JP4994869B2 - Liquid detergent composition - Google Patents

Description

  The present invention relates to a liquid cleaning composition and a method for cleaning clothes using the same.

  Dirt derived from sebum and protein adhering to heels and cuffs, yellowish stains, and sock stains are very stubborn stains, and it is difficult to drop them to a satisfactory level with normal washing. It takes a lot of work. As a method for obtaining a simpler and higher cleaning effect, a coating cleaning agent has been proposed, and Patent Documents 1 and 2 disclose such cleaning technology. In addition, it is known to use a fluorescent brightening agent as a liquid detergent for the purpose of washing clothes whiter. However, when a liquid detergent containing a fluorescent brightening agent is applied directly to clothing and washed, there is a problem that the fluorescent brightening agent becomes uneven. Patent Documents 3 to 5 disclose techniques for suppressing unevenness of the fluorescent whitening agent blend product.

  Even if the optical brightener is blended as it is in Patent Documents 1 and 2, the unevenness at the time of coating and washing cannot be improved, and even if the techniques of Patent Documents 3 to 5 are used, the unevenness suppressing effect is still satisfactory. The level is not reached.

Patent Documents 6 and 7 use a liquid detergent composition that contains a chelating agent and has improved performance against spilled dirt, Eli / Sode dirt, and stain stains. Even if the fluorescent brightening agent is added, the unevenness of the fluorescent brightening agent cannot be suppressed.
Japanese Patent Laid-Open No. 10-298599 JP 11-269500 A JP 2001-254100 A Japanese Patent Laid-Open No. 2-20600 JP-A-2-73900 JP 2003-277790 A JP 2004-75796 A

  An object of the present invention is to provide a liquid cleaning composition which has no unevenness due to the blending of a fluorescent brightening agent during coating and cleaning and has a high cleaning effect against dirt such as stubborn wrinkles and socks derived from sebum and protein. There is. Furthermore, the problem of the present invention is that in the cleaning method in which the object to be cleaned is brought into direct contact without dilution, the unevenness due to the blending of the fluorescent brightening agent does not occur, and dirt such as stubborn wrinkles and socks derived from sebum and protein It is an object of the present invention to provide a cleaning method that gives a high cleaning effect to the above.

  The present invention relates to (a) a fluorescent brightening agent, (b) a polyether type non-polymer having one or more alkyl groups or alkenyl groups having 10 to 20 carbon atoms and having a polyoxyethylene group and / or an oxypropylene group. An ionic surfactant 25 to 80% by mass, (c) an anionic surfactant 0.1 to 15% by mass, and (d) a chelating agent having a phosphonic acid group. The present invention relates to a liquid detergent composition having a weight ratio of 2 to 500.

  Moreover, this invention relates to the washing | cleaning method of clothing including the process which makes the stock solution of the said liquid cleaning composition of this invention contact the stain | pollution | contamination adhering to clothing directly.

  The liquid detergent composition of the present invention has no unevenness due to the blending of the fluorescent brightening agent at the time of coating and washing, and has a high washing effect against dirt such as stubborn wrinkles and socks derived from sebum and protein. In addition, according to the present invention, even if it is brought into direct contact with the object to be cleaned without being diluted, the unevenness due to the blending of the optical brightener does not occur, and it is possible to prevent stubborn dirt and socks derived from sebum and protein. And a cleaning method that provides a high cleaning effect.

  In the liquid detergent composition of the present invention, the fluorescent brightener is dissolved in a specific concentration of a polyether-type nonionic surfactant in a mixed micelle state, and the concentration of the fluorescent dye existing outside the mixed micelle is reduced. Thus, the effect of suppressing unevenness due to the fluorescent brightening agent at the time of coating and washing is confirmed, and the effect is further improved by using a phosphonic acid chelating agent in combination. Although the mechanism of action of this phosphonic acid chelating agent is not clear, the unevenness of the fluorescent whitening agent promoted by the calcium ions derived from fibers and dirt as a binder has been improved by the phosphonic acid chelating agent. I guess it is.

  Furthermore, by including a polyether type nonionic surfactant and an anionic surfactant in a specific ratio, it is possible to obtain a sufficient effect of the fluorescent whitening agent in a use situation of a washing machine after dilution with tap water. I found it.

[(A) component]
The liquid detergent composition of the present invention contains a fluorescent brightener as the component (a). The liquid detergent composition of the present invention preferably uses a fluorescent whitening agent having a sulfonic acid group or a salt thereof, more preferably a biphenyl type fluorescent whitening agent and / or a stilbene type fluorescent whitening agent. Biphenyl type optical brighteners such as 4,4′-bis (2-sulfostyryl) biphenyl dialkali metal salt (preferably sodium) and 4,4′-bis (2-sulfo-4-chlorostyryl) biphenyl dialkali metal salt (Preferably sodium). In particular, 4,4′-bis (2-sulfostyryl) biphenyl disodium is preferable from the viewpoint of excellent whitening effect and excellent solubility in a liquid detergent. As the stilbene type fluorescent whitening agent, the compound of the general formula (1) (M is sodium) is particularly preferred.

  In the liquid detergent composition of the present invention, in order to obtain a good whitening effect, the content of the component (a) is preferably 0.01 to 1% by mass, particularly 0.05 to 0.00% in the composition. 8% by mass.

[Component (b)]
The liquid detergent composition of the present invention contains a specific nonionic surfactant as the component (b). The component (b) has at least one alkyl group or alkenyl group having 10 to 20 carbon atoms, and has an oxyethylene group and / or an oxypropylene group from the viewpoint of the cleaning effect and the effect of suppressing unevenness of the fluorescent dye. A polyether type nonionic surfactant having As the component (b), a nonionic surfactant represented by the following general formula (2) is suitable.

R ₄ -T-[(R ₅ O) _p -H] _q (2)
[Wherein, R ₄ is an alkyl or alkenyl group having 10 to 18 carbon atoms, and R ₅ is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group. Moreover, p is an average addition mole number, and shows the number of 2-100, Preferably it is 2-40, Most preferably, it is 2-20. Further, T is —O—, —N— or —CON—, q is 1 when T is —O—, and q is 2 when T is —N— or —CON—. ]

Specific examples of the compound of the general formula (2) include the following compound (3) or (4).
R ₆ —O— (C ₂ H ₄ O) _r —H (3)
[Wherein, R ₆ is an alkyl group having 10 to 16 carbon atoms, r is an average number of added moles, and is a number of 5 to 20, preferably 5 to 15. ]
_{R 7 -O- (C 2 H 4} O) s (C 3 H 6 O) t -H (4)
[In the formula, R ₇ is an alkyl group having 10 to 16 carbon atoms, s and t are average addition mole numbers, each independently 2 to 20, preferably 2 to 10, ethylene oxide (hereinafter EO) and propylene oxide (hereinafter referred to as PO) may be random or block adducts. ]

  Moreover, nonionic surfactants, such as aliphatic alkanolamide of General formula (5) or (6), can also be used.

[Wherein, R ₄ has the same meaning as described above, and the sum of u and v is a number of 5 to 100, preferably 5 to 80. ]

  The liquid detergent composition of the present invention has a high cleaning effect against stubborn wrinkles and socks that are derived from sebum and protein, and suppresses unevenness due to the fluorescent whitening agent. The content of is 25 to 80% by mass, preferably 25 to 60% by mass, and particularly preferably 30 to 45% by mass.

[Component (c)]
The liquid detergent composition of the present invention contains an anionic surfactant as the component (c). Examples of the anionic surfactant include alkylbenzene sulfonic acid or a salt thereof, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, olefin sulfonate, alkane sulfonate, fatty acid or salt thereof, alkyl or alkenyl ether carboxylic acid or The salts thereof, α-sulfo fatty acid salts, α-sulfo fatty acid esters can be used, and in particular, alkylbenzenesulfonic acid having an alkyl group having 10 to 20 carbon atoms, preferably 10 to 15 carbon atoms, or a salt thereof, polyoxyethylene Alkyl or alkenyl (C10-C20, preferably 10-15) ether sulfate, alkyl or alkenyl (C10-C20, preferably 10-15) sulfate, saturated fatty acid or salt thereof Is preferred. When polyoxyethylene alkyl or alkenyl sulfate is used, the average number of moles of ethylene oxide added is preferably 1 to 6, particularly 1.5 to 4.

  In the liquid detergent composition of the present invention, the component (c) is 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, particularly 1 to 10% by mass for the purpose of improving the detergency against mud dirt. It is preferable to contain.

  Moreover, (b) component / (c) component (weight ratio) is 2-500, More preferably, 3-100, Especially 5-50 are suitable. By containing in such a specific ratio, it has an extremely high cleaning effect against stubborn wrinkles and socks dirt derived from sebum and protein, and also has a sufficient effect of suppressing unevenness during application using a fluorescent whitening agent Can be demonstrated.

  Furthermore, the total content of the component (b) and the component (c) is 20 to 80%, preferably 25 to 70% by mass, more preferably 30 to 55% by mass in the composition from the viewpoint of improving detergency. .

[Component (d)]
The liquid detergent composition of the present invention contains a chelating agent having a phosphonic acid group. Such chelating agents include 1-hydroxyethane-1,1-diphosphonic acid, aminotri (methylenephosphonic acid) ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), 1-hydroxyethylidene 1-1, 1-diphosphonic acid, 4-dimethylamino-1-hydroxybutane-1,1-diphosphonic acid, pyrrolidone-5,5-diphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, dimethylaminomethanediphosphonic acid, N -Carboxymethylamino-alkanediphosphonic acid, other phosphonic acids such as azacycloalkane-2,2-diphosphonic acid having a cyclic moiety and cyclic aminophosphonic acid. Among these, 1-hydroxyethane-1,1-diphosphonic acid, 4-dimethylamino-1-hydroxybutane-1,1-diphosphonic acid, and azacycloalkane-2,2-diphosphonic acid are preferable.

  Also, orthophosphoric acid having one phosphonic acid group in the molecule, which is polycondensed and having two or more phosphonic acid groups per molecular unit, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid Hexametaphosphoric acid, polyphosphoric acid, etc. can also be used.

  In the liquid detergent composition of the present invention, the content of the component (d) is preferably 0.01 to 5% by mass for the purpose of suppressing the unevenness of the fluorescent whitening agent and improving the detergency against stubborn dirt. Is preferably 0.05 to 3% by mass, particularly 0.1 to 1% by mass. Although the mechanism of the effect of suppressing the unevenness of the fluorescent whitening agent is not clear, when the stock solution is applied to the stain, the component (d) captures the hardness component in the stain on the fiber or fiber surface. I think that the high-density dyeing could be suppressed. In general, blending a chelating agent is desirable for improving the detergency of the liquid detergent composition. However, by using the component (d) of the present invention, the components (b) and (c) are combined. In the surfactant system used in combination under specific conditions, it is an unexpected effect that not only the detergency is improved but also the unevenness of the fluorescent brightener is suppressed. As shown as a comparative product to be described later, with other chelating agents, improvement in detergency and suppression of unevenness of the fluorescent brightening agent as in the component (d) of the present invention are not achieved.

  Furthermore, the mass ratio of component (a) / component (d) is preferably 0.01 to 100, more preferably 0.03 to 50, still more preferably from the viewpoint of preventing unevenness of the fluorescent brightening agent. Is from 0.03 to 50, more preferably from 0.05 to 3, particularly preferably from 0.1 to 1.

[(E) component]
The liquid detergent composition of the present invention may contain an inorganic alkaline agent as the component (e). Examples of the inorganic alkali agent include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, borax, sodium silicate (SiO ₂ / Na ₂ O = 1/1 to 4/1, preferably 2 / 1-2.5 / 1). Among these, sodium hydroxide and potassium hydroxide are preferable from the viewpoint of the cleaning effect. The liquid detergent composition of the present invention may also contain an organic alkaline agent such as ethanolamine, but it has a problem that it tends to turn yellowish brown after long-term storage when used in combination with a fluorescent brightening agent. preferable.

  In the liquid detergent composition of the present invention, from the viewpoint of adjusting the pH to be described later, the component (e) is 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and particularly 0.2 to 2% by mass. % Content is preferred.

[Component (f)]
The liquid detergent composition of the present invention may contain an organic solvent. Examples of the organic solvent include an organic solvent represented by the general formula (7), an ester organic solvent (for example, methyl acetate, ethyl acetate, methyl propionate, etc.), a ketone organic solvent (for example, acetone, diethyl ketone, methyl ethyl ketone, And diether ketone, methyl isobutyl ketone, methyl isopropyl ketone, etc.) and ether organic solvents (dioxane, tetrahydrofuran, triethylene glycol dimethyl ether, etc.).

R ¹ —O— (AO) _n —H (7)
(In the formula, R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a phenyl group or a benzyl group, and A represents a linear or branched alkylene group having 2 to 4 carbon atoms. And n A may be the same or different, and n is a number of 0 to 10 indicating the average number of moles of alkylene oxide added.)

  Specific examples of the organic solvent represented by the general formula (7) include alcohols such as ethanol, propanol and butanol, and glycols such as ethylene glycol, propylene glycol, trimethylene glycol, butyl diglycol, diethylene glycol and triethylene glycol. And polyalkylene glycol monoalkyl or aryl ethers such as diethylene glycol butyl ether and triethylene glycol phenyl ether.

  As the component (f), an organic solvent represented by the general formula (7) is preferable, and an organic solvent containing two sites having a hydroxy group such as ethylene glycol, propylene glycol, trimethylene glycol, polyethylene glycol, and butylene glycol. Are more preferable, and propylene glycol and polyethylene glycol are more preferable.

  In the liquid detergent composition of the present invention, the component (f) is 0.1 to 20% by mass, more preferably 1 to 15% by mass, and particularly 2 to 10% by mass for the purpose of improving the coating detergency against stubborn dirt. It is preferable to contain.

[(G) component]
The liquid detergent composition of the present invention may contain hydrogen peroxide as the component (g). The content of the component (g) in the liquid detergent composition of the present invention is preferably 0.1 to 6% by mass, more preferably 0.5 to 5% by mass, and still more preferably 1 to 4.5% by mass. Especially preferably, it is 1-3 mass%. In such a range, it is possible to obtain a further cleaning effect against stubborn dirt derived from sebum adhering to the heels and cuffs.

[Other ingredients]
The liquid detergent composition of the present invention is not limited to the nonionic surfactant as the component (b) and the anionic surfactant as the component (c). It may contain a cationic surfactant, an anionic surfactant and an amphoteric surfactant described in Japan Patent Office, March 26, 1998, P4-22.

  The liquid detergent composition of the present invention may contain a pH jump base as described in JP-A-2006-143907 in order to improve the washing effect after dilution with water.

  The liquid detergent composition of the present invention may contain a radical trapping agent from the viewpoint of improving the stability of hydrogen peroxide and the bleach activator. As the radical trapping agent, phenol-based compounds, that is, derivatives having phenolic OH groups, derivatives thereof such as ester derivatives and ether derivatives thereof are preferable. Preferable examples include dimethoxyphenol, catechol, hydroquinone, methoxyphenol, dibutylhydroxytoluene (BHT) and the like.

  In addition, the liquid detergent composition of the present invention may contain optional components such as hydrotropes, silicones, bactericides, enzymes, and fragrances. As a fragrance | flavor, the fragrance | flavor of patent publication 2003-213295 paragraphs 0007-0022 can be used, for example.

  The liquid detergent composition of the present invention exhibits excellent cleaning performance when the pH at 20 ° C. is 2 to 9, preferably 3 to 8, and more preferably 4 to 7. In particular, in a cleaning method in which the object to be cleaned is brought into direct contact without being diluted, by adjusting to the above-mentioned limited pH, a high cleaning effect against stubborn wrinkles and socks dirt derived from epithelial fat and protein Can be given.

[How to wash clothes]
The liquid detergent composition of the present invention may be directly put into a washing tub, but is attached to clothes (especially dirt derived from sebum and protein attached to heels and cuffs, yellowish dirt, and socks dirt). It can also be used as a liquid detergent composition for coating that is brought into direct contact with the liquid.

  Therefore, the washing | cleaning method of the clothing of this invention is a method including the process of making the stock solution of a liquid cleaning composition contact the stain | pollution | contamination adhering to clothing directly.

  A very high cleaning effect can be obtained by bringing the stock solution of the liquid detergent composition of the present invention into direct contact with dirt adhering to clothing by coating or the like.

Examples 1-7, Comparative Examples 1-4
A liquid detergent composition having the composition shown in Table 1 was prepared using the following ingredients. About the obtained liquid cleaning composition, the cleaning performance was evaluated by the following method. The results are shown in Table 1.

<Blending ingredients>
(A) Component a-1; Chino Pearl CBS-X (FWA-8, manufactured by Ciba Specialty Chemicals)
A-2; Chino Pearl TAS (FWA-102, manufactured by Ciba Specialty Chemicals)
(B) Component b-1; polyoxyethylene lauryl ether (EO average addition mole number = 11)
・ B-2: Non-ionic surface activity obtained by adding 6 mol of EO on average to a linear primary alcohol having 10 to 14 carbon atoms, adding 2 mol of PO on average, and then adding 3 mol of EO on average Agent / b-3: Nonionic surfactant obtained by adding an average of 7 mol of EO to a linear secondary alcohol having 10 to 14 carbon atoms (c) Component / c-1; Linear alkyl (carbon number 12) -14) Sodium benzenesulfonate · c-2; Sodium polyoxyethylene lauryl ether sulfate (Emal 20C manufactured by Kao Corporation)
(D) Component d-1; 1-hydroxyethane-1,1-diphosphonic acid (Daiquest 2010, manufactured by Solusia)
· D-2; orthophosphoric acid · d'-1; trisodium methylglycine diacetate (Trilon M Liquid, manufactured by BASF Japan Ltd.)
D′-2; edetate tetrasodium (KK-07, manufactured by Chubu Kirest Co., Ltd.)
Other components (e) Component / e-1; Sodium hydroxide (f) Component / f-1; Ethanol / f-2; Propylene glycol (g) Component / g-1; Hydrogen peroxide (h) Component / h- 1; Fragrance (i) Component / i-1; Ion exchange water

<Cleaning performance evaluation method>
(1) Cleaning performance against wrinkle stains The cotton / polyester blended shirts worn for 3 days in summer are cut off, and the scissors are divided into three groups according to the degree of soiling. did. Prepare 1 piece of 30 cm x 30 cm cotton cloth sewn with 5 scissors for cleaning evaluation. In the washing machine (National Washing Machine NA-F60E), apply the detergent composition to 1 scissor piece. Apply 4 ml (20 ml total). Thereafter, washing was performed in a washing machine standard course under conditions of 20 ° C. and 5 ° DH hard water without adding any detergent. After natural drying, 10 panelists (5 men in their 30s, 5 women) trained in regular work were evaluated according to the following criteria.
1: Dirt is removed to a satisfactory level. 2: Dirt remains, but is not worrisome. 3: Dirt remains to an extent of concern. 4: Dirt remains considerably.

(2) Washing performance against socks dirt Two socks (Gunze, Support & Clean, cotton / acrylic / polyester / polyurethane) that were worn by 10 elementary school boys for one day and washed heavily (washing made by National) Machine NA-F60E), and 5 ml / sheet (total 20 ml) of the detergent composition was applied directly to the soiled portion of the sock. Thereafter, washing was performed in a washing machine standard course under conditions of 20 ° C. and 5 ° DH hard water without adding any detergent. After natural drying, 10 panelists (5 men in their 30s, 5 women) trained in regular work were evaluated according to the following criteria.
1: Dirt has been removed to a satisfactory level 2: Dirt remains, but is not worrisome 3: Dirt remains to an extent of concern 4: Dirt remains considerably

<Evaluation method for unevenness of fluorescent whitening agent after coating and washing>
Prepare 5 sheets of fluorescent brightening agent undyed cotton cloth (gold width # 2023) cut to 8 cm × 8 cm, apply 0.4 ml of the cleaning composition of Table 1 to each cloth, and let stand for 5 minutes. Washing was performed without adding a detergent with a tartometer (water 1 L, hardness 5 ° DH, water temperature 20 ° C., 80 rpm, 10 minutes). Then, running water was rinsed with tap water for 5 minutes, and after dehydration, it was naturally dried indoors.

About the said clothing, under the black light of the dark room (Toshiba company make, FL20S-BLB), the evaluation with unevenness was performed by the following reference | standard by 10 panelists (5 men in their 30s, 5 women). Taking the average score, the average score is 3 or more and 4 or less, ◎, 2 or more and less than 3 points is judged as ◯, 1.5 or more and less than 2 points as △, and less than 1.5 as ×, Table 1 It was shown to. “One point” is a level that can be easily recognized even under an indoor fluorescent lamp.
(Judgment criteria with unevenness)
I do not know the unevenness 4-point unevenness is faintly visible 3-point unevenness is slightly seen 2-point unevenness is well understood 1 point

Claims (8)

(A) fluorescent whitening agent, (b) a polyether type nonionic surfactant having at least one alkyl group or alkenyl group having 10 to 20 carbon atoms and having a polyoxyethylene group and / or an oxypropylene group 25 to 80% by mass, (c) 0.1 to 15% by mass of an anionic surfactant , and (d) having a phosphonic acid group selected from 1-hydroxyethane-1,1-diphosphonic acid and orthophosphoric acid contain a chelating agent 0.01 to 1.5 wt%, Ri weight ratio 2 to 500 der component (b) / (c) component, pH at 20 ° C. is 4 to 8.5, liquid cleaning Agent composition.   The liquid cleaning composition of Claim 1 whose mass ratio of (a) component / (d) component is 0.01-100.   The liquid detergent composition of Claim 1 or 2 whose mass ratio of (a) component / (b) component is 1/10000-5/100.   The liquid detergent composition in any one of Claims 1-3 whose (a) component is a fluorescent whitening agent which has a sulfonic acid group or its salt.   Furthermore, the liquid cleaning composition in any one of Claims 1-4 which contains an inorganic alkaline agent as (e) component.   Furthermore, the liquid detergent composition in any one of Claims 1-5 containing an organic solvent as (f) component.   Furthermore, the liquid cleaning composition in any one of Claims 1-6 which contains hydrogen peroxide as (g) component. The washing | cleaning method of clothing including the process of apply | coating the stock solution of the liquid cleaning composition in any one of Claims 1-7 directly to the stain | pollution | contamination adhering to clothing, and making it contact.