TWI572710B - Liquid detergent compositions - Google Patents

Description

Liquid detergent composition

This invention relates to a liquid detergent composition for fibrous articles. Further, it relates to a liquid detergent composition for a fibrous product, especially a clothing.

In recent years, with the increase in core familyization, the number of dual-employee generation has increased, and families that wash at night or on holidays and dry indoors are increasing. Moreover, due to the recent increase in energy conservation awareness, as a washing and drying machine with less energy loss, a novel drying technique using low temperature drying of air conditioning dehumidification function has been proposed. However, the washed clothes tend to produce a semi-dry odor when the room is dried or dried at a low temperature.

On the other hand, the meaning of washing is also changing. Specifically, the tendency to adhere the odor as a criterion for washing without the presence of dirt is increasing. Previously, the adhesion of body odor after smoking or sports to the fiber product was used to remind the sufficient factor of washing, but recently it has become the object of reminding washing due to the adhesion or generation of a trace amount of unpleasant odor. Therefore, it is not desirable to produce an odor due to the continuous half-dry state of the fibrous product after drying after washing, and further, with the spread of information relating to the reproduction of semi-dry odor and bacteria, Raise interest in this. Here, "semi-dry" means a state in which the fibrous product is wet, in particular, a state in which the fibrous product is wetted by a small amount of moisture. Specifically, in relation to the cleaning and use of the fiber product, it is meant that the cleaned fiber product is dried in a humidified environment without using a dryer until the dry state is wet. And means a state in which the dried fibrous product is wetted by the wet hands or the body's wiping, rain or sweat.

As a cause of the semi-dry odor, various types of decomposed substances of sebum and dirt, specifically, metabolites produced by the growth of microorganisms, and the like are known as causative substances.埴原,园田, "The lotion for suppressing the odor of indoor drying", the fragrance, the report of the semi-dry odor (room drying odor) reported in No. 223, p.109-116, September, 2004 "Moldy odor" such as medium chain aldehydes, medium chain alcohols, and ketones, "acid odor" such as short-chain fatty acids and medium-chain fatty acids, and "bad odor" such as nitrogen compounds and complex odors composed of sulfur compounds, especially medium-chain fatty acids. The proportion is large. Takeuchi et al., "Analysis of the semi-dry odor of clothing", the agronomic chemistry meeting of the 2010 Agronomic Chemistry Association, p.149, described that 4-methyl-3-hexenoic acid has a strong odor and is used as a half of clothing. Dry odor, especially as a medium chain fatty acid odor. Further, it is proposed in Japanese Patent Laid-Open Publication No. 2009-244094 to use a chain fatty acid having a specific structure as an indicator substance for semi-dry odor.

The semi-dry odor which is the object of the present invention has an odor generated when it is dried indoors, a odor generated when the washed laundry is dehydrated, and a odor which is caused by sweat or rain after drying. And the smell is produced. The odor generated when the room is dried and the odor generated when placed in the washing tub can be removed or reduced by sufficiently drying. However, it is difficult to remove the odor which reappears when the same odor occurs again when it is dried and rewet, and if the semi-dry odor is generated in the fiber product, the odor can be temporarily removed by sufficient drying after washing. But it becomes easier to use again when it is used. The resurgence of odor can lead to odors such as cleaning tools used on floors or tables such as old rags or mops. Once odor is generated, this is easy to happen again The semi-dry odor is produced even if it is dried and dried outdoors, and can hardly be removed.

The characteristic aspect of the re-occurring semi-dry odor is that it is odorless or substantially odorless after washing and sufficiently dried, but is odor-producing due to moisture. Moreover, this semi-dry odor is likely to occur when it is accommodated in a wardrobe or the like for a long period of time. Moreover, underwear, handkerchiefs or towels have many opportunities for contact with human skin, and cleaning--the use of fiber products with a short period of use and a high frequency of use, if the re-occurring semi-dry odor is generated, not only most cases The odor is reoccurred during use, and the odor level of the semi-dry odor which reoccurs tends to increase as the number of times of washing increases.

Conventionally, as a method of removing an offensive odor caused by a fibrous product, it is known to deodorize a microorganism causing an offensive odor by using a fragrance component or using a sterilizing or antibacterial agent. A covering method using a fabric treating agent containing an alicyclic ketone compound as a stabilizer component or a stabilizer component of a flavoring component is known (for example, refer to Japanese Patent Laid-Open No. 2010-31285 and Japanese Patent Laid-Open No. 2007-314693). As a deodorizing method for antibacterial or sterilizing microorganisms causing odor, a method of using a treatment agent containing a diketone compound, a cationic organic antibacterial agent, a bactericide such as triclosan or dichloro acid, or the like is known. A technique for suppressing a semi-dry odor using a bactericide is disclosed in, for example, Japanese Patent Laid-Open No. 2009-263812. Further, an inhibitor of the formation of a volatile sulfur compound inhibited by an enzyme using a specific fragrance component is disclosed in Japanese Patent Laid-Open Publication No. 2008-173441.

Further, liquid bleaches containing hydrogen peroxide, a cationic surfactant, and a nonionic surfactant are also known. Japanese Patent Special Open 9-59675 A liquid bleach composition containing a hydrogen peroxide, a HLB (Hydrophile Lipophile Balance) having a hydrophilic/oil ratio of 5 to 12, and an anionic surfactant or a cationic surfactant in which a fragrance is formulated is disclosed. As such a liquid bleaching composition containing a nonionic surfactant and a cationic surfactant, there is a Japanese Patent Laid-Open No. Hei 9-188895 and Japanese Patent Laid-Open No. Hei 9-217090. Further, it is known that a hydrogen peroxide-containing liquid detergent composition which improves the cleaning power by changing the pH value to be alkaline when the boron compound and the polyol are blended in water at the time of use is exemplified by the Japanese patent. JP-A-2007-169530 and JP-A-2007-177145.

A liquid detergent composition containing hydrogen peroxide, a boron compound, a hydroxy compound, a bleach activator, a surfactant, and water is disclosed in Japanese Patent Laid-Open No. Hei. No. 2006-169515. Liquid bleach cleaner compositions containing hydrogen peroxide, a boron compound, a hydroxy compound, a bleach activator, a nonionic surfactant, and a quaternary ammonium salt are disclosed in Japanese Patent Laid-Open No. 2007-106903. A liquid detergent composition containing hydrogen peroxide, an acid agent, and a surfactant is disclosed in Japanese Patent Laid-Open No. 2010-059296. A liquid detergent composition containing a nonionic surfactant, an anionic surfactant, and a water-mixed organic solvent is disclosed in Japanese Patent Laid-Open No. 2011-063784. A liquid detergent composition containing a nonionic surfactant, an anionic surfactant, a cationic surfactant, and a water-mixed organic solvent is disclosed in Japanese Patent Laid-Open No. 2010-265445.

A detergent composition for a fibrous product containing a nonionic surfactant and a cationic surfactant is disclosed in Japanese Laid-Open Patent Publication No. 2011-116932, which is incorporated by reference. Japanese Patent Special Issue issued on September 1, 2011 A surfactant composition containing a nonionic surfactant and a nonionic compound is disclosed in 2011-168730. A liquid detergent composition containing a nonionic surfactant, a hydrophobic organic solvent, and water is disclosed in Japanese Patent Laid-Open No. 2011-168731, which issued on Sep. 1, 2011. A liquid detergent composition containing a nonionic surfactant, a nonionic compound, a water-soluble salt, and water is disclosed in Japanese Patent Laid-Open No. 2011-168732, which issued on Sep. 1, 2011. A liquid detergent composition containing a nonionic surfactant, a cationic compound, a nonionic compound, and water is disclosed in Japanese Patent Laid-Open No. 2011-168733, which issued on Sep. 1, 2011. A liquid detergent composition containing a nonionic surfactant, hydrogen peroxide, a hydrocarbon, an organic acid, and water is disclosed in Japanese Patent Laid-Open No. 2011-168734, which issued on Sep. 1, 2011. A liquid detergent composition containing a surfactant, a dissolution aid, hydrogen peroxide, a water-absorbent solvent, and water is disclosed in Japanese Patent Laid-Open No. 2011-246585, which issued on Dec.

The present invention relates to a liquid detergent composition comprising: a nonionic surfactant (A) [hereinafter referred to as (A) component] 15 to 70% by mass, and a cation interface represented by the following formula (B1) Active agent (B) [hereinafter referred to as (B) component] 0.3 to 5% by mass, hydrogen peroxide (D) [hereinafter referred to as (D) component] 0.3 to 10% by mass, and water; and in the composition 0.5 to 10% by mass of the nonionic compound (A1) represented by the following formula (A1) is at least a part of the component (A); and the anionic surfactant (c1) other than the fatty acid and the salt thereof is relative to (B) The ratio of the components is 0 to 1 in terms of the mass ratio of (c1)/(B); The pH at 20 ° C as described in 8.3 of JIS K3362: 1998 is 3.0 to 7.0.

RO-(C ₂ H ₄ O) _x -H (A1) [wherein, R is a linear alkyl group having a carbon number of 12, and a carbon atom of RO- bonded to R of the oxygen atom is a primary carbon atom. x is the addition molar number of the exoethyloxy group and is an integer of 2 to 5]. [wherein, R ^b1 is a chain hydrocarbon group having a carbon number of 12 to 18, and may contain -(A'O) _s - in R ^b1 ; A'O is a stretching ethyloxy group or a stretching propyloxy group, s The average addition molar number of A'O is 0~10, and R ^b2 , R ^b3 and R ^b4 are each independently a methyl group, an ethyl group, a benzyl group or a hydroxyalkyl group having a carbon number of 1 to 3, X ^- Is CH ₃ SO ₄ ^- or CH ₃ CH ₂ SO ₄ ^- , halogen ion].

Further, the present invention relates to a method of cleaning a fibrous product which is an aqueous solution for cleaning a fibrous product by dissolving the above liquid detergent composition of the present invention in water.

Further, the present invention relates to a method of cleaning a fibrous article comprising the steps of applying a liquid detergent composition to a fibrous article and producing a foam comprising: a nonionic surfactant (A) [ Hereinafter, it is referred to as (A) component] 15 to 70% by mass, and the cationic surfactant (B) represented by the following formula (B1) [hereinafter referred to as (B) component] is 0.3 to 5% by mass, hydrogen peroxide (D) [hereinafter referred to as (D) component] 0.3 to 10% by mass, and water; and the composition contains 0.5 to 10% by mass of the nonionic compound (A1) represented by the following formula (A1) as (A) component; the ratio of the anionic surfactant (c1) other than the fatty acid and its salt to the component (B) is 0 to 1 by mass ratio of (c1) / (B); and 8.3 of JIS K3362: 1998 The pH value at 20 ° C as stated in the item is 3.0 to 7.0.

RO-(C ₂ H ₄ O) _x -H (A1) [wherein, R is a linear alkyl group having a carbon number of 12, and a carbon atom of RO- bonded to R of the oxygen atom is a primary carbon atom. x is the addition molar number of the exoethyloxy group and is an integer of 2 to 5].

[wherein, R ^b1 is a chain hydrocarbon group having a carbon number of 12 to 18, and may contain -(A'O) _s - in R ^b1 ; A'O is a stretching ethyloxy group or a stretching propyloxy group, s The average addition molar number of A'O is 0~10, and R ^b2 , R ^b3 and R ^b4 are each independently a methyl group, an ethyl group, a benzyl group or a hydroxyalkyl group having a carbon number of 1 to 3, X ^- Represents CH ₃ SO ₄ ^- or CH ₃ CH ₂ SO ₄ -, halide ion].

Further, the present invention is a use of the above liquid detergent composition for cleaning a fibrous product.

The present invention provides a liquid detergent composition which inhibits the formation of a semi-dry odor of a fibrous product, and further provides a semi-dry odor which is difficult to remove in the semi-dry odor, and has a high inhibitory effect. Liquid detergent composition.

Further, the present invention also provides a liquid detergent composition excellent in visual property in which bacteria are present without using a foam to reduce the cleaning power, and a method of cleaning the fiber product by the visual inspection.

In view of the above problems, the inventors of the present invention have conducted research on the viewpoint of the cause of the semi-dry odor caused by the cleaning and use of the fibrous product, the pathogenic bacteria, and the mechanism of the production. As a result, the inventors of the present invention have focused on the semi-dry odor, not only on the semi-dry odor after the cleaning until the wet state of the dry state, but also on the fact that the fibrous product is sufficiently dried and then wetted again. The semi-dry odor that occurs again, gaining new insights. That is, it has been found that the re-occurring semi-dry odor of the fibrous product is such that even after the semi-dry odor is sufficiently removed by drying after cleaning, microorganisms, especially bacteria, surprisingly survive or proliferate in the fibrous product. The odor generated is further caused by drying, and a trace amount of odor is caught in the state of the fiber, and becomes undetectable after drying. However, since the fiber product is wet, that is, semi-dry, it is released again, because it is low in tolerance. Value, so it is easy to be felt. Further, it has been found that the compound which controls the recurring odor is a branched chain fatty acid odor mainly composed of the above 4-methyl-3-hexenoic acid (hereinafter sometimes referred to as 4M3H). Further, as a pathogen of 4M3H, it was identified as Moraxella sp. , and it was found to be resistant under dry conditions. According to the above background, it is understood that even if the deodorizing effect after the previous cleaning and drying is excellent, it does not directly mean that it is effective for suppressing the re-occurrence of the semi-dry odor. In order to accurately evaluate the effect on the re-occurring semi-dry odor, it is necessary to re-design and evaluate the liquid detergent composition from the viewpoint of understanding the cause of the problem.

Further, the present inventors have developed an effective liquid not only for suppressing the formation of the previous semi-dry odor but also for suppressing the occurrence of re-occurring semi-dry odor, particularly 4-methyl-3-hexenoic acid odor. Detergent composition.

The liquid detergent composition of the present invention has an excellent inhibitory effect on the semi-dry odor generated by the fiber product, and further on the re-occurring semi-dry odor due to wetting after drying, especially for 4M3H odor.

Further, in the case of using the method of applying the liquid detergent composition of the present invention to a fibrous product, since the foam which is easily visualized is formed by the presence of bacteria in the fibrous product, the presence of the bacteria can be confirmed. Apply on one side.

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

<(A) component>

The liquid detergent composition of the present invention contains a nonionic surfactant of the component (A) as a main surfactant.

Examples of the nonionic surfactant of the component (A) include a nonionic surfactant having a chain hydrocarbon group having a carbon number of 8 to 22 and a hydrophilic group such as an ethyloxy group or a hydroxyl group. Further, a polyoxyalkylenealkyl group having an exoethyloxy group as a stretching alkyloxy group or an alkenyl ether, and a polyoxyalkylenealkyl group having a stretching ethyloxy group as a stretching alkyloxy group (further Preferred is an alkyl ester ether fatty acid ester having 1 to 3 carbon atoms, an alkyl polyglycoside, an alkyl glycoside, a sorbitan fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, and a polysaccharide-type boundary. Surfactant, fatty acid monoglyceride, fatty acid alkanolamine, polyhydroxy fatty acid decylamine, polyglycerin fatty acid ester, polyglyceryl alkyl ether, and the like.

In particular, the component (A) is preferably a nonionic surfactant selected from one or more of the following (a1) to (a5) from the viewpoint of the cleaning power and the deodorizing effect. More preferably, the following (a1) and/or (a2) and (a3) are used for the cleaning power, the deodorizing effect, and the visual property of contact with the fibrous product having the bacteria by spraying and foaming (hereinafter also From the viewpoint of the foaming visual property, it is more preferable to use (a1) and (a3) in combination. In particular, the foaming property of the application is preferably a surfactant of (a1), and further has a PO group. Further, the necessary conditions for (a1), (a2), and (a3) are also described.

(a1): a polyoxyalkylene alkyl group or an alkenyl ether type nonionic surfactant represented by the following formula (a1) [hereinafter referred to as (a1) component]

R ^1a -O[(C ₂ H ₄ O) _p /(AO) _q ]H (a1) [wherein R ^1a is an alkyl group or an alkenyl group having a carbon number of 8 to 22. AO is a stretching alkyl group having a carbon number of 3 to 5. p, q is the average addition mole number, p is the number of 8~40, q is the number of 0~5. "/" means that the C ₂ H ₄ O group and the AO group may be bonded in any of random or block manners].

(a2): a polyoxyalkylene short-chain alkyl ether fatty acid ester represented by the following formula (a2) or an aliphatic alkyl ether type nonionic surfactant [hereinafter referred to as (a2) component]

R ^2a (CO) _l O-[(C ₂ H ₄ O) _m /(AO)n]R ^21a (a2) [wherein R ^2a is an alkyl group or an alkenyl group having a carbon number of 8 to 22. R ^21a is an alkyl group having 1 to 3 carbon atoms. l is a number of 0 or 1, and AO is a stretching alkyl group having a carbon number of 3 to 5. m and n are the average addition moles, m is 5 to 30, and n is 0 to 5. "/" means that the C ₂ H ₄ O group and the AO group may be bonded in any of random or block manners].

(a3): a polyoxyethylene alkyl ether type nonionic surfactant represented by the following formula (a3) [hereinafter referred to as (a3) component]

R ^3a -O-(C ₂ H ₄ O) _r -H (a3) wherein R ^3a is an alkyl group or an alkenyl group having a carbon number of 8 to 22. 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 the average addition mole number, and is 2 or less and less than 8].

(a4): a polyglycerol alkyl group or an alkenyl ether type nonionic surfactant [hereinafter referred to as (a4) component]

(a5) Polysaccharide-type surfactant [hereinafter referred to as (a5) component]

The preferred aspect of the component (a1) is as follows.

The component (a1) can be made by making ethylene oxide [hereinafter sometimes referred to as EO] and an alkylene oxide having a carbon number of 3 to 5 and having a carbon number of 8 to 22, preferably 10 to 18, more preferably The alkyl or alkenyl group of 12 to 16 is preferably obtained by a random or block addition reaction having an alkyl group or a secondary alcohol. In R ^1a in the formula (a1), the carbon atom of R ^{1a to which} the oxygen atom is bonded to the R ^1a -O- is preferably a primary carbon atom and/or a secondary carbon atom, and more preferably a primary carbon atom, and R ^{1a is} preferably a linear alkyl group.

Further, p in the formula (a1) is an average addition mole number of a pendant ethyloxy group (C ₂ H ₄ O, hereinafter sometimes referred to as an EO group), and the viewpoint of solubility in water and cleanability It is 8 to 40, preferably 10 to 40, more preferably 14 to 35, and still more preferably 16 to 30. q is the average addition mole number of the AO group, and is 0 to 5, preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3 in terms of cleaning performance. Further, when q = 0, p is preferably 18 to 35, and more preferably 20 to 30.

The AO group in the formula (a1) is obtained by subjecting an alkylene oxide having a carbon number of 3 to 5 to an addition reaction, and it is preferred that a portion bonded by an addition reaction has a methyl branch, B. The structure of the base branch or the propyl branch. Further, the AO group is preferably a stretching alkyloxy group having a carbon number of 3 and/or a stretching alkyloxy group having a carbon number of 4, and specific examples thereof include a trimethyleneoxy group and an oxypropane-1. 2-diyl, oxybutane-1,2-diyl, oxybutane-1,3-diyl, oxybutane-2,3-diyl, oxytetramethylene. The AO group is more preferably an oxypropane-1,2-diyl group (hereinafter, the oxypropane-1,2-diyl group is sometimes referred to as a propyloxy group or a PO group in the present invention).

In the present invention, the following nonionic surfactant (hereinafter referred to as a nonionic surfactant (a1')] is used for the application, in terms of low-temperature storage stability, cleaning performance, and foaming visual properties at the time of application. Therefore, preferably, the nonionic surfactant is in the formula (a1), and R ^{1a has} a carbon number of 10 to 18, more preferably 12 to 16, and R ^1a -O- is bonded to an oxygen atom. The carbon atom of R ^1a is a linear alkyl group of a primary carbon atom, and the average addition molar number p of the EO group is 14 to 35, further preferably 16 to 30, and the AO group is a stretching propyl group, and the average thereof The addition molar number q is from 1 to 4, more preferably from 1 to 3, still more preferably from 2 to 3. Since the nonionic compound of the formula (A1) has a strong hydrophobicity, it can be used in a composition by using a surfactant having a molar amount of an extended ethyl group and having a high hydrophilicity. The nonionic compound represented by the formula (A1) is stably contained in the middle, and the present effect can be exerted. Further, by having a propyloxy group, not only the stabilization and cleaning power of the further liquid detergent composition can be obtained, but also it is easy to foam and easily visually detect in the presence of bacteria in the case of application. Thereafter, the foam easily disappears quickly, and the liquid detergent composition is excellent in the permeability to the inside of the fiber. From this point of view, in the present invention, it is preferred to use a nonionic surfactant (a1') as the component (A).

In the formula (a1), "/" means that the relationship between the EO group and the AO group of the component (a1) of the present invention may be either a random bond or a block bond. Further, the AO group can also be divided into a plurality of block bodies.

Examples of the nonionic surfactant represented by the formula (a1) include nonionic surfactants represented by the following formulae (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 have the above meanings, and p11 and p12, p13 are average additions. The number of ears is not 0, p=p11+p12+p13 or p=p11+p12. "." means a random key].

The nonionic surfactant represented by the general formulae (a1-1) to (a1-6) can be produced by considering the reaction ratio of the alkylene oxide to R ^1a OH and the reaction sequence. In the formulae (a1-1) to (a1-6), the average addition mole number of each alkylene group may be the number of moles of each alkylene oxide used in the reaction relative to R ^1a OH. Or it may be any of the average addition mole numbers of the alkylene groups of the obtained compounds. Furthermore, p11 and p12 are preferably independently from 1 to 20, more preferably from p11 of from 3 to 20 and p12 of from 1 to 15, more preferably p11 of from 4 to 15, and p12 of from 3 to 15. Further, p13 is preferably 0.1 to 10. The range of p11, p12, and p13 is set to each range condition of p or q subordinate to the general formula (a1) or preferably each range condition. Further, the concept of the lower order of the nonionic surfactant (a1') is more preferably defined by the above formula (a1-1) to (a1-6).

R ^1a in the formula (a1) can be used as described above for the alcohol derived from natural oils and fats. In terms of storage stability, a nonionic surfactant of the above formula (a1-2), (a1-4), (a1-5) or (a1-6) is preferred, and more preferably The nonionic surfactant of the formula (a1-5) or (a1-6) is more preferably a nonionic surfactant of the formula (a1-5).

The component (a1) of the present invention can be reacted with an alkylene oxide having a carbon number of 3 to 5 and an ethylene oxide with R ^1a OH by, for example, a structure according to the general formulae (a1-1) to (a1-6). And get. The order or conditions of the formulation can be studied according to the target structure, and the addition reaction can be carried out in a block or random manner. Further, the reaction ratio of the alkylene oxide having a carbon number of 3 to 5 to the R ^1a OH per 1 mole of the ethylene oxide may be in the range of p and q of the above formula (1), that is, p=8 to 40. , q = 0 to 5, and the condition of p = p11 + p12 + p13 or p = p11 + p12 or the preferred range described above. In other words, the reaction ratio of the alkylene oxide to the ethylene oxide having a carbon number of 3 to 5 added to the aliphatic alcohol may be within the range of p and q, p11, p12, and p13.

In general, the ratio of addition of each ethylene oxide or propylene oxide to the above 1 mole of R ^1a OH and the average addition mole number of the alkyleneoxy group represented by the above formula are substantially The same can be different in the present invention depending on the manufacturing method. As the component (a1) of the present invention, a more preferable nonionic surfactant is a structure of the formula (a1-5) or (a1-6), and further preferably a structure of the formula (a1-5). Further, in the formula (a1-5), p11/(p11+p12) is preferably 0.2 to 0.8.

The production conditions including the steps A to D below are exemplified as the optimum production conditions for further limiting the range of the above p11, p12, p13, and q.

Step A: with respect to ethylene oxide per 1 mole of R ^1a OH at a ratio of 4 moles to 14 moles, preferably 8 to 12 moles (the range of values may also be defined as p11 in the above formula) Addition reaction.

Step B: Next, propylene oxide 1~3 moles, preferably 2~3 moles (the numerical range can also be defined as q in the above formula) and ethylene oxide 0~4 moles (the numerical range is also A random or block addition reaction can be carried out by specifying p13) in the above formula. More preferably, only the propylene oxide 2 to 3 moles (the numerical range may be defined as n in the above formula) may be subjected to an addition reaction.

Step C: Thereafter, an addition reaction of ethylene oxide 4 to 14 mol, preferably 8 to 12 mol (the numerical range may also be defined as p12 in the above formula) is again carried out.

Step D: The treatment of the catalyst used for the reaction is carried out. For example, in the case of using an alkali catalyst, neutralization with an acid, or in the case of a solid catalyst, filtration or the like.

The p and q of the component (a1) can be determined by NMR (Nuclear Magnetic Resonance) or liquid chromatography, and the alkyl group is shorter, for example, the alkyl group is relatively linear per 1 mole. In the case where the primary alcohol is a compound obtained by an addition reaction with ethylene oxide in a ratio of less than 8 moles, gas chromatography can also be used. Or in the present invention, p and q may be a ratio of alkylene oxide and ethylene oxide having a carbon number of 3 to 5 per 1 mol of R ^1a OH.

Further, a preferred aspect of the component (a2) is as follows.

In the formula (a2) of the component (a2), R ^2a is an alkyl group or an alkenyl group having a carbon number of 8 to 22, preferably an alkyl group or an alkenyl group having a carbon number of 10 to 18, more preferably 12 to 14. Further, it is preferably a linear alkyl group having a carbon number of 12 to 14. R ^21a is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group. l is a number of 0 or 1, and is preferably a number of one. AO is a stretching alkyloxy group having a carbon number of 3 to 5, which is obtained by addition reaction of an alkylene oxide having 3 to 5 carbon atoms, and a portion bonded by an addition reaction preferably has The structure of a methyl branch, an ethyl branch or a propyl branch. Further, the AO group is preferably a stretching alkyloxy group having a carbon number of 3 and/or a stretching alkyloxy group having a carbon number of 4, and specific examples thereof include a trimethyleneoxy group and an oxypropane-1,2. -diyl, oxybutane-1,2-diyl, oxybutane-1,3-diyl, oxybutane-2,3-diyl, oxytetramethylene. Among them, the AO group is preferably an oxypropane-1,2-diyl group (hereinafter, the oxypropane-1,2-diyl group is sometimes referred to as a propyloxy group or a PO group in the present invention). m and n are the average addition molar number, and m is preferably 5 to 30, more preferably 8 to 25, still more preferably 10 to 20, and n is preferably 0 to 5, and further preferably 0. ~3 number.

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

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

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

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

Further, preferred aspects of the component (a3) are as follows.

In the formula (a3) of the component (a3), R ^3a is an alkyl group or an alkenyl group having a carbon number of 8 to 22, preferably an alkyl group or an alkenyl group having a carbon number of 10 to 18, more preferably 12 to 14. Further, it is preferably a linear alkyl group having a carbon number of 12 to 14. Further, the carbon atom to which R ^3a -O- is bonded to the R ^3a of the oxygen atom is a primary carbon atom and/or a secondary carbon atom. Further, in the present invention, in order to distinguish from a branched hydrocarbon group, it may also be a straight chain in the case of an alkyl group or an alkenyl group having a secondary carbon atom. The average addition molar number r of the ethyloxy group is 2 or more and less than 8, preferably 2.5 to 7.5, more preferably 3 to 7.

The production of a nonionic surfactant in which a carbon atom of R ^3a bonded to an oxygen atom is a primary carbon atom is exemplified by a method of adding ethylene oxide to a primary alcohol. Further, as for the production of a nonionic surfactant in which a carbon atom of R ^3a bonded to an oxygen atom is a secondary carbon atom, addition of ethylene oxide to a secondary alcohol or ethylene oxide may be used. A known production method such as a method of reacting an olefin or an internal olefin, a method of reacting polyethylene glycol with an olefin, a method of introducing a hydroxyl group into a normal alkane, and adding ethylene oxide.

Further, a preferred aspect of the component (a4) is as follows.

The component (a4) is preferably a compound represented by the following formula (a4).

R ^4a -O-[(AO) _s /(Gly) _t ]-H (a4) wherein R ^4a is an alkyl group or an alkenyl group having a carbon number of 8 to 22. AO represents an extended ethyloxy group or a propyloxy group, Gly represents a residue derived from glycerol, s represents an average addition mole number of AO, t represents an average addition mole number of Gly, and s is 0. ~5, t is 2~10. / indicates that AO and Gly can be random or block].

R ^4a in the formula (a4) preferably has a carbon number of 12 to 16, more preferably a carbon number of 12 or 14, and further preferably R ^4a is a linear alkyl group, especially R ^4a -O- The carbon atom to which the oxygen atom is bonded to R ^4a is a linear alkyl group of the first-order carbon atom. s is preferably 0. t represents the average addition mole number, preferably 2 to 5.

The compound represented by the formula (a4) may also be a mixture of compounds containing s = 0, Gly having a molar addition t' (integer value). In this case, it is preferred to contain a mixture of one or more, and more preferably two or more compounds having a t' of 3, 4 or 5. In the mixture, the ratio of the total of compounds having a t' of 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, and further, at a low temperature. From the viewpoint of 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, in the mixture, the proportion of the compound having t' of 1 or 2 is preferably less than 50% by mass, more preferably less than 35% by mass.

Further, preferred aspects of the component (a5) are as follows.

The (a5) component is, for example, a polysaccharide-type surfactant represented by the following formula (a5).

R ^5a -(OR ^51a ) _x Z _y (a5) wherein R ^5a represents an alkyl or alkenyl group having a carbon number of 8 to 18, R ^51a represents an alkylene group having a carbon number of 2 to 4, and Z represents carbon. The number is 5 or 6 residues derived from reducing sugars, x is the average addition molar number, x is the number 0 to 6, y is the average condensation degree, and y is the number 1 to 10.

In the formula (a5), R ^5a preferably has a carbon number of 12 to 16, more preferably a carbon number of 12 or 14, and further, R ^{5a is} preferably a linear alkyl group, especially R ^5a -O- The carbon atom to which the oxygen atom is bonded to R ^5a is a linear alkyl group of the first-order carbon atom. x is preferably 0. Further, Z is preferably a glucose residue. The average degree of condensation of y is preferably from 1.2 to 3. The compound represented by the formula (a5) may also be a mixture of compounds containing a degree of condensation y' (integer value) of Z. In this case, a mixture of one or more, and more preferably two or more, compounds having x=0 and y' of 1, 2 or 3 is preferred. In the mixture, the ratio of the total of the compounds wherein y' is 1, 2 or 3 is preferably 60% by mass or more, more preferably 80% by mass or more.

The liquid detergent composition of the present invention contains a nonionic compound represented by the following formula (A1) [hereinafter sometimes referred to as (A1) component] as the component (A).

RO-(C ₂ H ₄ O) _x -H (A1) [wherein, R is a linear alkyl group having a carbon number of 12, and a carbon atom of RO- bonded to R of the oxygen atom is a primary carbon atom. x is the addition molar number of the exoethyloxy group and is an integer of 2 to 5].

From the viewpoint of achieving the object of the present invention, it is important that R in the formula (A1) is a linear alkyl group having 12 carbon atoms, and the hydrocarbon group of the oxygen-bonded alkyl group is a primary carbon atom. By using the nonionic compound of the component (A1) in combination with the cationic surfactant of the component (B), it is possible to suppress not only the odor of the fiber product caused by the semi-drying of 4M3H, which was previously difficult to remove, but also It can suppress the recurring semi-dry odor. Further, the compound having an EO group of 3, 4 and 5 moles in the component (A1) is excellent in suppressing the semi-dry odor, particularly the re-occurring semi-dry odor, and therefore is preferably in the formula (A1). The x is 3, 4 or 5. Further, in the component (A1), x in the formula (A1) is 3, 4 or The total of the compounds of 5 is preferably from 70 to 100% by mass, and more preferably from 80 to 100% by mass.

The component (A1) can be synthesized into a composition of the present invention by synthesizing a compound having a single molar molar addition of a polyethyloxy group, or can be formulated with a polyoxyl group having a different molar amount of a methyl group. A component of a nonionic surfactant produced and obtained in the form of a mixture of vinyl alkyl ethers. The component (A1) may be, for example, a component derived from the component (a1) or the component (a3) from the viewpoint of economical manufacture, and R ^{3a of the} general formula (a3) in the case of the component derived from the (a3) component. It is a linear alkyl group having a carbon number of 12, and a carbon atom of R ^3a to which an oxygen atom is bonded to R ^3a -O- is a primary carbon atom. In the case of the nonionic surfactant of the formula (a3), it is preferred to contain, for example, an epoxy resin having an average of 2 moles or more and less than 8 moles by addition of a base catalyst or an acid catalyst to the lauryl alcohol. A nonionic surfactant obtained by using an alkane is a nonionic surfactant containing the component (A1). In this case, the component (a3) is produced as a mixture of a vinyloxy group-added mole-dispersed polyoxyethylene lauryl ether, and the component (A1) is contained in the mixture. The content of the compound corresponding to the component (A1) in the component (a3) must be confirmed in advance, and the content of the component (A) or the component (A1) in the composition or the like is adjusted.

The component (A1) varies depending on the production method, but when the component (a1) is q=0, and the case where R ^{1a is} derived from lauryl alcohol (in the case of lauryl), there is also a small amount of inclusion. . Therefore, the component (a1) may be prepared by appropriately confirming the content of the compound corresponding to the component (A1), adjusting the content of the component (A) or the component (A1) in the composition, etc., according to the structure, the production method, and the like. In the case where the component (a1) is q≧1 or more, when the propyloxy group is contained as AO, the component (A1) derived from the component (a1) is hardly contained.

The component (A1) may also be the same as the component (a3). E.g. on component (a3), R ^3a having a carbon number in the straight-chain alkyl of 12, and R ^3a -O- the oxygen atom bonded to R ^3a of the carbon atoms of a carbon atom, an ethyl group, extending the When the addition molar number is a single addition molar number which is not dispersed, the average addition mole number r may be 2, 3, 4 or 5, so that such a compound can be used as the (A1) component. That is, the component (a3) may contain the component (A1). Further, the component (A1) may be used in combination of two or more.

Further, when the component (A1) is blended as a component in the component (a3), the amount of addition of the ethylene oxide used in the reaction is small, and therefore it is usually obtained as a mixture containing an unreacted alcohol. When 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 ratio of the unreacted alcohol and the compound having 1 mol of the EO group, that is, the aliphatic alcohol having a hydrocarbon group having 8 to 22 carbon atoms and the compound having 1 mol of the EO group added to the alcohol, The nonionic surfactant of the component A) is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. Among them, the lower limit is studied in terms of the energy applied by the distillation step and the environment.

The liquid detergent composition of the present invention contains 0.5 to 10% by mass of the nonionic compound of the component (A1), preferably 1 to 8 from the viewpoint of suppressing the semi-dry odor of the fiber product, particularly suppressing the odor of 4M3H. The mass% is more preferably 2 to 5% by mass. Furthermore, the (A1) component constitutes a nonionic interface activity as the component (A). One part of the sex agent.

From the viewpoint of cleanability, the liquid detergent composition of the present invention contains the nonionic surfactant of the component (A) in an amount of 15 to 70% by mass, preferably 20 to 65% by mass, more preferably 25 to 60% by mass. More preferably, it is 30 to 55 mass%. The content of the component (A1) is contained in this amount.

Further, as a specific example of the nonionic surfactant, the total concentration of the (a1) component to the (a5) component and further the (a1) component to the (a3) component nonionic surfactant is in the component (A). The proportion is preferably from 50 to 100% by mass, more preferably from 60 to 100% by mass, and still more preferably from 80 to 100% by mass. Among them, a nonionic surfactant of the component (a1) and/or the component (a2), and more preferably a nonionic surfactant of the component (a1) is preferably used as the main nonionic surfactant. The liquid detergent composition of the present invention contains (a1) component and/or (a2) component, and further preferably contains (a1) component, from the viewpoint of cleanability and foaming visibility in the case of application. It is 10 to 60% by mass, more preferably 15 to 55% by mass, and still more preferably 20 to 50% by mass. Further, the liquid detergent composition of the present invention preferably contains the component (a3) in an amount of from 0.5 to 20% by mass, more preferably from 1 to 18% by mass, even more preferably from the viewpoint of deodorizing effect and liquid stability. 2~15% by mass.

In order to stably contain the component (A1) and the component (B) in the composition, and sufficiently exhibit the cleaning power and the semi-dry odor suppressing effect, the liquid detergent composition of the present invention preferably satisfies the conditions shown below. The component (A) and the component (A1) are contained in at least one of (1) to (8).

Condition (1): The liquid detergent composition contains the component (A) in an amount of 20 to 65 mass%, preferably 25 to 60 mass%.

Condition (2): The liquid detergent composition contains 1 to 8 mass%, preferably 2 to 5 mass% of the component (A1).

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 in the formula (a1), and further, in the formula (a1-5), R ^1a is a carbon number of 12 to 16. And the carbon atom of R ^1a -O- bonded to the oxygen atom of R ^1a is an alkyl group of a primary carbon atom, the AO group is a propyloxy group, p = 14 to 35 [in the formula (a1-5) In the case, p11=1~20, p12=1~20], q=1~3.

Condition (5): The liquid detergent composition contains 15 to 55 mass% of the component (a1), preferably 20 to 50 mass%.

Condition (6): The component (a3) is contained as the component (A).

Condition (7): containing the component (a3) as the component (A), the component (a3) is in the formula (a3), and R ^3a is a linear alkyl group having a carbon number of 12 to 14, R ^3a -O- The carbon atom bonded to R ^3a of the oxygen atom is a primary carbon atom, and r is 3-7.

Condition (8): The liquid detergent composition contains 1 to 18% by mass of the component (a3), preferably 2 to 15% by mass.

According to the above conditions, the liquid detergent composition of the present invention preferably contains the component (A) in an amount of 20 to 60% by mass, preferably 25 to 55% by mass in the liquid detergent composition; and is contained in the liquid detergent composition. The component (A1) is 1 to 8 mass%, preferably 2 to 5 mass%, and the liquid detergent composition contains 15 to 55 mass% of the component (a1), preferably 20 to 50 mass% as the component (A). the component (a1) based in the general formula (a1), and further the general formula (A1-5) are, R ^1a is a 12 to 16 carbon atoms, and R ^1a -O- bonded to the oxygen atom of R ^1a The carbon atom is an alkyl group of a primary carbon atom, and the AO group is a propyloxy group, p=14-35 [in the case of the general formula (a1-5), further p11=1~20, p12=1~20 ], q = 1 to 3; and contains (a3) a component of 1 to 18% by mass, preferably 2 to 15% by mass as the component (A), and the component (a3) is in the formula (a3), R ^3a It is a linear alkyl group having a carbon number of 12 to 14, and a carbon atom of R ^3a -O- bonded to the oxygen atom of R ^3a is a primary carbon atom, and r is 3 to 7.

Among them, the component (A1) may be derived not only from the component (a3) but also from the component (a1). Furthermore, the structurally preferred aspects of the components are based on the above-mentioned requirements. In addition, the concentration range of the compound of each of the nonionic surfactants of the lower-order concept and the concentration range of the total of these may be included in the range of the concentration range of the component (A) as a superior concept, or may be combined. Each preferred concentration range.

Further, the description of the above conditions (1) to (8) and the preferable requirements are also preferable in terms of the foaming visual property at the time of application.

<(B) component>

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

[wherein, R ^b1 is a chain hydrocarbon group having a carbon number of 12 to 18, and may also contain -(A'O) _s - in R ^b1 ; A'O is a stretching ethyloxy group or a propyloxy group. s represents the average addition molar number of A'O, and is 0 to 10, and R ^b2 , R ^b3 and R ^b4 are each independently a methyl group, an ethyl group, a benzyl group or a hydroxyalkyl group having a carbon number of 1 to 3. X ^- is CH ₃ SO ₄ ^- or CH ₃ CH ₂ SO ₄ ^- , halogen ion].

The carbon number of R ^b1 in the formula (B1) is preferably from 14 to 18, more preferably from 14 to 16. Further, the chain hydrocarbon group of R ^b1 is a benzene ring or a substituent of a cyclic structure. The chain hydrocarbon group is preferably a linear alkyl group or a linear alkenyl group, and more preferably a natural oil or fat. Also, s is preferably 0.

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

As the cationic surfactant of the component (B), for example, the following (b1) to (b4) can be used, and a compound selected from the group consisting of (b1) and (b3) is more preferable. The compound of (b1) is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 80% by mass or more. The carbon number of R ^b1 of the compound of (b1) to (b4) is preferably from 12 to 16, more preferably from 14 to 16, and the chain hydrocarbon group is preferably a linear alkyl group, and more preferably derived from nature. Grease. The counter ion is preferably CH ₃ SO ₄ ^- or CH ₃ CH ₂ SO ₄ ^- .

(b1) is a quaternary ammonium salt in which R ^b1 in the 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) is a quaternary ammonium salt in which R ^b1 in the 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) is a quaternary ammonium salt in which R ^b1 in the 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) is a linear alkyl group of the formula (B1) wherein R ^b1 is a linear alkyl group having 12 to 18 carbon atoms, s is 1 to 5, and R ^b2 , R ^b3 and R ^b4 are each a methyl group or an ethyl group. Ammonium salt.

The cationic surfactant of component (B) can be used with nonionic compounds (A1) The combination inhibits the growth of the odor pathogenic bacteria of the fiber product excellent in drying resistance. That is, in the case of the semi-dry odor, after the fibrous product is sufficiently dried, the semi-dry odor which reoccurs due to moisture generation exhibits an excellent suppressing effect. That is, it is effective in suppressing the generation of the above-mentioned 4-methyl-3-hexenoic acid as a middle chain fatty acid odor.

The liquid detergent composition of the present invention contains the component (B) in an amount of 0.3 to 5% by mass, preferably 0.3 to 4% by mass, more preferably from the viewpoint of suppressing the semi-dry odor, particularly suppressing 4M3H odor and cleanability. It is 0.5 to 3% by mass, and more preferably 0.8 to 3% by mass.

<(C) component>

However, the liquid detergent composition of the present invention contains, as a surfactant, a nonionic surfactant (A) containing a nonionic compound (A1) and a cationic surfactant (B) as essential components, but may be limited. Further, another surfactant (C) such as an anionic surfactant and an amphoteric surfactant is contained [hereinafter referred to as a component (C)].

Among the anionic surfactants, the anionic surfactant other than the fatty acid and the salt thereof has a concern of lowering the odor suppressing effect of the liquid detergent composition of the present invention, and therefore, it is described separately from the fatty acid and the salt thereof. Further, when the pH of the liquid detergent composition of the present invention is acidic, it may be present as an acid type compound depending on the surfactant, and the acid type compound is also considered as a surfactant.

(c1) anionic surfactants other than fatty acids and their salts

Specific examples of the anionic surfactant other than the fatty acid and the salt thereof include: (c1-1) an alkylbenzenesulfonate having an alkyl group having an average carbon number of 10 to 20, and (c1-2) a polyoxyalkylene alkyl ether sulfate having an average carbon number of 10 to 20 The alkyl group derived from a linear primary alcohol or a linear secondary alcohol or an alkyl group derived from a branched alcohol. The average addition molar number of the alkyloxy group is 1 to 5, and the ethyl ethoxy group is used as a stretching. The alkyloxy group may also have a propyloxy group in an average addition molar number of 0.2 to 2 moles, and (c1-3) an alkyl group or an alkenyl group having an average carbon number of 10-20. An alkyl or alkenyl sulfate salt, and (c1-4) a polyoxyalkylene alkyl ether carboxylate having an average carbon number of 10 to 20 derived from a linear primary alcohol or a linear secondary alcohol An alkyl group or an alkyl group derived from a branched alcohol. The average addition molar number of the alkylene group is 1 to 5, and the ethylideneoxy group is used as the alkyleneoxy group, and the average molar number is also added. It contains a stretching propyloxy group in the range of 0.2 to 2 moles. The salt is an alkali metal salt such as sodium or potassium, and is preferred in terms of suppressing the semi-dry odor.

In the present specification, a bleach activator having an anionic group, especially an alkyl nonyloxybenzenesulfonic acid or alkynyloxybenzenecarboxylic acid having a linear or branched alkyl group having a carbon number of 8 to 22 Or such an alkali metal salt as an anionic surfactant (c1) other than a fatty acid and a salt thereof.

(c2) fatty acids and their salts

The fatty acid and its salt are preferably fatty acids having a carbon number of 10 to 18 and salts thereof, and those having a fatty acid distribution obtained from natural fats and oils may also be used. The fatty acid and its salt can be formulated as a defoaming agent in the liquid detergent composition of the present invention. The salt is preferably an alkali metal salt such as sodium or potassium.

(c3) amphoteric surfactant

The amphoteric surfactant may, for example, be a sulfobetaine having an alkyl group having 8 to 22 carbon atoms or the carbonylbetaine or a fatty acid amidinopropyl group having a carbon number of 7 to 21 (or hydroxypropyl group). Base) betaine or the carbonyl betaine.

(c4) Cationic surfactant other than (B)

The cationic surfactant other than the component (B) may, for example, be a quaternary ammonium compound other than the component (B) or an amine compound, for example, an amine compound such as a fatty acid guanamine dimethylamine having a carbon number of 7 to 21.

Since the anionic surfactant (c1) other than the fatty acid and its salt lowers the bactericidal effect of the component (A1) and the component (B), the content thereof is limited in order to sufficiently suppress the generation of the semi-dry odor of the fiber product. Specifically, the ratio of the ratio of the anionic surfactant (c1) other than the fatty acid and its salt to the cationic surfactant (B), that is, the ratio of (c1)/(B) is 0 to 1, preferably 0 to 0.8. More preferably, it is 0 to 0.5, more preferably 0 to 0.1. As described above, in the present invention, it is also considered that a bleach activator having an anionic group is used as an anionic surfactant (c1) other than a fatty acid and a salt thereof, and the blending ratio is preferably as low as possible. The mass of the anionic surfactant (c1) is set to a value assumed to be an acid form. When the mass ratio of (c1)/(B) is satisfied, the content of the anionic surfactant (c1) other than the fatty acid and the salt thereof is preferably 5% by mass or less, and more preferably 3 mass, in the liquid detergent composition. % or less is further preferably 2% by mass or less, and more preferably 0.4% by mass or less.

The amphoteric surfactant may be formulated to such an extent that the effect of the present invention is not impaired, and it is preferably used in such a manner that the mass ratio of [(c1)+(c3)]/(B) becomes the range of the above (c1)/(B). . Moreover, after satisfying the above mass ratio, the (c3) component is combined The content is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less.

The content of the fatty acid and the salt (c2) in the composition is 0.05 to 5% by mass, more preferably 0.1 to 4% by mass, still more preferably 0.1 to 3% by mass, based on the fatty acid (in terms of the acid compound). In the composition, the fatty acid salt has an acid form in the relationship of pH. The salt is an alkali metal salt such as sodium or potassium, and is preferred in terms of suppressing the semi-dry odor.

<(D) component>

In order to suppress the semi-dry odor, the liquid detergent composition of the present invention contains hydrogen peroxide as the component (D). In the present invention, by using the above nonionic compound (A1), cationic surfactant (B) and hydrogen peroxide (D) under specific conditions, it has been shown that the previously insufficiently solved inhibition is as described above. The effect of the overall odor of the semi-dry odor fiber product.

The liquid detergent composition of the present invention contains (D) a component in an amount of 0.3 to 10% by mass, preferably 0.5 to 8% by mass, more preferably 1 to 1 from the viewpoint of suppressing the semi-dry odor and the stability of hydrogen peroxide. 6% by mass. Further, the concentration of hydrogen peroxide in the composition can be determined by a reverse titration method using a potassium iodide solution.

<Other ingredients>

Hereinafter, other components which can be used in the liquid detergent composition of 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 so-called water-miscible organic solvent in the present invention means at 25 ° C When the ion-exchanged water is dissolved in 1 L of 50 g or more, it means a solvent having a degree of dissolution of 50 g/L or more.

The (E) component is preferably a mixed aqueous organic solvent having a hydroxyl group and/or an ether group.

Examples of the water-soluble organic solvent include (e1) an alcohol such as ethanol, 1-propanol, 2-propanol or 1-butanol, and (e2) a glycol such as propylene glycol, butanediol or hexanediol. E3) glycols such as diethylene glycol, 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 monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy 2-propanol, 1-methyl glyceryl ether, 2-methyl glyceryl ether, 1,3-dimethyl glyceryl ether, 1-ethyl glyceryl ether, 1,3-diethyl glyceryl ether, triethyl Alkyl ethers such as 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 monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, phenoxypropanediol, 2-benzyloxyethanol, diethyl An aromatic ether such as diol monobenzyl ether.

The component (E) is effective as a viscosity modifier and a gelation inhibitor of the composition, and is preferably selected from the above (e1) alkanols, (e2) glycols, (e4) alkyl ethers, (e5). One or more of the aromatic ethers, more preferably one or more selected from the group consisting of (e2) diols, (d4) alkyl ethers, and (e5) aromatic ethers, can be more efficiently carried out Viscosity adjustment and gelation inhibition of the composition.

Further, in the liquid detergent composition of the present invention, in order to make hydrogen peroxide Stabilizing and suppressing semi-dry odor, preferably (e4) alkyl ethers and/or (e5) aromatic ethers, of which diethylene glycol monobutyl ether and diethylene glycol monophenyl ether are preferred. , triethylene glycol monophenyl ether, or phenoxy propylene glycol. More preferably, it is diethylene glycol monobutyl ether and/or triethylene glycol monophenyl ether.

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

[(F) ingredient]

In the liquid detergent composition of the present invention, for the stability of the composition, it is preferred to formulate a dissolution aid as the component (F). The dissolution aid of the present invention is an organic compound having an anionic group, and further includes an alkylbenzene having 1 to 2 alkyl groups selected from a methyl group, an ethyl group or a propyl group and having a sulfonic acid group or a carboxylic acid group. A carboxylic acid or an alkylbenzene sulfonic acid or a salt thereof, and a benzoic acid or a salt thereof. More specifically, it is p-toluenesulfonic acid, cumenesulfonic acid, m-xylenesulfonic acid, and benzoic acid, and the salt is preferably an alkali metal salt. In the present invention, p-toluenesulfonic acid or an alkali metal salt thereof is preferably used, and an acid may be formulated and neutralized by an alkali agent in the composition. The component (F) imparts stability without inhibiting the suppression of the semi-dry odor.

The component (F) is preferably a salt of an alkali metal. The liquid detergent composition of the present invention contains the component (F) in an amount of 0.1 to 5% by mass, preferably 0.5%, in terms of converting the component (F) into an acid compound. 4% by mass, more preferably 1 to 3% by mass.

[(G) component]

In the liquid detergent composition of the present invention, in the case of adjusting the stability of hydrogen peroxide or the like, it is used as a condition for adjusting an anionic surfactant, a dissolution aid, a chelating agent, or the like in an acid type compound. Neutralization of pH As the agent or the like, an alkali agent [hereinafter referred to as a component (G)] is preferably used. When the pH of the liquid detergent composition of the present invention is 7.0 or less as described below, it is considered that there is almost no free alkali agent. Further, as the alkali agent for neutralization, an alkali metal hydroxide is preferably used, and more preferably potassium hydroxide and/or sodium hydroxide.

In addition, an alkanolamine compound (hereinafter sometimes referred to as a (G') component) having a total carbon number of 6 or less, such as a water-mixed organic amine compound, further monoethanolamine, diethanolamine or triethanolamine, is used as the neutralization. In the case of the agent, the content in the composition is preferably less than 1% by mass, more preferably 0.5% by mass or less, still more preferably 0.08% by mass in terms of the effect of suppressing the semi-dry odor. the following. The (G') component is a component which is formulated as a salt of an anionic compound other than an alkalizing agent (for adjusting a pH neutralizing agent), and is also included in the amount of the (G') component.

[(H) component]

The liquid detergent composition of the present invention preferably contains an organic chelating agent capable of chelating a polyvalent metal ion [hereinafter referred to as a (H) component] in terms of maintaining the effect of the present invention over time. Examples of the organic chelating agent of the component (H) include nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol ether diaminetetraacetic acid, and hydroxyethylamide. Aminopolyacetic acid such as aminodiacetic acid, triethylenetetraamine hexaacetic acid or melamine, or a salt thereof, diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid Polycarboxylic acid or a salt thereof other than aminopolyacetic acid such as malic acid, oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid or carboxymethyl tartaric acid, aminotris(methylenephosphonic acid), 1-hydroxyl Ethylene-1,1-diphosphine An organic phosphonic acid such as an acid, ethylenediaminetetrakis (methylenephosphonic acid) or diethylenetriamine penta (methylenephosphonic acid) or a salt thereof may, for example, be an alkali metal salt. In the present invention, it may also be a salt which is neutralized by an acid in an aqueous solution. Among them, an organic phosphonic acid or a salt thereof, particularly 1-hydroxyethylidene-1,1-diphosphonic acid, is preferred. Further, the counter ion is preferably an alkali metal salt.

In the present invention, it is preferred to contain an organic chelating agent in terms of suppressing the effect of the present invention caused by storage, and in many cases, it contributes to inhibition by an organic chelating agent. Decomposition of hydrogen peroxide produced by heavy metal ions. On the other hand, since the organic chelating agent is a compound which has a property of suppressing the fluctuation of the pH value at the time of dilution, in order to obtain the excellent cleaning power, it is easy to change the pH value of the water to be neutral. In the vicinity, it is preferably a small amount and an effective agent. As such an organic chelating agent, the above organic phosphonic acid or a salt thereof is preferred, and the salt is preferably a potassium salt or a sodium salt.

The content of the component (H) in the composition is preferably from 0.01 to 0.5% by mass, more preferably from 0.03 to 0.3% by mass, even more preferably from 0.05 to 0.2% by mass, based on the amount of the acid compound. Further, the component (H) preferably contains 1-hydroxyethylidene-1,1-diphosphonic acid within the limits of the concentration range.

[(I) component]

As the component (I), it is preferred to prepare a water-soluble polymer for the purpose of improving the effect of suppressing the semi-dry. The polymer is preferably a polymer comprising a constituent unit having a carboxylic acid group, and examples thereof include polyacrylic acid, an acrylic acid-maleic acid copolymer, acrylic acid or maleic acid, and a carbon number of a copolymer of 2 to 5 olefins. Also, the content of the surfactant is higher In many high-concentration surfactant systems, it is preferred to use a high molecular polymer containing both a constituent unit including a monomer having a carboxylic acid group and a constituent unit containing a monomer having a polyoxyethylene chain. For example, a polymer described in JP-A-H05-60476 or JP-A-2004-155937 can be cited. The blending ratio of the component (I) in the composition is preferably from 0.1 to 5% by mass, more preferably from 0.5 to 4% by mass.

[Ingredients other than the above]

Further, the components shown in the following (i) to (vii) can be blended in the liquid detergent composition of the present invention to the extent that the effects of the present invention are not impaired.

(i) enzymes such as cellulase, amylase, pectinase, protease, lipase, etc.

(ii) Calcium ion source (calcium ion supply compound), dihydroxy compound, enzyme stabilizer such as formic acid

(iii) a fluorescent dye such as a fluorescent dye sold by Tinopal CBS (trade name, manufactured by Ciba Specialty Chemicals) or Whitex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.)

(iv) antioxidants such as butylhydroxytoluene, distyryl cresol, sodium sulfite and sodium hydrogen sulfite

(v) The gelation preventing polymer described in JP-A-H11-513067, and further preferably a polypropylene glycol or polyethylene glycol having a weight average molecular weight of 600 to 5,000, more preferably 1,000 to 4,000. Further, the weight average molecular weight can be determined by a light scattering method, and can be measured by a dynamic light scattering photometer (DLS-8000 series, manufactured by Otsuka Electronics Co., Ltd., etc.).

(vi) alkanes such as octane, decane, dodecane and tridecane, olefins such as terpene and dodecene, halogenated alkyl groups such as dichloromethane and 1,1,1-trichloroethane Non-mixed aqueous organic solvents such as terpenes such as D-limonene

(vii) In addition to pigments, perfumes, antibacterial preservatives, polyfluorene defoamers, etc.

The concentration which is used as an index in the case where the above-mentioned optional component is blended in the liquid detergent composition of the present invention is shown below, but may be appropriately adjusted to the extent that the effect is not impaired, and is not suitable for the case of blending.

The content of the enzyme (i) is preferably 0.001 to 2% by mass. The content of the enzyme stabilizer (ii) is preferably 0.001 to 2% by mass. The content of the fluorescent dye of (iii) is preferably 0.001 to 1% by mass. The content of the antioxidant of (iv) is preferably from 0.01 to 2% by mass. The polyalkylene glycol-based gelation preventing polymer of (v) is preferably from 0.01 to 2%. The non-mixed aqueous organic solvent of (vi) is preferably 0.001 to 2% by mass. The other components of (vii) can be formulated, for example, at a known concentration.

In the liquid detergent composition of the present invention, the bleach activator, for example, an anionic group-containing bleach activator is preferably less than 1% by mass, more preferably from the viewpoint of liquid stability and inhibition of decomposition of hydrogen peroxide. It is 0.4% by mass or less, and more preferably does not contain a bleach activator. The bleach activator of the present invention refers to a compound which reacts with hydrogen peroxide in water and then reacts under stable conditions such as in a domestic environment to form an organic peracid. As the bleach activator, an alkyl group having a linear or branched alkyl group having a carbon number of 8 to 22, which is known to be blended in a liquid bleach composition other than TAED (Tetraacetyl Ethylene Diamine), may be mentioned. Mercaptooxybenzenesulfonic acid or alkylnonyloxybenzenecarboxylic acid or such alkali metal salts. It is known that among these, an alkyl decyloxybenzenesulfonic acid or an alkyl decyloxy benzene carboxylic acid having a linear or branched alkyl group having a carbon number of 8 to 22 or such an alkali metal salt can be stabilized. Formulated with hydrogen peroxide, but in the present invention, these are anionic The bleach activator is also an anionic surfactant (c1) other than a fatty acid and a salt thereof, and may be subjected to bleach activation as long as it is limited by the mass ratio of (c1)/(B) and the mass ratio is within a specific range. Agent. However, in the case where the bleach activators are formulated in the liquid detergent composition of the present invention, the effect of the bleach activator cannot be sufficiently exerted. Further, in order to stably mix the bleach activator, not only the composition is limited but also the deodorizing effect of the present invention is lowered.

Generally, in the case of a cleaning liquid or a bleach containing hydrogen peroxide, the bleaching effect is enhanced by increasing the pH of the solution during the treatment. However, the liquid detergent composition of the present invention is also preferably substantially free of a boron compound for making the pH alkaline when diluted in water. The boron compound reduces the cleaning power in the present invention. Here, the boron compound is boric acid, borax or borate. Specifically, examples of the borate include sodium borate, potassium borate, ammonium borate, sodium tetraborate, potassium tetraborate, and ammonium tetraborate. In addition, the term "substantially not contained" means, for example, a case where an enzyme preparation which is a stabilizer of an enzyme is mixed in a very small amount, and the like. Specifically, it is converted into boric acid in the composition, wherein the borax is not more than 0.1% by mass, and further less than 0.01% by mass, based on the mass of itself. Further, the lower limit value is 0% by mass.

The remainder of the liquid detergent composition of the present invention is water. Preferably, the water is sterilized deionized water.

From the viewpoint of the cleaning power and the deodorizing effect, the pH of the liquid detergent composition of the present invention at 20 ° C as described in 8.3 of JIS K3362:1998 is preferably 3.0 to 7.0, more preferably 3.5. ~7.0, and thus better 4.0~6.0.

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

In terms of ease of handling, the liquid detergent composition of the present invention preferably has a viscosity of 10 to 1,000 mPa at 20 ° C. s, more preferably 50~600 mPa. s, and further preferably 100 to 300 mPa. s. The viscosity can be adjusted according to the ratio of the component (a1), the component (a2), the component (E), water, and the like in the formulation component. The above nonionic surfactant (a1') is generally easy to use as the component (a1) in terms of making the composition low in viscosity.

In the present invention, the viscosity is measured by a B-type viscometer. The rotor system is selected to match the viscosity. The rotation was performed at a rotation number of 60 r/min, and the viscosity after 60 seconds from the start of the rotation was taken as the viscosity of the liquid detergent composition.

The liquid detergent composition of the present invention is used as a detergent composition for a fibrous product. Among them, a liquid detergent composition such as a clothing, a towel, a foot pad, a bed sheet bedding product, or the like, which is used in household life, and the like, is preferably used as a liquid detergent composition for clothing. Further preferred as a liquid detergent composition for water washable fibrous articles.

In the present invention, excellent cleaning power can be obtained by using a cleaning liquid containing the liquid detergent composition of the present invention and water, for example, an aqueous solution in which the liquid detergent composition of the present invention is dissolved in water to clean the fibrous product. Stinky effect. The cleaning liquid is preferably used in a liquid detergent composition in a ratio 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 For washing liquid. The temperature of the cleaning liquid at the time of cleaning is not particularly limited. According to the liquid detergent composition of the present invention, the cleaning power and the deodorizing effect can be obtained in a wide temperature range of a water temperature of 5 ° C to 40 ° C. Alternatively, the immersion placement step can be provided prior to cleaning. In the case where the immersion placing step is provided, it is preferably carried out at a concentration at which the concentration of the liquid detergent composition is 3 to 6 times the concentration at the time of cleaning.

Furthermore, the liquid detergent composition of the present invention is applied by applying (in a non-foamed state) to the finished fiber product, and then applying the finished fiber product to the fiber product, and the fiber product is present in the fiber product. In the case, a foam that is easy to visualize is formed. The foam is produced by a disproportionation reaction caused by catalase in bacteria. Interestingly, no foaming was observed in the new product that was only used or worn for one day. Foaming due to application of the liquid detergent composition of the present invention is observed in the fibrous articles used or worn and washed several times. Further, the use of the old fiber product, even after washing and drying, may sometimes confirm foaming due to application of the liquid detergent composition of the present invention.

Accordingly, in addition, a method of cleaning a fibrous article comprising the step of applying a liquid detergent composition of the present invention to a fibrous article to produce a foam is also provided. By this method, the presence of bacteria can be confirmed by the generation of the foam, and one part of the liquid detergent composition can be applied to the fiber product in part.

By the cleaning method of the fibrous product of the present invention which is applied by this method, not only the presence of bacteria of the fibrous product but also the liquid detergent composition can be applied intensively around the presence of the bacteria. This idea is revealed in Guan Japanese Patent Laid-Open No. 2010-59296, which is used for a hard surface cleaning agent. Further, a liquid bleach composition for a fiber product containing hydrogen peroxide in a previous part may sometimes be foamed by the presence of bacteria. However, previous liquid bleach compositions incorporating hydrogen peroxide have lower surfactant concentrations and do not provide sufficient foam visuality. Further, the conventional bleaching agent for fiber products has a bleaching effect as a main problem, and therefore it is intended to be used intensively for visually checking the stains of the stains or the cuffs. On the other hand, in the case of considering the problem of deodorization related to bacteria as in the present invention, it is very meaningful to use the visualization of foaming.

The liquid detergent composition of the present invention is foamed by contact with bacteria. The composition of the composition excellent in the visibility by the bacteria of the foam is based on the preferred conditions of the above liquid detergent composition. In particular, as the nonionic surfactant (A), a compound of the formula (a1) and the formula (a2) is preferred, and further, a PO group having an average of 1 mol or more and 3 mol or less in the molecule is present due to bacteria. The presence of the foam is easy to produce, and the time from foaming to defoaming is also appropriate.

The present invention also relates to a process comprising applying a liquid detergent composition of the present invention to a fibrous product and foaming, and contacting the fibrous product coated with the liquid detergent composition with a cleaning liquid containing water for cleaning treatment. The method of cleaning the fibrous product of the step. In the case where the liquid detergent composition of the present invention is used for application, the applied fibrous product and any detergent can be put into a washing tank and cleaned together with any other fibrous product. Further, it is not denied that any cleaning liquid contains the liquid detergent composition or other cleaning agent of the present invention for application. in particular, A portion of the liquid cleansing composition of the present invention for cleaning (i.e., the total amount of the liquid cleanser composition of the present invention for cleaning) may be applied to the fibrous article such that the liquid cleansing composition is applied. The fibrous product is cleaned by contact with a liquid detergent composition of the present invention containing the remainder in contact with a cleaning liquid of water. More specifically, for example, by the method of cleaning a fibrous product, it is also possible to impart an excellent deodorizing effect to a fibrous product other than the portion to which the liquid detergent composition is applied or the fibrous product of the present invention: After a portion of the detergent composition is applied to the fibrous product, the coated fibrous product, and optionally any fibrous product, and the remaining portion of the liquid detergent composition of the present invention and water are placed in a washing tank. The cleaning treatment is carried out in an aqueous solution. Further, all of the liquid detergent composition of the present invention for cleaning may be applied to the fibrous product for cleaning. In the case of the step of applying, in order to obtain a sufficient effect, it is preferred that the concentration of the liquid detergent composition of the present invention in the cleaning liquid is 0.3 to 1.0 g/L as described above (this concentration may be based on the amount of application) Used to calculate the range of values).

Further, the cleaning or cleaning treatment referred to herein includes, in addition to mechanical stirring by a washing machine, a treatment by hand washing, such as rubbing, tapping, stepping, and the like.

Further, the cleaning method of the fibrous product of the present invention can be clearly distinguished from the previous use purpose by the deodorizing method or the deodorizing cleaning method of the fibrous product.

Example

The following examples are illustrative of the practice of the invention. Embodiment is against this The description of the invention is not intended to limit the invention.

<Test example (designation of semi-dry odor-causing substance)>

After washing and drying in a household, a cotton towel having a semi-dry odor was strongly produced, and 50 g was cut, and the odor component was extracted by 500 mL of dichloromethane, followed by concentration under reduced pressure. Further, 200 mL of a 1 M aqueous sodium hydroxide solution was added to the extraction solution, and the aqueous layer was recovered, and 200 mL of 2 M hydrochloric acid was added to make it acidic. Methylene chloride (200 mL) was added to the solution, and the organic layer was concentrated under reduced pressure.

Then, a gas chromatograph manufactured by Agilent was used to connect a device of a Preparative Fraction Collector (PFC) manufactured by Gerstel, and GC (Gas chromatography) was used under the following conditions. The analyzer is used to distinguish the concentrate, and the GC30 batch around the target component is captured in a glass tube filled with an inner diameter of 6 mm and a length of 117 mm (trade name: TENAX TA, manufactured by GL Sciences) ) 200 mg.

(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

Hold at 40 ° C for 1 min. → from 6 ° C / min to 60 ° C → 4 ° C / min to 300 ° C

Injection volume: 2 μL

PFC (manufactured by Gerstel): capture time is 18 min to 24 min, 30 times

Capturer: TENAX TA (trade name, manufactured by GL Sciences) 200 Mg

Finally, the target component captured in TENAX TA was connected to Agilent's GC-MS (Gas Chromatography-Mass Spectrophotometer) by a Thermal Desorption system (TDS, Thermal Desorption System) manufactured by Gerstel. The device was analyzed under the following conditions.

(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, flow rate of 50 mL / min, purification time of 3 min

Pipe column: DB-FFAP (trade name, manufactured by Agilent), length 30 m, inner diameter 250 μm, film thickness 0.25 μm

Hold at 40 ° C for 1 min → at 6 ° C / min to 60 ° C → 2 ° C / min to 240 ° C

As a result of the analysis, it was detected that 4M3H was the intermediate-stage branched fatty acid as a semi-dry odor.

<Examples and Comparative Examples> (1) Evaluation of cleaning power (1-1) Method for preparing collar film

The collar portion of the cotton/polyester blended white shirt that was worn for 3 days was cut and the same degree of dirt in the collector was selected as the collar soil test cloth. Cut the selected collar dirt test cloth into half, and sew it to a 30 cm × 30 cm cotton cloth (hereinafter referred to as the collar piece), for each of the liquid cleaners of Tables 1-3. The composition was prepared in 6 groups (all 12 pieces). Six sheets cut into one half were used for the composition of the example or the comparative example, and the other six sheets were used for the indicator detergent for cleaning power determination.

(1-2) Preparation method of clean water

The water used for cleaning is used to dissolve calcium chloride by ion exchange water of 2966.13 g in order to make calcium/magnesium = 8/2 as a hardness component. Dihydrate 25.14 g and magnesium chloride. The 400 ° DH hard water obtained by 8.70 g of hexahydrate was used for the cleaning power test by diluting with ion-exchange water and adjusting to 4 ° DH.

(1-3) Determination method

In the cleaning test, a washing machine (NA-FV8001, Panasonic) was used, and water prepared by the above method was used. The determination of the cleaning power was carried out by a 10-person evaluation group (30-year-old male). 6 pieces of the collar sheets which were cleaned by the liquid detergent composition (evaluation lotion) of Tables 1-3 were visually cleaned in the same manner except that the lotion was replaced with the indicator lotion described in JIS K3362:1998. The degree of cleaning of the 6 pieces of the collar of the treatment. It is judged which one of the pair of collar pieces is excellent in cleaning power, and the case where the cleaning power is more excellent in the use of the evaluation lotion is set to "+1", and the case where the cleaning power of the indicator lotion is more excellent is set to "-1" point ( The total score of each evaluation team is "+6" to "-6". Ten people in the evaluation team evaluated one lotion, and evaluated the cleansing power by the total score of the evaluation group. When the total is divided into +5~-5, it can be judged that the cleaning agent is equivalent to the cleaning power of the indicator lotion. When it is above +6, it can be judged that the cleaning power of the lotion is superior, below -6. In the case of the situation, it can be judged to evaluate the lotion Poor cleaning power. Further, it can be judged that the larger the value, the more excellent the cleaning power.

(2) Evaluation of semi-dry odor

Collecting a pair of shirts that are repeatedly washed and worn in a twenties-to-ten-year-old adult man's tights, which are not stinky when washed and fully dry, but give the same odor and semi-dry odor when they are wet. (cotton 100%). The tight-fitting shirt is cut into 5 cm × 5 cm, and a cutting cloth which is confirmed by a professional evaluator to have the same odor level as the odor generated by the moisture is selected. In addition, when the semi-dry odor of the same odor was qualitatively analyzed, it was confirmed that the middle stalk fatty acid odor or sulfur odor was mainly contained in 4M3H odor.

In order to make the collected and selected cutting cloth as the initial state as possible and evaluate as a sturdy clothing test cloth, the selected cut cloth was prepared using a reference lotion containing the following composition without fragrance, and the concentration was 0.67 g. /L washing solution, cleaning by a stirring cleaning tester (Targot-o-Meter) at 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 sufficiently rinsed with tap water, and immediately placed in an environment of 25 ° C and a relative humidity of 35% for 24 hours, and sufficiently dried. The odor intensity of the sturdy fabric test cloth after drying was selected as the sturdy fabric test cloth by the following evaluation criteria 1 ("completely odorless") according to the agreement of five professional evaluators. Further, it was confirmed that the sturdy fabric test cloth treated by the standard lotion produced a odor containing 4M3H by being in a semi-dry state.

The composition of the reference lotion is (1) alkyl (carbon number 12, linear) sodium benzenesulfonate 10% by mass, (2) alkyl (carbon number 12) sulfate sodium salt 2% by mass, (3) ) 2% by mass of sodium fatty acid derived from coconut oil, (4) polyoxyethylene (average addition of moles) 10) alkyl (carbon number 12 to 14) ether 10% by mass, (5) sodium carbonate 15% by mass, (6) zeolite 10% by mass, (7) acrylic acid-maleic acid copolymer (weight average) The molecular weight was 70,000, the acrylic acid/maleic acid molar ratio was 6/4) 5 mass%, the (8) sodium citrate 1% by mass, and the (9) sodium sulfate remaining portion (total 100% by mass).

Then, using the liquid detergent composition shown in Tables 1 to 3, the sturdy clothing test cloth was washed, and the following odor strength evaluation test (odor strength evaluation A, B) was performed.

. Estimation of odor intensity A (Evaluation of odor generated by fiber products in a semi-dry state in a short period of time)

The liquid detergent composition described in Tables 1 to 3 was prepared to prepare a washing liquid having a concentration of 0.67 g/L, and 5 pieces of the above-mentioned sturdy clothing test cloth were used as one set by a stirring type cleaning test machine (Targot-o-Meter). The cleaning treatment was carried out under the 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 the cleaning, the sturdy fabric test cloth was sufficiently washed with tap water, and stored in a culture chamber at 30 ° C and a relative humidity of 90% in an environment where semi-dry odor was likely to occur for 3 hours. Five of the professional evaluators conducted a functional evaluation of the semi-dry odor (including a complex odor such as S odor, N odor, aldehyde odor, lower fatty acid odor, and intermediate branched fatty acid odor such as 4M3H odor) on the sturdy clothing test cloth after storage.

. Estimation of odor intensity B (evaluation of re-occurring semi-dry odor generated by fiber products in a dry state)

The liquid detergent composition described in Tables 1 to 3 was prepared to prepare a washing liquid having a concentration of 0.67 g/L, and 5 pieces of the above-mentioned sturdy clothing test cloth were set as one set by stirring. A cleaning tester (Targot-o-Meter) was cleaned at 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 cleaning, the sturdy fabric test cloth is thoroughly rinsed with tap water, and stored in a culture chamber at 30 ° C and a relative humidity of 90% in an environment where semi-dry odor is likely to occur, after 12 hours at 25 ° C, relative humidity. Allow to dry for 3 nights in an environment of 35%. The dried cloth test cloth did not produce a semi-dry odor.

Thereafter, 0.1 g of tap water was sprayed on the sturdy clothing test cloth using a spray container, and the semi-dry odor was re-occurred by the same professional evaluator for 5 persons to re-wet the sturdy clothing test cloth (4M3H odor-based intermediate-branched fatty acid) Functional evaluation of odor).

The evaluation results of the odor intensity evaluations A and B are determined based on the following evaluation criteria and are determined according to the agreement of the professional evaluator.

(evaluation benchmark)

1: Not stinky at all

2: Generally not stinky

3: I always feel stinky

4: always smells bad

5: obvious smell

The results of the above odor intensity evaluations A and B are shown in Tables 1 to 3.

At least 4 people felt odor when evaluating the criteria 3 to 5.

Hereinafter, the formulation of the liquid detergent composition of the present invention is shown in Table 4.

The ingredients in the respective tables are shown below.

<mixing ingredients>

In the description of the following components, ethylene oxide is abbreviated as EO, and propylene oxide is abbreviated as PO. Further, the concentration of the anionic organic compound to be a salt is shown in the table in terms of the concentration of the acid compound. The pH of the composition is adjusted using an aqueous solution of sodium hydroxide or an aqueous solution of hydrochloric acid.

(A) component (a1) component

. A1-1: polyoxyethylene (9) polyoxypropylene (2) polyoxyethylene (9) alkyl ether (the average value of the molar addition in the brackets) [in order to make ethylene oxide 9 m, a propylene oxide 2 molar, an ethylene oxide 9 mole, and a linear addition of a linear first-order saturated alcohol having a carbon number of 10 to 14 per mole, as in the formula (a1-5), P11=9, q=2, p12=9 compound; does not contain (A1) component].

. A1-2: polyoxyethylene (8) polyoxypropylene (2) polyoxyethylene (8) alkyl ether (the average value of the molar addition in the brackets) [in order to make ethylene oxide 8 m, a propylene oxide 2 mole, an ethylene oxide 8 mole, and a linear addition of a linear first-order saturated alcohol having a carbon number of 10 to 14 per mole, as in the formula (a1-5), Compound with p11=8, q=2, p12=8; does not contain (A1) component].

. A1-3: polyoxyethylene (15) polyoxypropylene (2) polyoxyethylene (15) alkyl ether (the average value of the molar addition in the brackets) [in order to make ethylene oxide 15 m, a propylene oxide 2 molar, an ethylene oxide 15 mole, and a linear addition of a linear first-order saturated alcohol having a carbon number of 10 to 14 per mole, as in the formula (a1-5), P11=15, q=2, p12=15 compound; does not contain (A1) component].

. A1-4: polyoxyethylene (20) polyoxypropylene (2) alkyl ether (the average value of the molar addition in the brackets is the number of moles) [sequential ethylene oxide 20 moles, propylene oxide 2 moles Block addition with a linear primary saturated alcohol having 1 mole of carbon number of 10 to 14; in the general formula (a1-2), a compound of p=20, q=2; excluding (A1) )ingredient].

. A1-5: polyoxyethylene (14) polyoxypropylene (2) polyoxyethylene (4) alkyl ether (the average value of the molar addition in the brackets) [in order to make ethylene oxide 14 m, Propylene oxide 2 moles, ethylene oxide 4 moles and a carbon number of 10 to 14 per 1 mole The chain-first saturated alcohol is subjected to block addition, and is a compound of the formula (a1-5) wherein p11=14, q=2, and p12=4; and the component (A1) is not included.

(a2) component

. A2-1: a nonionic surfactant in which R ^2a in the formula (a2) is a linear primary alkyl group having a carbon number of 11, 1 is 1, m is 15, n is 0, and R ^21a is a methyl group. A2-2: a nonionic surfactant in which R ^2a in the formula (a2) is a linear primary alkyl group having a carbon number of 11, 1 is 1, m is 10, n is 0, and R ^21a is a methyl group.

(a3) component

. a3-1: general formula (a3) of, R ^3a is a linear alkyl group having a carbon number of 12 to 14, R ^3a -O- the oxygen atom of R bonded to the carbon atom ^3a the two carbon atoms, And a nonionic surfactant of r=7 (addition of 7 moles of EO to a secondary linear saturated alcohol having a carbon number of 12 to 14 per mole, and then removing unreacted alcohol by distillation. R ^a2 The OH content is less than 0.1% by mass).

. a3-2: general formula (a3) of, R ^3a is a C 12 straight-chain alkyl group of, R ^3a -O- the oxygen atom of R bonded to a carbon atom ^3a of carbon atoms, and r = 3 (which is a single distribution) of a nonionic surfactant, and as the component (A1), in the formula (A1), a compound of x = 3 accounts for about 100%.

. A3-3: in the formula (a3), R ^3a is a linear alkyl group having a carbon number of 12, and a carbon atom of R ^3a bonded to the oxygen atom of R ^3a -O- is a primary carbon atom, and r A nonionic surfactant of =5 (which is a single distribution), and as the component (A1), in the formula (A1), a compound of x = 5 accounts for about 100%.

. A3-4: in the formula (a3), R ^3a is a linear alkyl group having a carbon number of 14, and the carbon atom of R ^{3a to which} the oxygen atom is bonded to R ^3a -O- is a primary carbon atom, and A nonionic surfactant having r = 5 (wherein a single distribution). Does not contain (A1) ingredients.

. A3-5: in the formula (a3), R ^3a is a linear alkyl group having a carbon number of 10, and a carbon atom of R ^3a bonded to the oxygen atom of R ^3a -O- is a primary carbon atom, and A nonionic surfactant having r = 5 (wherein a single distribution).

. A3-6: An average EO addition of lauryl alcohol to an ethylene oxide having a molar content of 3 moles of a nonionic surfactant. That is, R ^3a represented by the formula (a3) is a linear alkyl group having a carbon number of 12, and a carbon atom of R ^3a bonded to the oxygen atom of R ^3a -O- is a primary carbon atom, and r = 3 a nonionic surfactant, and as the component (A1), the nonionic compound of x=2, 3, 4, and 5 represented by the formula (A1) is contained in a total amount of 50% by mass in a3-6, and further x=3. The nonionic compounds of 4 and 5 contained 32% by mass in total in a3-6. Further, for the sake of convenience, the essential condition of R represented by the structural formula of the general formula (A1) is the same as that of the general formula (A1), but the nonionic compound of x=0, 1 contains 33 in total in a3-6. quality%.

. A3-7: A nonionic surfactant having an average EO addition of 6 moles to the addition of ethylene oxide to lauryl alcohol. That is, R ^3a represented by the formula (a3) is a linear alkyl group having a carbon number of 12, and the carbon atom of R ^3a bonded to the oxygen atom of R ^3a -O- is a primary carbon atom, and r=6 A nonionic surfactant, and as the component (A1), the nonionic compound of x=2, 3, 4, and 5 represented by the formula (A1) contains 34% by mass in total of a3-7, and further x=3. The nonionic compounds of 4 and 5 contained 27% by mass in total in a3-7. Further, for the sake of convenience, the necessary condition of R represented by the structural formula of the general formula (A1) is the same as that of the general formula (A1), but the nonionic compound of x=0, 1 contains 10 in total in a3-7. quality%.

. A3-8: In the formula (a3), R ^3a is a linear alkyl group having a carbon number of 12, and a carbon atom of R ^3a bonded to the oxygen atom of R ^3a -O- is a primary carbon atom, and r = 8 (which is a single distribution) of a nonionic surfactant. Although the component (A1) is not contained, it is represented by the formula (A1) for the sake of convenience, and in the formula (A1), the compound of x=8 accounts for about 100%.

(B) component

. B1-1: N-(1-dodecyl)-N,N,N-trimethylammoniumethyl sulfate.

. B1-2: N-(1-Tetradecyl)-N,N-dimethyl-N-ethylammoniumethyl sulfate.

. B1-3: N-(1-octadecyl)-N,N,N-trimethylammonium methyl sulfate.

(C) component

. LAS: an alkylbenzenesulfonic acid having a linear alkyl group having a carbon number of 10 to 14 (having an average carbon number of 11.7)

. Coconut oil fatty acid: Lunac L-55 (trade name), manufactured by Kao Co., Ltd.

. Di-long-chain alkyl (C14) cation: a di-linear alkyl group (having a carbon number of 14) dimethylammonium ethyl sulfate. Here, the carbon atoms of the two alkyl groups having a carbon number of 14 bonded to the nitrogen atom are all primary carbon atoms.

(E) component

. E-1: diethylene glycol monobutyl ether (also known as butoxy diglycol)

. E-2: triethylene glycol monophenyl ether (PHG-30: manufactured by Japanese emulsifier)

. E-3: ethanol

(F) component

. F-1: sodium p-toluenesulfonate (wherein the concentration in the table is based on the acid compound) concentration)

(H) component

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

(1) Ingredients

. I-1: Utilizing the paragraph 0020 of the fourth page of Japanese Patent Laid-Open No. 10-60476 Polymer compound synthesized by the method of Example 1

(other)

. Fluorescent dye: Tinopal CBS-X (trade name) (made by Ciba Specialty Chemicals)

. Enzyme: Everlase 16.0L-EX (trade name) (protease, manufactured by Novozymes)

<Using the smear foaming property>

The liquid detergent compositions of Examples Nos. 7 to 20 of Table 2 and Comparative Example No. 11 of Table 3 were prepared. At the time of evaluation, black cotton socks obtained by performing the following steps 10 times were used: 12 hours from an adult man of any length from 20 to 40, and washed with the basis of the evaluation of the semi-dry odor described above. After washing, the mixture was dried in a room at 20 ° C and 60% RH and worn again.

If the liquid detergent composition is applied to the portion of the leg of the sock which is repeatedly worn and washed, the foaming is different depending on the wearer, but any of the compositions of the examples can be clearly foamed. . The foaming system is produced within 15 seconds after application, and is defoamed within 60 seconds from the application. Comparative Example 11 containing no hydrogen peroxide was completely unfoamed.

Claims (12)

A liquid detergent composition containing a nonionic surfactant (A) [hereinafter referred to as (A) component] in an amount of 15 to 70% by mass, and a cationic surfactant (B) represented by the following formula (B1) (hereinafter referred to as (B) component] 0.3 to 5% by mass, hydrogen peroxide (D) [hereinafter referred to as (D) component] 0.3 to 10% by mass, and water; and the composition contains the following 0.5 to 10% by mass of the nonionic compound (A1) represented by the formula (A1) as the component (A); and (c1) to the ratio of the anionic surfactant (c1) other than the fatty acid and its salt to the component (B) The mass ratio of /(B) is 0~1; the pH value at 20 °C as described in 8.3 of JIS K3362:1998 is 3.0-7.0; and the composition does not contain a bleach activator; RO-(C ₂ H ₄ O) _x -H (A1) [wherein, R is a linear alkyl group having a carbon number of 12, and the carbon atom of R-bonded to the R of the oxygen atom is a primary carbon atom; and x is an ethylideneoxy group. Adds a molar number and is an integer from 2 to 5] [wherein, R ^b1 is a chain hydrocarbon group having a carbon number of 12 to 18, and may contain -(A'O) _s - in R ^b1 ; A'O is a stretching ethyloxy group or a stretching propyloxy group, s It represents the average addition molar number of A'O, and is 0~10, and R ^b2 , R ^b3 and R ^b4 are each independently a methyl group, an ethyl group, a benzyl group or a hydroxyalkyl group having a carbon number of 1 to 3, X. ^- is CH ₃ SO ₄ ^- or CH ₃ CH ₂ SO ₄ ^- , halogen ion]. The liquid detergent composition according to claim 1, which comprises 10 to 60% by mass of the nonionic surfactant represented by the following formula (a1) and/or formula (a2) as the component (A) R ^1a -O [(C ₂ H ₄ O) _p /(AO) _q ]H (a1) [wherein R ^1a is an alkyl or alkenyl group having a carbon number of 8 to 22; AO is an alkylene having a carbon number of 3 to 5 The base group; p, q is the average addition mole number, p is the number of 8~40, q is the number of 0~5; "/" means that the C ₂ H ₄ O group and the AO group can be random or block Any one of them is bonded] R ^2a (CO) _l O-[(C ₂ H ₄ O) _m /(AO) _n ]R ^21a (a2) [wherein R ^{2a has} a carbon number of 8~ 22 alkyl or alkenyl; R ^21a is an alkyl group having 1 to 3 carbon atoms; 1 is a number 0 or 1, AO is a stretching alkyl group having a carbon number of 3 to 5; m and n are average additions Mole number, and m is 5~30, n is 0~5; "/" means that C ₂ H ₄ O group and AO group can be bonded in any way of random or block. ]. The liquid detergent composition according to claim 1 or 2, which contains 0.5 to 20% by mass of the nonionic surfactant represented by the following formula (a3) as the component (A) R ^3a -O-(C ₂ H ₄ O) _r -H (a3) [wherein R ^3a is an alkyl or alkenyl group having a carbon number of 8 to 22; 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 the average addition mole number, and is 2 or more and less than 8]. The liquid detergent composition according to claim 1 or 2, which further contains a fatty acid and a salt thereof (c2) in an amount of from 0.05 to 5% by mass in terms of the fatty acid. The liquid detergent composition according to claim 1 or 2, which further contains the mixed aqueous organic solvent (E) in an amount of from 1 to 40% by mass. The liquid detergent composition according to claim 1 or 2, which further contains 0.01 to 0.5% by mass of the organic chelating agent (H). The liquid detergent composition according to claim 1 or 2, wherein the content of the water-containing organic amine compound is less than 1% by mass. A method of cleaning a fibrous article, which comprises cleaning the fibrous product with an aqueous solution obtained by dissolving the liquid detergent composition according to any one of claims 1 to 7 in water. A method of cleaning a fibrous product, comprising the steps of applying a liquid detergent composition to a fibrous product and producing a foam comprising: a nonionic surfactant (A) [hereinafter referred to as (A) component 15 to 70% by mass of the cationic surfactant (B) represented by the following formula (B1) [hereinafter referred to as (B) component] 0.3 to 5% by mass, hydrogen peroxide (D) [hereinafter referred to as ( D) a component: 0.3 to 10% by mass, and water; and the composition contains 0.5 to 10% by mass of the nonionic compound (A1) represented by the following formula (A1) as the component (A); The ratio of the anionic surfactant (c1) to the component (B) other than the salt is 0 to 1 by mass ratio of (c1) / (B); and 20 ° C as described in 8.3 of JIS K3362:1998 The pH is 3.0~7.0 RO-(C ₂ H ₄ O) _x -H (A1) [wherein, R is a linear alkyl group having a carbon number of 12, and the carbon atom of RO-bonded to the R of the oxygen atom Is a primary carbon atom; x is the addition molar number of the extended ethyloxy group, and is an integer of 2 to 5] [wherein, R ^b1 is a chain hydrocarbon group having a carbon number of 12 to 18, and may contain -(A'O) _s - in R ^b1 ; A'O is a stretching ethyloxy group or a stretching propyloxy group, s It represents the average addition molar number of A'O, and is 0~10, and R ^b2 , R ^b3 and R ^b4 are each independently a methyl group, an ethyl group, a benzyl group or a hydroxyalkyl group having a carbon number of 1 to 3, X. ^- is CH ₃ SO ₄ ^- or CH ₃ CH ₂ SO ₄ ^- , halogen ion]. The method for cleaning a fibrous product according to claim 9, wherein the liquid detergent composition contains 10 to 60% by mass of the nonionic surfactant represented by the following formula (a1) and/or formula (a2) as (A) a component, R ^1a -O[(C ₂ H ₄ O) _p /(AO) _q ]H (a1) [wherein R ^1a is an alkyl or alkenyl group having a carbon number of 8 to 22; AO is a carbon number 3~5 alkyloxy; p, q is the average addition mole number, p is 8~40, q is 0~5; "/" means C ₂ H ₄ O base and AO base It can be bonded in any of random or block] R ^2a (CO) _l O-[(C ₂ H ₄ O) _m /(AO) _n ]R ^21a (a2) [wherein R ^2a Is an alkyl or alkenyl group having a carbon number of 8 to 22; R ^21a is an alkyl group having 1 to 3 carbon atoms; 1 is a number of 0 or 1, and AO is a stretching alkyloxy group having a carbon number of 3 to 5; m, n is the average addition molar number, and m is the number of 5~30, n is the number of 0~5; "/" means that the C ₂ H ₄ O group and the AO group can be random or block A way to bond together]. A method of cleaning a fibrous product according to claim 9 or 10, wherein a portion of the above liquid detergent composition for cleaning is applied to the fibrous product, the fibrous product to which the liquid detergent composition is applied and the liquid containing the liquid The remainder of the detergent composition is contacted with a cleaning solution of water for cleaning. A use of the liquid cleanser composition of claim 1 for cleaning a fibrous article.