JP2009173908A - Liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition having a high detergent effect, excellent in re-contamination-inhibiting effect and imparting a softening effect to textile products. <P>SOLUTION: This liquid detergent composition contains (a) a nonionic surfactant, (b) a predetermined di-long chain type tertiary amine compound having an R-CONH-group (R is an 11-21C alkyl group or alkenyl group) in the molecule, or its neutralized products (b) with an inorganic acid or an organic acid, and (c) water, with the composition having a pH of 1-3 at 20°C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a liquid detergent composition.

There have been many studies on imparting a softening effect to a cleaning composition for clothing. For example, a technique using a clay mineral or a technique using a complex of a monoalkyl quaternary ammonium compound and an anionic surfactant is known. It has been. Patent Documents 1 and 2 disclose a liquid detergent composition containing a nonionic surfactant, a long-chain amine, and a di-long-chain alkyl type quaternary ammonium compound. Patent Document 3 discloses a detergent composition in which an amino-modified silicone, a surfactant, and a specific dilong chain amine compound are combined. On the other hand, in Patent Document 4, a nonionic surfactant and a specific quaternary ammonium compound or a specific anionic compound are combined in order to stabilize the bleach activator in the liquid bleach composition. Liquid bleach compositions are disclosed.
JP 2003-206500 A, JP 2005-023123 A Japanese Patent Laid-Open No. 10-60483 JP-A-7-82591

  However, by blending the bases of Patent Documents 1 to 3 (di-long chain alkyl type quaternary ammonium compounds, di-long chain amine compounds, etc.), so-called re-contamination occurs in which dirt such as carbon adheres again during washing. , Cleaning performance may be significantly reduced. For this reason, the compounding quantity of these bases needs to be made into a small quantity, and the softness | flexibility was not fully exhibited. In addition, the method of adding a clay mineral such as bentonite does not deteriorate the cleaning performance, but since bentonite hardly remains in the clothing, it cannot exhibit sufficient flexibility.

  Patent Document 4 is a technique for improving a composition that is essentially intended for bleaching, and does not mention any design in consideration of imparting a softening effect. In Patent Document 4, it is necessary to combine a specific quaternary ammonium compound or a specific anionic compound depending on the ionicity of the bleach activator, and when the bleach activator is anionic, it is quaternary. An ammonium salt is used, but in this combination, an anionic bleach activator inhibits the amount of quaternary ammonium salt adsorbed on the fiber product. Therefore, in the formulation that maintains the intended bleaching effect of Patent Document 4, Flexibility could not be expressed.

  The subject of this invention is providing the liquid detergent composition which has a high washing | cleaning effect, is excellent in the recontamination prevention effect, and can provide a softness | flexibility effect to textiles.

The present invention
(A) a nonionic surfactant (hereinafter referred to as component (a));
(B) a di-long-chain tertiary amine compound having two groups (hereinafter referred to as long-chain groups) containing an alkyl group or alkenyl group having 11 to 21 carbon atoms in the molecule, One is an R—CONH— group (wherein R is an alkyl or alkenyl group having 11 to 21 carbon atoms), a di-long-chain tertiary amine compound, or a neutralized product thereof with an inorganic or organic acid [hereinafter, ( b) component ”
(C) water,
And a liquid detergent composition having a pH of 1 to 3 at 20 ° C.

  Further, the present invention provides a textile product cleaning, wherein an aqueous medium containing the liquid detergent composition of the present invention is brought into contact with the textile product to simultaneously wash the textile product and impart flexibility to the textile product. Regarding the method.

  ADVANTAGE OF THE INVENTION According to this invention, the liquid detergent composition which has a high cleaning effect, is excellent in the recontamination prevention effect, and can provide a softness | flexibility effect to a textile product is provided.

<(A) component>
Component (a) is a nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, polyoxyethylene polyoxypropylene block polymer, fatty acid Examples include alkanolamides, alkyl polyglycosides, polyhydroxy fatty acid amides, and polyoxyalkylene alkyl ethers are particularly preferable. (A) As a component, it has one alkyl group or alkenyl group having 8 to 22 carbon atoms, and an average added mole number of 1 to 100 polyoxyalkylene group (the carbon number of the alkylene group is 2 or 3). Compounds having 1 or 2 are preferred. Specifically, the nonionic surfactant of the following general formula (a1) is good.

R ^1a -E - [(R ^2a O) _d -R ^3a] _e (a1)
[Wherein, R ^1a is an alkyl or alkenyl group having 8 to 22 carbon atoms, preferably 8 to 16 carbon atoms. R ^2a is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. R ^3a is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. d is an average of 2 to 100, preferably 4 to 80, more preferably 5 to 60, and particularly preferably 6 to 50. E is -O-, -COO-, -CON <or -N <, e is 1 when E is -O- or -COO-, and e is E when -CON <or -N <. Is 2. ]

Specific examples of the compound represented by the general formula (a1) include compounds represented by the following formulas (a1-1) to (a1-4).
R ^1a —O— (C ₂ H ₄ O) _f —H (a1-1)
[Wherein, R ^1a has the above-mentioned meaning. f is a number of 2 to 100, preferably 6 to 50. ]
_{^{R 1a -O - [(C 2}} H 4 O) g / (C 3 H 6 O) h] -H (a1-2)
[Wherein, R ^1a has the above-mentioned meaning. g and h are each independently a number of 2 to 100, preferably 5 to 20, and (C ₂ H ₄ O) and (C ₃ H ₆ O) may be random or block adducts. ]

[Wherein, R ^1a has the above-mentioned meaning. p, q, r and s are each independently a number of 0 to 40, p + q + r + s is a number of 5 to 100, preferably 5 to 60, and (C ₂ H ₄ O) and (C ₃ H ₆ O) May be random or block adducts. R ^3a is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

  Especially in this invention, the compound shown by (a1-1) is suitable from the point of a washing | cleaning effect. In the component (a), the ratio of the nonionic surfactant of the formula (a1) and the compound represented by the formula (a1-1) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.

<(B) component>
The component (b) is a di-long-chain tertiary amine compound having two predetermined long-chain groups, or a neutralized product thereof with an inorganic acid or an organic acid. The component (b) has one or more R—CONH— groups (R is an alkyl group or alkenyl group having 11 to 21 carbon atoms) as a long chain group.

The long chain group of the component (b) is a group having a structure containing an alkyl group or an alkenyl group having 11 to 21 carbon atoms, and preferably has a total carbon number of 12 to 22. Examples of the long chain group of the component (b) include the following, and the component (b) has at least one group (b1).
(B1) R—CONH— group (R is an alkyl or alkenyl group having 11 to 21 carbon atoms)
(B2) R—NHCO— group (R is an alkyl or alkenyl group having 12 to 22 carbon atoms)
(B3) R′—COO— group (R ′ is an alkyl or alkenyl group having 11 to 21 carbon atoms)
(B4) R′—OCO— group (R ′ is an alkyl or alkenyl group having 12 to 22 carbon atoms)
(B5) C12-22 alkyl group or alkenyl group

  As the component (b), a compound having the R′—COO— group of (b3) (R ′ is an alkyl group or alkenyl group having 11 to 21 carbon atoms) as a long chain group is preferable.

  As the component (b), a di-long-chain tertiary amine compound represented by the following general formula (b1) or a neutralized product thereof with an inorganic acid or an organic acid is preferable.

[Wherein, R ^1b is an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, R ^2b and R ^3b are each an alkyl group or alkenyl group having 11 to 21 carbon atoms, and m and n are each 1 It is a number of ~ 3. ]
Particularly preferred are compounds with m = 2 and n = 3.

  Specific examples of the component (b) include a di-long tertiary amine compound represented by the following general formula (b1-1) or a neutralized product thereof with an inorganic acid or an organic acid.

[Wherein, R ^1b , R ^2b and R ^3b are as defined above, and m ′ is a number of 2 or 3. ]

R ^2b CO— and R ^3b CO— in the above general formula are usually saturated higher fatty acids such as stearic acid and palmitic acid, unsaturated higher fatty acids such as oleic acid, elaidic acid, linoleic acid and linolenic acid, beef tallow and lard. , Palm oil, palm kernel oil, soybean oil, safflower oil, sunflower oil, olive oil and other natural fats and oils, which are derived from fatty acids obtained by decomposing and refining, especially oleic acid, stearic acid, beef tallow Fatty acids, hardened beef tallow fatty acids, palm oil fatty acids, hardened palm oil fatty acids, palm kernel oil fatty acids, and hardened palm kernel oil fatty acids are preferred. As the unsaturated higher fatty acid, the stereoisomer may be a cis isomer, a trans isomer, or a mixture of both, and the ratio of the cis isomer / trans isomer is particularly 25/75 to 100/0. (Mass ratio) is preferable. R ^2b CO— and R ^3b CO— may be the same or different.

  Moreover, the di long chain type | mold tertiary amine represented by the following general formula (b1-2) can also be mix | blended as a compound applicable to (b) component.

[In the formula, R ^4b is an alkyl group or alkenyl group having 16 to 23 carbon atoms including a splitting group, and is an alkyl group or alkenyl group splitting with an amide group, and R ^5b has 16 to 23 carbon atoms including a splitting group, It is an alkyl group or alkenyl group separated by an amide group or an ester group, or an alkyl group or alkenyl group having 14 to 22 carbon atoms, and R ^6b is an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms. . ]

  Specific examples of the di long-chain tertiary amine represented by (b1-2) include those represented by the following general formulas (b1-2-1) to (b1-2-5).

[Wherein, R ^7b is an alkyl group or an alkenyl group, and the total carbon number of R ^7b and R ^8b is 12 to 25. R ^8b is an alkylene group having 1 to 4 carbon atoms, R ^9b is an alkyl group or an alkenyl group, and the total carbon number of R ^9b and R ^10b is 12 to 25. R ^10b is an alkylene group having 1 to 4 carbon atoms. R ^11b is an alkyl group or an alkenyl group, and the total carbon number of R ^11b and R ^8b is 12-25. R ^12b is an alkyl group or an alkenyl group, and the total carbon number of R ^12b and R ^10b is 12 to 25. R ^13b is an alkyl group or alkenyl group having 11 to 22 carbon atoms. R ^14b is an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. ]

R ^7b CO- and R ^9b CO- in the above general formula are usually saturated higher fatty acids such as stearic acid and palmitic acid, unsaturated higher fatty acids such as oleic acid, elaidic acid, linoleic acid and linolenic acid, beef tallow, lard , Palm oil, palm kernel oil, soybean oil, safflower oil, sunflower oil, olive oil and other natural fats and oils, which are derived from fatty acids obtained by decomposing and refining, especially oleic acid, stearic acid, beef tallow Fatty acids, hardened beef tallow fatty acids, palm oil fatty acids, hardened palm oil fatty acids, palm kernel oil fatty acids, and hardened palm kernel oil fatty acids are preferred. As the unsaturated higher fatty acid, the stereoisomer may be a cis isomer, a trans isomer, or a mixture of both, and the ratio of the cis isomer / trans isomer is particularly 25/75 to 100/0. (Mass ratio) is preferable.

R ^7b and R ^9b may be the same or different. R ^8b and R ^10b are each an alkylene group having 1 to 4 carbon atoms, specifically a methylene group, an ethylene group, a propylene group, or a butylene group, and may be linear or branched. R ^22b and R ^24b may be the same or different. Specific examples of R ^11b , R ^12b and R ^13b include a lauryl group, a myristyl group, a palmityl group, a stearyl group, an oleyl group, a linole group, and a linolenic group. R ^28b is an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, or a hydroxybutyl group. Among them, a methyl group, an ethyl group, and a hydroxyethyl group are particularly preferable.

  The di-long tertiary amine (b1-2) is neutralized with a commonly used acid. Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as benzoic acid, citric acid, and polymeric acrylic acid.

<(C) component>
The component (c) is water. As the water of the present invention, distilled water, ion exchange water, ground water, tap water and the like can be used.

<Liquid cleaning composition>
In the present invention, the mass ratio of the component (a) to the component (b) is preferably (a) / (b) = 1/1 to 100/1, more preferably 2 /, from the viewpoint of flexibility and detergency. 1-80 / 1, more preferably 3 / 1-50 / 1. Moreover, it is preferable that the liquid cleaning composition of this invention contains (a) component 10-50 mass%, 15-45 mass%, especially 17-43 mass%. Moreover, it is preferable to contain (b) component 0.5 mass% or more, 1-10 mass%, especially 3-8 mass%.

  The liquid detergent composition of the present invention may contain a cationic surfactant, an amphoteric surfactant, and an anionic surfactant as a surfactant other than the component (a) [hereinafter referred to as component (d)]. However, since an anionic surfactant (hereinafter referred to as the component (d1)) may affect the softening effect, it must be used with care. When component (d1) is used, the molar ratio of component (d1) / component (b) should be 0.5 or less, more preferably 0.2 or less, and particularly 0.1 or less.

  The component (d) that can be used in the present invention includes N-alkyl (10 to 14 carbon atoms) -N, N-dimethyl-N- [2-hydroxysulfopropyl] ammonium betaine, N-alkyl (10 to 14 carbon atoms). ) -N, N-dimethyl-N-carboxymethylammonium betaine, N-alkyl (10 to 14 carbon atoms) -N, N-dimethylamine oxide, N-alkanoyl (10 to 14 carbon atoms) aminopropyl-N, N -Dimethyl-N- [2-hydroxysulfopropyl] ammonium betaine, N-alkanoyl (10 to 14 carbon atoms) aminopropyl-N, N-dimethyl-N-carboxymethylammonium betaine, N-alkanoyl (10 to 14 carbon atoms) ) Aminopropyl-N, N-dimethylamine oxide, dialkyl (8 to 14 carbon atoms) dimethyl An ammonium salt, an alkyl (carbon number 8 to 14) dimethylbenzylammonium salt, an alkyl (carbon number 8 to 16) benzene sulfonate, a polyoxyalkylene alkyl (carbon number 10 to 16) ether sulfate, and the like can be mentioned. .

  In the present invention, a metal sequestering agent can be contained as the component (e), but care must be taken when using it because it may affect the softening effect. When the component (e) is used, the compounding ratio of the component (e) is 3% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less in the composition.

  Usable sequestering agents include tripolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, hexametaphosphoric acid and alkali metal salts thereof; ethylenediaminetetraacetic acid, hydroxyiminodiacetic acid, dihydroxyethylglycine, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid , Triethylenetetramine hexaacetic acid and alkali metal salts or alkaline earth metal salts thereof; aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, amino Trimethylenephosphonic acid and alkali metal or alkaline earth metal salts thereof; single polymer or copolymer of monomers selected from acrylic acid and methacrylic acid , Acrylic acid-maleic acid copolymer, poly α-hydroxyacrylic acid and alkali metal salts thereof; polyvalent carboxylic acid selected from citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid And one or more selected from alkali metal salts thereof; alkylglycine-N, N-diacetic acid, aspartic acid-N, N-diacetic acid, serine-N, N-diacetic acid, glutamic acid diacetic acid, ethylenediamine disuccinic acid Or these salts etc. are mentioned. In the present invention, among them, ethylenediaminetetraacetic acid and citric acid, or sodium salts and potassium salts thereof can be mentioned.

  In the present invention, from the viewpoint of improving storage stability, the component (f) is substituted with a benzenesulfonic acid (salt) which may be substituted with an alkyl group having 1 to 3 carbon atoms and an alkyl group with 1 to 3 carbon atoms. A compound selected from benzenecarboxylic acid (salt) which may be used can be contained, but care must be taken when using it because it may affect the softening effect. When the component (f) is used, the compounding ratio of the component (f) is 5% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less in the composition. Specific examples of the component (f) include toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid and their sodium, potassium or magnesium salts, and p-toluenesulfonic acid is particularly preferable.

  In the present invention, a solvent can be contained as the component (g), and selected from ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Water-soluble organic solvents are preferred. When the component (g) is used, the compounding ratio of the component (g) is 0.1 to 10% by mass, preferably 0.3 to 5% by mass in the composition.

  In addition, components that are usually blended in liquid detergents can be blended. For example, disinfecting components, preservatives, turbidity agents, colorants and the like can be mentioned.

  Moreover, the liquid detergent composition of this invention can also contain a bleaching activator in the range which does not impair the effect of this invention. However, an anionic bleach activator (a bleach activator having an anionic group), for example, a bleach activator having a group described in paragraph 0036 of JP-A-7-82591, improves bleaching properties. Is preferable, but when blended in the liquid detergent composition of the present invention, flexibility is lowered, so that the blending requires caution. In the present invention, it is desirable not to contain an anionic bleach activator (a bleach activator having an anionic group), for example, a bleach activator having a group described in paragraph 0036 of JP-A-7-82591. .

  The liquid detergent composition of the present invention contains component (c) water, and the balance of the composition is usually water. The liquid detergent composition of the present invention has a pH of 1 to 3 at 20 ° C. A pH in this range is preferable from the viewpoint of flexibility.

  The liquid detergent composition of the present invention is a liquid detergent composition for imparting a softening effect to a textile product. By treating the fiber product by bringing the aqueous medium containing the liquid detergent composition of the present invention into contact with the fiber product, it is possible to simultaneously wash the fiber product and impart flexibility to the fiber product. The aqueous medium contains water, and it is usually preferable that the concentration of the component (a) is 50 to 500 ppm. The textile product washing method of the present invention can be carried out by performing a washing step using the liquid detergent composition of the present invention in the same manner as ordinary washing. As for the quantity (bath ratio) of the aqueous medium per kg of textiles, 5-30 kg is preferable.

[Method for preparing liquid detergent composition]
Master corresponding to 3 to 3.9 times the content of each component excluding a-3 and a-4 shown in Table 1 (3.9 times when the standard usage is 27 ml and 3 times when 30 ml) Batch A was prepared (Step A), and then a liquid detergent composition was prepared through a step (Step B) in which master batch A was diluted with a-3 and / or a-4 and ion-exchanged water. The details are as follows. In addition, the standard usage-amount in Table 1 was defined for convenience for this test.

Step A: Preparation of Master Batch A Master Batch A corresponding to 3 to 3.9 times the content of each component described in Table 1 was prepared. In a 1000 mL glass beaker, ion-exchanged water corresponding to 95% by mass of the amount necessary for the finished mass to be 1000 g was added and heated to 70 ° C. with a water bath. While stirring at 400 r / min with a turbine type stirring blade having three blades (blade diameter 3 cm), the antifoaming agent a-1 is added, and ethylene glycol is further added as necessary. These were added and stirred for 10 minutes. To this composition, b-1 and / or a comparative amine compound and a-2 were mixed, heated to 70 ° C., melted and uniformly mixed, and a premixed mixture was added with stirring (400 r / min) for 10 minutes. Stir. Next, it was cooled to 50 ° C. while stirring in a 20 ° C. water bath. Next, a predetermined amount of hydrochloric acid (if necessary), calcium chloride, edible blue No. 1 and fragrance necessary for neutralizing b-1 and / or comparative amine compound are added and stirred for 5 minutes while maintaining 50 ° C. did. Next, it was cooled to 30 ° C. with stirring in a 5 ° C. water bath. After cooling, Silicone A was added as necessary. The pH is adjusted to 2.0 to 2.5 using a 10% hydrochloric acid aqueous solution and a 10% sodium hydroxide aqueous solution, the stirring blade is taken out, and the resulting mass is adjusted to 1000 g with ion-exchanged water. Got.

Step B: Preparation of liquid detergent composition In a 2000 mL glass beaker, 1350 g when the standard amount used is 27 ml, and 1050 g when 30 ml is used as the final mass, and from the final mass, a-3 and / or a- The amount of ion-exchanged water corresponding to 95% by mass of the amount excluding the amount of 4 and the master batch A 350 g was charged, and heated to 60 ° C. in a water bath. While stirring with the stirring blade (100 r / min), a-3 and / or a-4 were added so that the composition shown in Table 1 was obtained when completed. After stirring for 60 minutes, the mixture was cooled to 30 ° C. with a 25 ° C. water bath, and 350 g of the master batch A was added. After stirring for 5 minutes (100 r / min), the pH was adjusted to 2 to 2.5 in Table 1 using a 10% aqueous hydrochloric acid solution or a 10% aqueous sodium hydroxide solution. The stirring blade was taken out and ion-exchanged water was used to adjust the finished mass to 1350 g when the standard amount used was 27 ml and 1050 g when 30 ml.

[Evaluation]
The following evaluation was performed about the liquid detergent composition obtained above. The results are shown in Table 1.

<Flexibility evaluation method>
Put 30 liters of tap water in the washing tub of a fully automatic washing machine (NW-7FY manufactured by Hitachi Appliances), 3 towels (70 g / sheet), 700 g of underwear (cotton), TC blend (45% polyester, 45% cotton) ) 600g shirt. Further, the liquid detergent composition shown in Table 1 (immediately after preparation) was added in the amounts shown in Table 1 and washed on a standard course. The tap water was adjusted to 20 ° C. and used. After completion of washing, it was left to dry in a constant temperature and humidity chamber at 20 ° C. and 65% RH for 24 hours. The softness of the towel after drying was evaluated by five panelists skilled in the following criteria in comparison with towels similarly treated with the control detergents in Table 1. The evaluation score was a total of 5 people.
-2 points: poorly flexible compared to towels treated with control detergents -1 points: poorly flexible compared to towels treated with control detergents 0 points: compared with towels treated with control detergents The softness does not change 1 point: The softness is better than the towel treated with the control detergent 2 points: The softness is remarkably better than the towel treated with the control detergent

<Storage test (flexibility evaluation after storage)>
100 g of the liquid detergent composition was put in a sample bottle, sealed, and stored in a constant temperature room at 40 ° C. for 2 weeks. The flexibility of the liquid detergent composition after storage for 2 weeks was evaluated by the above flexibility evaluation method.

<Cleaning performance evaluation method>
The liquid detergent composition was added to 100 ml of ion-exchanged water at 20 ° C. so as to be 10 times the standard use concentration (0.9 ml for 27 ml / 30 L, 1 ml for 30 ml / 30 L), and stirred and dissolved. . Next, 100 ml of 20 ° C. 40 ° DH hard water (CaCl ₂ : 632 mg / L, MgCl ₂ .6H ₂ O: 289 mg / L) prepared in advance and 800 ml of 20 ° C. ion-exchanged water are added and stirred uniformly. did. This liquid was transferred to a sample cup of a stirring type detergency tester (Terg-O-Tometer). Patent No. 3448358, Example 1, Artificial soiled cloth (composite soiled soil containing carbon black) of composition 8 in Table 1 was cut into a size of 6 cm × 6 cm, and this was mixed with 5 sheets of stirring type detergency tester (tar The sample was put into a sample cup of a gotometer (Terg-O-Tometer) and stirred at a rotation speed of 100 rpm ± 3 rpm for 10 minutes. Next, the artificially contaminated cloth was taken out, lightly squeezed by hand so that the water content was 200% or less, then gently stirred by hand for 1 minute in 10 L of tap water, and squeezed by hand was repeated twice. Then, it was dehydrated with a two-tank washing machine (NA-W305 manufactured by Matsushita Electric Industrial Co., Ltd.) for 1 minute and dried using a press (160 ° C., manufactured by Nippon Press Mfg. Co., Ltd. for 30 seconds). The reflectance at 550 nm before and after the test of this artificially contaminated cloth was measured (Nippon Denshoku Co., Ltd. colorimetric color difference meter), and the recontamination prevention rate was determined by the following equation.
Washing rate (%) = [(reflectance of artificially contaminated cloth after test) / (reflectance of artificially contaminated cloth before test)] × 100

<Carbon recontamination prevention evaluation method>
The liquid detergent composition was added to 100 ml of ion-exchanged water at 20 ° C. so as to be 10 times the standard use amount concentration shown in Table 1, and stirred and dissolved. To this was added 0.25 g of carbon black (manufactured by Asahi Carbon Co., Ltd.) selected by Japan Oil Chemical Association, and ultrasonically dispersed for 30 minutes to uniformly disperse the carbon black. Next, 100 ml of 20 ° C. 40 ° DH hard water (CaCl ₂ : 632 mg / L, MgCl ₂ .6H ₂ O: 289 mg / L) prepared in advance and 800 ml of 20 ° C. ion-exchanged water are added and stirred uniformly. did. This carbon black dispersion is transferred to a sample cup of a stirrer type detergency tester (Terg-O-Tometer), and 5 pieces of 6 cm x 6 cm cotton white cloth (exposed to gold sill unsilled by Tanigami Shoten Co., Ltd.) And stirred at a rotational speed of 100 rpm ± 3 rpm for 10 minutes. Next, the cotton cloth was taken out and lightly squeezed by hand so that the water content was 200% or less, and then gently squeezed by hand for 1 minute in tap water and rinsed, and squeezing by hand was repeated twice. Then, it was dehydrated with a two-tank washing machine (NA-W305 manufactured by Matsushita Electric Industrial Co., Ltd.) for 1 minute and dried using a press machine (160 ° C., manufactured by Nippon Press Mfg. Co., Ltd. for 30 seconds). The reflectance of this cotton cloth at 550 nm before and after the test was measured (Nippon Denshoku Co., Ltd. colorimetric color difference meter), and the recontamination prevention rate was determined by the following equation.
Recontamination prevention rate (%) = [(reflectance of white cotton cloth after test) / (reflectance of white cotton cloth before test)] × 100

The components in the table are as follows. The (a) / (b) mass ratio is such that the content of the di-long-chain tertiary amine salt compound corresponding to the component (a) and b-1 [(b) component is 96% by mass. ] And the mass ratio.
A-1: polyoxyethylene (ethylene oxide average addition mole number 20) lauryl ether a-2: stearic acid monoglyceride a-3: polyoxyethylene (ethylene oxide average addition mole number 10) lauryl ether a-4 : Polyoxyethylene (ethylene oxide average addition mole number 7) C12, C14 secondary alkyl ether, Nippon Shokubai Co., Ltd. Softanol 70
B-1: Reaction product containing di-long chain type tertiary amine salt compound produced by the following methodComparison amine compound: Distearyldimethylammonium chloride Silicone A: Silicone BY22 manufactured by Toray Dow Corning Co., Ltd. −019
-Antifoaming agent: Silicone FS Antifoam 025 manufactured by Toray Dow Corning Co., Ltd.

<Manufacturing method of b-1>
A fatty acid prepared by mixing stearic acid and palmitic acid at a molar ratio of 6/4 and N- (3-alkanoylaminopropyl) -N- (2-hydroxyethyl) -N-methylamine at a molar ratio of 1.8 / 1. After mixing, dehydration condensation was performed according to a conventional method. When the acid value reached 9, the reaction was stopped to obtain a condensate. The total amine number of this condensate was measured. This condensate was heated to 70 ° C. and melted. To this condensate, 9 times the amount of ion-exchanged water (65 ° C.) is added, and while stirring, 35% aqueous hydrochloric acid solution necessary for neutralization, calculated based on the total amine value, is added dropwise to the water. The mixture was neutralized with and stirred for 10 minutes, and then cooled to 30 ° C. Next, this compound was freeze-dried to obtain a reaction product containing the target amine salt compound. As a result of quantifying the amount of the di-long-chain tertiary amine salt compound corresponding to the component (b) in the reaction product by liquid chromatography, the content was 96% by mass.

Claims (8)

(A) a nonionic surfactant (hereinafter referred to as component (a));
(B) a di-long-chain tertiary amine compound having two groups (hereinafter referred to as long-chain groups) containing an alkyl group or alkenyl group having 11 to 21 carbon atoms in the molecule, One is an R—CONH— group (wherein R is an alkyl or alkenyl group having 11 to 21 carbon atoms), a di-long-chain tertiary amine compound, or a neutralized product thereof with an inorganic or organic acid [hereinafter, ( b) component ”
(C) water,
A liquid detergent composition having a pH of 1 to 3 at 20 ° C.   The liquid detergent composition according to claim 1, wherein the component (b) is a compound having an R'-COO- group (R 'is an alkyl group or alkenyl group having 11 to 21 carbon atoms). The liquid detergent composition according to claim 1 or 2, wherein the component (a) and the component (b) are contained at a mass ratio of (a) component / (b) component = 1/1 to 100/1.   The liquid detergent composition according to claim 1, which contains 10 to 50% by mass of component (a).   (B) The liquid cleaning composition of any one of Claims 1-4 which contains 0.5 mass% or more of components. (A) A component is a nonionic surfactant represented by the following general formula (a1), The liquid cleaning composition in any one of Claims 1-5.
R ^1a -E - [(R ^2a O) _d -R ^3a] _e (a1)
[In formula, R < ^1a > is a C8-C22 alkyl group or an alkenyl group. R ^2a is an alkylene group having 2 or 3 carbon atoms. R ^3a is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. d shows the number of 2-100 on average. E is -O-, -COO-, -CON <or -N <, e is 1 when E is -O- or -COO-, and e is E when -CON <or -N <. Is 2. ] The component (b) is a di-long-chain tertiary amine compound represented by the following general formula (b1), or a neutralized product thereof with an inorganic acid or an organic acid, according to any one of claims 1 to 6. Liquid detergent composition.

[Wherein, R ^1b is an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, R ^2b and R ^3b are each an alkyl group or alkenyl group having 11 to 21 carbon atoms, and m and n are each 1 It is a number of ~ 3. ]   A fiber product, wherein an aqueous medium containing the liquid detergent composition according to any one of claims 1 to 7 is brought into contact with a fiber product to simultaneously perform cleaning of the fiber product and imparting flexibility to the fiber product. Cleaning method.