single distribution) and (A1) component .
A3-4: In general formula (a3), R ^3a is a linear alkyl group having 14 carbon atoms, and the carbon atom of R ^3a bonded to the oxygen atom of R ^3a —O— is the first carbon atom. A nonionic surfactant where r = 5 (but with a single distribution). (A1) Contains no component.
A3-5: In general formula (a3), R ^3a is a linear alkyl group having 10 carbon atoms, and the carbon atom of R ^3a bonded to the oxygen atom of R ^3a —O— is the first carbon atom. A nonionic surfactant where r = 5 (but with a single distribution).
A3-6: a nonionic surfactant obtained by adding ethylene oxide to lauryl alcohol and having an average EO addition mole number of 3 moles. That is, it is represented by the general formula (a3), R ^3a is a linear alkyl group having 12 carbon atoms, and the carbon atom of R ^3a bonded to the oxygen atom of R ^3a —O— is the first carbon atom. , R = 3, and as the component (A1), a nonionic compound represented by the general formula (A1) and having x = 2, 3, 4, and 5 is a3-6. A total of 50% by mass of nonionic compounds with x = 3, 4, 5 are contained in a3-6 in a total of 32% by mass. For convenience, the non-ionic compound represented by the structural formula of the general formula (A1) and having the same R requirements as the general formula (A1) but x = 0, Contain 33% by mass.
A3-7: a nonionic surfactant obtained by adding ethylene oxide to lauryl alcohol and having an average EO addition mole number of 6 moles. That is, it is represented by the general formula (a3), R ^3a is a linear alkyl group having 12 carbon atoms, and the carbon atom of R ^3a bonded to the oxygen atom of R ^3a —O— is the first carbon atom. , R = 6, and as the component (A1), a nonionic compound represented by the general formula (A1) and having x = 2, 3, 4, and 5 is represented by a3-7. A total of 34% by mass of nonionic compounds with x = 3, 4, 5 are contained in a3-7 in a total of 27% by mass. For convenience, the non-ionic compound represented by the structural formula of the general formula (A1) and the requirements for R are the same as those of the general formula (A1), but x = 0, 1, are the total in a3-7. 10% by mass is contained.
A3-8: In general formula (a3), R ^3a is a linear alkyl group having 12 carbon atoms, and the carbon atom of R ^3a bonded to the oxygen atom of R ^3a —O— is the first carbon atom. A nonionic surfactant where r = 8 (but with a single distribution). Although it does not contain the component (A1), for convenience, when represented by the general formula (A1), in the general formula (A1), x = 8 compounds occupy about 100%.

(B) Component 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 / coconut oil fatty acid having a linear alkyl group having 10 to 14 carbon atoms (average carbon number: 11.7): Lunac L-55 (trade name), manufactured by Kao Corporation Long chain alkyl (C14) cation: Dilinear alkyl (C14) dimethylammonium ethyl sulfate. Here, the carbon atoms of the two C14 alkyl groups bonded to the nitrogen atom are both the first carbon atoms.

(E) component * e-1: Diethylene glycol monobutyl ether (also called butoxy diglycol)
E-2: Triethylene glycol monophenyl ether (PHG-30; manufactured by Nippon Emulsifier)
E-3: ethanol

Component (F) f-1: sodium paratoluenesulfonate (however, the concentration in the table is the concentration as an acid type compound)
Component (H) h-1: 1-hydroxyethylidene-1,1-diphosphonic acid (I) component i-1: synthesized by the method of Synthesis Example 1 on page 4, paragraph 0020 of JP-A-10-60476 High molecular compounds (others)
・ Fluorescent dye: Chino Pearl CBS-X (trade name) (manufactured by Ciba Specialty Chemicals)
Enzyme: Everase 16.0L-EX (trade name) (protease, manufactured by Novozyme)

<Foamability by application>
Liquid detergent compositions of Example Nos. 7 to 20 in Table 2 and Comparative Example No. 11 in Table 3 are prepared. For evaluation, any adult male in their 20s to 40s wears for 12 hours, and after washing with the standard detergent described in the evaluation of the raw dry odor, it is dried in a room at 20 ° C. and 60% RH, and again. Black cotton socks obtained by performing the wearing process 10 times are used.

  When the liquid detergent composition is applied to the soles of the socks that have been repeatedly worn and washed in this manner, there is a difference in foaming depending on the wearer. Seen. Foaming occurs within 15 seconds after application and defoams within 60 seconds of application. Comparative Example 11 containing no hydrogen peroxide does not foam at all.

In view of the above problems, the present inventors have conducted intensive studies from the viewpoints of causative substances, causative bacteria, and generation mechanisms of raw dry odors based on the washing and use of textile products. As a result, the present inventors have not only a fresh dry odor as a fresh dry odor but also a wet state until the drying after washing, as well as a recurrent property that is reappeared when the textile is sufficiently dried and then wetted. Focusing on the raw dry odor, new knowledge was obtained. That is, the recurrent raw dry odor of a textile product is surprisingly that microorganisms, especially bacteria, can survive or grow in the textile product, even after the dry odor has been sufficiently removed by drying after washing. In addition, a small amount of odor is trapped in the fiber by drying and becomes undetectable after drying, but it is released again by the wetness of the fiber product, that is, by dry drying, and it feels because it is a low threshold. I found it easy to be done. And the compound which controls the recurrent odor was found to be a branched medium chain fatty acid odor mainly composed of the 4-methyl-3-hexenoic acid (hereinafter sometimes referred to as 4M3H). And it identified that it was Moraxella sp . ( Moraxella sp .) As a causative bacterium of 4M3H, and discovered that this bacterium was resistant under a dry condition. From such a background, it has been clarified that even if the deodorizing effect after washing and drying is excellent, it does not immediately mean that it is effective in suppressing recurrent dry odor. In order to correctly evaluate the effect on recurrent dry odor, it is necessary to design and evaluate a new liquid detergent composition from the viewpoint of recognizing the cause of this problem.

Examples of the nonionic surfactant represented by the general formula (a1) include nonionic surfactants represented by the following general 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 ] H (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 H (a1-6)
Wherein, R ^1a, p, q, AO is defined above, pi 1 and p12, p13 is the average number of moles added, respectively, a few non-zero, at p = p11 + p12 + p13 or p = p11 + p12 is there. “·” Indicates a random bond. ]

The component (a1) of the present invention reacts, for example, an alkylene oxide having 3 to 5 carbon atoms and ethylene oxide according to the structure of the general formulas (a1-1) to (a1-6) with respect to R ^1a OH. It is obtained by. From the target structure, the blending order and conditions may be examined, and the addition reaction may be performed in a block or random manner. Further, the reaction ratio of the alkylene oxide having 3 to 5 carbon atoms and ethylene oxide per mole of R ^1a OH is within the range of p and q in the general formula (1), that is, p = 8 to 40, q = 0 to 0. 5. It is possible to have the conditions of p = p11 + p12 + p13 or p = p11 + p12 and the preferable ranges described above. In other words, the reaction ratio of the alkylene oxide having 3 to 5 carbon atoms to be added to the aliphatic alcohol and ethylene oxide may be in the numerical range of p and q, p11, p12, and p13.

(B1) A quaternary ammonium salt in which R ^b1 in the general formula (B1) is a linear alkyl group having 12 to 18 carbon atoms, and R ^{b2 to} R ^b4 are each a methyl group or an ethyl group .
(B2) A quaternary ammonium salt in which R ^b1 in the general formula (B1) is a branched alkyl group having 12 to 18 carbon atoms, and R ^{b2 to} R ^b4 are each a methyl group or an ethyl group .
(B3) A quaternary ammonium salt in which R ^b1 in the general formula (B1) is a linear alkyl group having 12 to 18 carbon atoms, and R ^b3 and R ^b4 are each a methyl group or an ethyl group .
(B4) R ^b1 in formula (B1) is a linear alkyl group having 12 to 18 carbon atoms, s is 1-5, with R ^b2, R ^b3, R ^b4 are each a methyl group or an ethyl group A quaternary ammonium salt.

Claims (12)

Nonionic surfactant (A) [hereinafter referred to as component (A)] is 15 to 70% by mass, cationic surfactant (B) represented by the following general formula (B1) [hereinafter referred to as component (B)] A liquid detergent composition containing 0.3 to 5% by mass, hydrogen peroxide (D) (hereinafter referred to as component (D)) 0.3 to 10% by mass, and water,
(A) 0.5-10 mass% of nonionic compounds (A1) shown by the following general formula (A1) as a component are contained in the composition,
The ratio of the anionic surfactant (c1) other than the fatty acid and its salt to the component (B) is 0 to 1 in a mass ratio of (c1) / (B),
The pH at 20 ° C. described in 8.3 of JIS K3362: 1998 is 3.0 to 7.0.
Liquid detergent composition.
R—O— (C ₂ H ₄ O) _x —H (A1)
[Wherein, R is a linear alkyl group having 12 carbon atoms, and the carbon atom of R bonded to the oxygen atom of R—O— is a primary carbon atom. x is an added mole number of ethyleneoxy group and is an integer of 2 to 5. ]

Wherein, R ^b1 is a chain hydrocarbon group having 12 to 18 carbon atoms, in R ^b1 - (A'O) _s - may contain. A′O is an ethyleneoxy group or a propyleneoxy group, s represents an average added mole number of A′O and is 0 to 10, and R ^b2 , R ^b3 and R ^b4 are each independently a methyl group, ethyl Group, a benzyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and X ⁻ is CH ₃ SO ₄ ^— or CH ₃ CH ₂ SO ₄ ⁻ , a halogen ion. ] (A) The liquid cleaning composition of Claim 1 which contains 10-60 mass% of nonionic surfactant shown by the following general formula (a1) and / or general formula (a2) as a component.
R ^1a —O [(C ₂ H ₄ O) _p / (AO) _q ] H (a1)
[Wherein, R ^1a represents an alkyl group or alkenyl group having 8 to 22 carbon atoms. AO is an alkyleneoxy group having 3 to 5 carbon atoms. p and q are average addition mole numbers, p is a number of 8-40, and q is a number of 0-5. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded randomly or in blocks. ]
_{^{R 2a (CO) l O -}} [(C 2 H 4 O) m / (AO) n] R 21a (a2)
[Wherein, R ^2a is an alkyl group or alkenyl group having 8 to 22 carbon atoms. R ^21a is an alkyl group having 1 to 3 carbon atoms. l is a number of 0 or 1, and AO is an alkyleneoxy group having 3 to 5 carbon atoms. m and n are average addition mole numbers, m is a number of 5-30, n is a number of 0-5. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded randomly or in blocks. ] (A) The liquid cleaning composition of Claim 1 or 2 which contains 0.5-20 mass% of nonionic surfactant shown by the following general formula (a3) as a component.
R ^3a —O— (C ₂ H ₄ O) _r —H (a3)
[Wherein, R ^3a is an alkyl group or alkenyl group having 8 to 22 carbon atoms. The carbon atom of R ^3a bonded to the oxygen atom of R ^3a —O— is a primary carbon atom and / or a secondary carbon atom. r is an average added mole number, and is a number of 2 or more and less than 8. ] Furthermore, the liquid detergent composition in any one of Claims 1-3 which contains a fatty acid and its salt (c2) 0.05-5 mass% in conversion of a fatty acid. Furthermore, the liquid detergent composition in any one of Claims 1-4 which contains 1-40 mass% of water miscible organic solvents (E). Furthermore, the liquid cleaning composition in any one of Claims 1-5 which contains 0.01-0.5 mass% of organic chelating agents (H). The liquid detergent composition in any one of Claims 1-6 whose content of a water miscible organic amine compound is less than 1 mass%. The liquid detergent composition according to any one of claims 1 to 7, which does not contain a bleach activator. A method for washing a textile product with an aqueous solution in which the liquid detergent composition according to claim 1 is dissolved in water. Nonionic surfactant (A) [hereinafter referred to as component (A)] is 15 to 70% by mass, cationic surfactant (B) represented by the following general formula (B1) [hereinafter referred to as component (B)] A liquid detergent composition containing 0.3 to 5% by mass, hydrogen peroxide (D) (hereinafter referred to as component (D)) 0.3 to 10% by mass, and water,
(A) 0.5-10 mass% of nonionic compounds (A1) shown by the following general formula (A1) as a component are contained in the composition,
The ratio of the anionic surfactant (c1) other than the fatty acid and its salt to the component (B) is 0 to 1 in a mass ratio of (c1) / (B),
The pH at 20 ° C. described in 8.3 of JIS K3362: 1998 is 3.0 to 7.0.
A method for cleaning a textile product, comprising a step of applying a liquid detergent composition to the textile product to generate foam.
R—O— (C ₂ H ₄ O) _x —H (A1)
[Wherein, R is a linear alkyl group having 12 carbon atoms, and the carbon atom of R bonded to the oxygen atom of R—O— is a primary carbon atom. x is an added mole number of ethyleneoxy group and is an integer of 2 to 5. ]

Wherein, R ^b1 is a chain hydrocarbon group having 12 to 18 carbon atoms, in R ^b1 - (A'O) _s - may contain. A′O is an ethyleneoxy group or a propyleneoxy group, s represents an average added mole number of A′O and is 0 to 10, and R ^b2 , R ^b3 and R ^b4 are each independently a methyl group, ethyl Group, a benzyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and X ⁻ is CH ₃ SO ₄ ^— or CH ₃ CH ₂ SO ₄ ⁻ , a halogen ion. ] The liquid detergent composition contains 10 to 60% by mass of a nonionic surfactant represented by the following general formula (a1) and / or general formula (a2) as the component (A). How to wash textile products.
R ^1a —O [(C ₂ H ₄ O) _p / (AO) _q ] H (a1)
[Wherein, R ^1a represents an alkyl group or alkenyl group having 8 to 22 carbon atoms. AO is an alkyleneoxy group having 3 to 5 carbon atoms. p and q are average addition mole numbers, p is a number of 8-40, and q is a number of 0-5. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded randomly or in blocks. ]
_{^{R 2a (CO) l O -}} [(C 2 H 4 O) m / (AO) n] R 21a (a2)
[Wherein, R ^2a is an alkyl group or alkenyl group having 8 to 22 carbon atoms. R ^21a is an alkyl group having 1 to 3 carbon atoms. l is a number of 0 or 1, and AO is an alkyleneoxy group having 3 to 5 carbon atoms. m and n are average addition mole numbers, m is a number of 5-30, n is a number of 0-5. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded randomly or in blocks. ] A part of the liquid detergent composition used for washing is applied to the textile product, and the textile product coated with the liquid detergent composition is used as a washing liquid containing the remaining liquid detergent composition and water. The method for cleaning a textile product according to claim 10 or 11, wherein the cleaning treatment is performed by contacting the fibers.