JP5985429B2 - Liquid detergent composition - Google Patents

Description

  The present invention relates to a liquid detergent composition.

  As a liquid detergent composition, a composition mainly composed of an alkaline agent and a nonionic surfactant is known. For example, in liquid detergents for dishwashers, alkaline agents solubilize dirt mainly by hydrolysis, so nonionic surfactants mainly wash and remove dirt, and also wash oil dirt. Used to improve power.

  When used in an automatic dishwasher, the cleaning liquid is sprayed and washed at a pressure higher than that of the nozzle. Therefore, if there is a lot of foaming of the surfactant, the foam overflows and the discharge pressure of the spray device decreases. Therefore, it is required that there is little foaming, that is, low foaming properties.

  On the other hand, it is necessary to mix a certain amount of nonionic surfactant in order to ensure the cleaning performance, and sufficiently obtain the low foaming property required for the dishwashing agent while maintaining the cleaning power. This is difficult (see Patent Documents 1, 2, and 3).

  In general, aqueous liquid detergents using a combination of an alkaline agent and a nonionic surfactant cause white turbidity and separation due to a decrease in the cloud point of the nonionic surfactant, resulting in poor stability. A solubilizer is used in combination (see Patent Document 4). However, the solubilizing agent itself often causes foaming, and a solubilizing agent having a lower foaming property is desired.

  In addition, in Patent Document 5, a surfactant having a sulfonate group obtained by reacting bisulfite with glycidyl ether obtained by reacting alcohol or an alkylene oxide adduct thereof with epichlorohydrin is combined with an alkali agent. An alkaline cleaning agent is disclosed. However, there is no disclosure about combining a specific nonionic surfactant with a surfactant and an alkali agent having these sulfonate groups, and it is possible to achieve both storage stability, low foamability and detergency. It wasn't.

JP 2010-047731 A JP 2010-037414 A JP 2012-193228 A JP 2000-096097 A JP 05-311200 A

  An object of this invention is to provide the liquid detergent composition which is excellent in the storage stability of a product in view of the above point, is low-foaming property, and is excellent in a detergency.

  The liquid detergent composition according to the present invention contains a compound (A) represented by the following general formula (1), an alkaline agent (B), and a nonionic surfactant (C), and the nonionic The surfactant (C) is at least one selected from a polyoxyalkylene alkyl ether (Ca) represented by the following general formula (2) and a polyoxyethylene polyoxypropylene block polymer (Cb). Is.

^{_{R 1 O- (AO) n -CH}} 2 CH (OH) CH 2 -SO 3 Na ... (1)
In the formula, R ¹ is a linear or branched alkyl group having 4 to 8 carbon atoms, a phenyl group, or an alkylphenyl group having an alkyl group having 1 to 4 carbon atoms, and AO is an oxy having 2 to 4 carbon atoms. An alkylene group, n represents the average number of moles added and is a number from 0 to 5;

_{^{R 2 O - [(EO)}} x / (PO) y] -H ... (2)
In the formula, R ² is a linear or branched alkyl group having 8 to 14 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group. x and y each represent an average addition mole number, and are x = 5-15 and y = 1-6. The addition form of EO and PO may be random addition, block addition, or a combination thereof.

  ADVANTAGE OF THE INVENTION According to this invention, the cleaning composition which is excellent in the storage stability of a product, is low-foaming property, and is excellent in a detergency can be provided.

  The liquid detergent composition according to this embodiment contains the compound (A) represented by the general formula (1), the alkali agent (B), and the specific nonionic surfactant (C). By using these three components, it is possible to achieve both cleanability and low foamability while being excellent in storage stability. Hereinafter, each of these components will be described in detail.

<Compound (A)>
The compound (A) represented by the general formula (1) is a sulfonate having a hydrocarbon group represented by R ¹ and has a hydroxyl group inside the molecule.

In Formula (1), R ¹ is a linear or branched alkyl group having 4 to 8 carbon atoms, a phenyl group, or an alkylphenyl group having a linear or branched alkyl group having 1 to 4 carbon atoms. . Thus, when the carbon number of the alkyl group is 8 or less, or the carbon number of the phenyl group having no alkyl group or the alkylphenyl group is 4 or less, the water solubility of the compound (A) is ensured. Thus, the stability of the cleaning composition can be improved. Further, when the alkyl group has 4 or more carbon atoms, desired performance can be exhibited. R ¹ is preferably an alkyl group having 4 to 8 carbon atoms for the purpose of obtaining more excellent detergency and low foamability.

Specific examples of R ¹ include alkyl groups such as n-butyl, n-pentyl, n-hexyl, n-octyl and 2-ethylhexyl, alkylphenyl groups such as tolyl group, butylphenyl group, xylyl group and mesityl group, And a phenyl group etc. are mentioned.

  In the formula (1), AO is an oxyalkylene group having 2 to 4 carbon atoms. Specific examples include an oxyethylene group, an oxypropylene group, and an oxybutylene group, and these are used alone or in combination of two or more. Preferably, AO is an oxyethylene group and / or an oxypropylene group. n represents the average added mole number of AO, and is a number of 0-5. n = 0 may be sufficient, that is, the compound (A) may not have AO.

  Compound (A) can be produced, for example, by reacting sodium sulfite with glycidyl ether. Moreover, the glycidyl ether used as the raw material is obtained by making epichlorohydrin react with alcohol, phenol, alkylphenol, or those alkylene oxide adducts. The alkylene oxide adduct can also be produced by a known method. For example, an alkali or acid catalyst is added to a raw material alcohol, the temperature is increased, and propylene oxide and / or ethylene oxide is appropriately added and reacted. Thereafter, it can be produced by neutralizing the system.

<Alkaline agent (B)>
Examples of the alkali agent (B) include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate. Alkali metal silicates such as salt, sodium silicate, potassium silicate, alkali metal phosphates such as sodium phosphate, potassium phosphate, dibasic sodium phosphate, dibasic potassium phosphate, sodium citrate, potassium citrate, etc. Alkali metal citrate, monoethanolamine, diethanolamine, triethanolamine, methylamine, dimethylamine, ethylamine, diethylamine, triethylamine, morpholine, cyclohexylamine, tetramethylammonium hydroxide, tetraethylan Onium hydroxide, trimethyl-2-hydroxyethyl ammonium hydroxide (common name: choline), ethylenediamine tetraacetic acid tetrasodium salt. These alkali agents can be used alone or in combination of two or more.

<Nonionic surfactant (C)>
Examples of the nonionic surfactant (C) include the polyoxyalkylene alkyl ether (Ca) represented by the general formula (2) and the polyoxyethylene polyoxypropylene block polymer (Cb). It is done.

In the polyoxyalkylene alkyl ether (Ca), R ² in the above formula (2) is a linear or branched alkyl group having 8 to 14 carbon atoms and having 8 or more carbon atoms. The detergency can be improved, and when the number of carbon atoms is 14 or less, it is possible to improve the bubble breakage and improve the low bubble property. The carbon number of R ² is more preferably in the range of 9 to 13 from the viewpoint of detergency.

  In the above formula (2), EO represents an oxyethylene group, and PO represents an oxypropylene group. x and y represent the average added mole numbers of EO and PO, respectively, where x = 5 to 15 and y = 1 to 6. The addition form of EO and PO may be random addition, block addition, or a combination thereof. When x is 5 or more, solubility in water can be improved, preferably x> y, and more preferably x = 7-12. Moreover, when y is 1 or more, low-foaming property can be improved.

  The polyoxyalkylene alkyl ether (C-a) can be produced by a known method. For example, an alkali or acid catalyst is added to the starting alcohol, the temperature is raised, and then propylene oxide and / or ethylene oxide is added. After an appropriate addition reaction, it can be produced by neutralizing the system.

  As a polyoxyethylene polyoxypropylene block polymer (Cb), the thing of the structure represented by following General formula (3) and / or General formula (4) is mentioned.

HO- (EO) _p- (PO) _q- (EO) _r- H (3)
HO- (PO) _s- (EO) _t- (PO) _u -H (4)

  In formulas (3) and (4), EO represents an oxyethylene group and PO represents an oxypropylene group. p, r and t represent the average added mole number of EO, preferably p + r ≦ 300, more preferably p + r is a number from 50 to 180, and preferably t ≦ 300, more Preferably t is a number from 50 to 180. q, s, and u represent the average number of moles added of PO, preferably q ≦ 100, more preferably q is a number from 20 to 60, and preferably s + u ≦ 100, Preferably s + u is a number from 20 to 60. Further, p + r> q is preferable, and t> s + u is preferable. In more detail, it is preferable that the content rate of EO is 50 mass% or more, More preferably, it is 60-85 mass%. Note that p, q, r, s, t, and u are all numbers greater than zero.

  Any one of these nonionic surfactants (C) may be used, or two or more thereof may be used in combination.

<Liquid cleaning composition>
In the liquid detergent composition according to this embodiment, the content of the compound (A) is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and still more preferably. 1 to 10% by mass. Moreover, it is preferable that content of an alkaline agent (B) is 0.5-50 mass%, More preferably, it is 3-30 mass%, More preferably, it is 5-25 mass%. Moreover, it is preferable that content of a nonionic surfactant (C) is 0.1-30 mass%, More preferably, it is 0.5-10 mass%, More preferably, it is 0.5-5. % By mass.

  In the liquid detergent composition according to this embodiment, the compounding ratio of the compound (A), the alkali agent (B), and the nonionic surfactant (C) is a mass ratio of compound (A) / alkali agent ( B) / Nonionic surfactant (C) = 1 / 0.1-30 / 0.1-10 is preferable. That is, when the compounding amount of the compound (A) is 1, the compounding amount of the alkaline agent (B) is 0.1-30, and the compounding amount of the nonionic surfactant (C) is 0.1-10. It is preferable that By setting it as such a compounding ratio, the said desired performance can be exhibited more effectively. The blending ratio is more preferably (A) / (B) / (C) = 1/1 to 15 / 0.2 to 3, and more preferably (A) / (B) / (C) = 1/2 to 10 / 0.2 to 1.

  In the liquid cleaning composition according to the present embodiment, water is used as the base component. That is, in the liquid cleaning composition of the present embodiment, the balance other than the compound (A), the alkali agent (B) and the nonionic surfactant (C) and other compounding components added as necessary, Usually water.

  In addition, the liquid detergent composition according to this embodiment contains a surfactant other than the above, an enzyme, a bleaching agent, an antifoaming agent, a rust preventive, a hydrotrope, a surface modifier, a fragrance, and the like. Can do.

  Since the liquid detergent composition according to the present embodiment includes an alkaline agent and a nonionic surfactant, for example, for cleaning dirt such as oil and fat adhering to a metal surface, glass surface or ceramic surface, resin surface, and the like. It can be preferably used. In particular, the liquid detergent composition according to the present embodiment has a low-foaming property capable of being spray-washed and is excellent in detergency, so that it is particularly suitably used as a detergent for a dishwasher, for example. it can. Moreover, it is not limited to the cleaning agent for tableware washing machines, It can also be used as a cleaning agent for various hard surfaces.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

<Synthesis of C ₄ -2EO-H glycidyl ether>
A 500 mL glass Separa flask was charged with 162 g of diethylene glycol monobutyl ether (Nacalai Tesque), 138 g of epichlorohydrin, 167 g of a 48% by mass aqueous sodium hydroxide solution and 0.5 g of tetramethylammonium bromide at 50 ° C. with vigorous stirring. The reaction was performed for 3 hours. The obtained reaction mixture was cooled to room temperature, and the organic layer was washed with water. C ₄ -2EO-H glycidyl ether was obtained by distillation from this organic layer under reduced pressure.

<Synthesis of C ₄ -2PO-3EO-H glycidyl ether>
C ₄ -2EO-H glycidyl ether, except that C ₄ -2PO-3EO-H obtained by sequentially reacting 2 mol of PO and 3 mol of EO in place of diethylene glycol monobutyl ether was used. In the same manner as in the above synthesis, glycidyl ether of C ₄ -2PO-3EO-H was obtained.

<Production Example 1>
A 500 mL glass Separa flask is charged with 100 g of Epogosay 2EH (Yokkaichi Synthesis, 2-ethylhexyl glycidyl ether), 53.2 g of sodium bisulfite (Nacalai Tesque), 6.3 g of sodium sulfite (Nacalai Tesque), and 300 g of water. The mixture was reacted at 105 ° C. for 10 hours under reflux to obtain sodium 2-ethylhexyl glyceryl ether sulfonate (A-1) represented by the above formula (1) (in the formula (1), R ¹ had 8 carbon atoms. An alkyl group of n = 0). ^The purity by ¹ H-NMR was 99 mol% or more.

<Production Example 2>
A sodium phenylglyceryl ether sulfonate represented by the above formula (1) (A-2) was prepared in the same manner as in Production Example 1, except that Epiol P (Nippon Oil Co., Ltd., phenylglycidyl ether) was used instead of Epogosay 2EH. (In formula (1), R ¹ is a phenyl group, n = 0). ^The purity by ¹ H-NMR was 99 mol% or more.

<Production Example 3>
O-sec- represented by the above formula (1) in the same manner as in Production Example 1 except that OSBP-EP (Yokkaichi Synthesis Co., Ltd., o-sec-butylphenylglycidyl ether) was used instead of Epogosay 2EH. Sodium butylphenyl glyceryl ether sulfonate (A-3) was obtained (in formula (1), R ¹ is an o-sec-butylphenyl group, n = 0). ^The purity by ¹ H-NMR was 99 mol% or more.

<Production Example 4>
A sodium glyceryl ether sulfonate of C ₄ -2EO-H represented by the above formula (1) in the same manner as in Production Example 1 except that glycidyl ether of C ₄ -2EO-H was used instead of Epogosay 2EH. (A-4) was obtained (in formula (1), R ¹ is an alkyl group having 4 carbon atoms, n = 2, AO = oxyethylene group). ^The purity by ¹ H-NMR was 99% mol or more.

<Production Example 5>
Except for using glycidyl ethers of _C 4 -2PO-3EO-H is in place Epogose 2EH, in the same manner as in Production Example 1, _C 4 glyceryl -2PO-3EO-H represented by the above formula (1) Sodium ether sulfonate (A-5) was obtained (in formula (1), R ¹ is an alkyl group having 4 carbon atoms, n = 5, AO = oxyethylene group and oxypropylene group). ^The purity by ¹ H-NMR was 99 mol% or more.

  The detail of each component used with the cleaning composition of an Example is as follows.

<Compound (A)>
(A-1) to (A-5): described in the above Production Examples 1 to 5. (A′-1): sodium 2-ethylhexanoate (Wako Pure Chemical Industries, Ltd.)
(A′-2): AG6202 (Akzo Nobel, octyl polyglucoside)
Here, (A′-1) and (A′-2) are not the compound (A) represented by the above formula (1).

<Alkaline agent (B)>
(B-1): 3Na citric acid
(B-2): ethylenediaminetetraacetic acid 4Na
・ (B-3): KOH

<Nonionic surfactant (C)>
-(C-a1): In the general formula (2), after using LINEPOL 911 (manufactured by Shell Chemicals Japan, C _9-11 alcohol) as the raw material alcohol, 3 mol of PO was added thereto, and then 12 mol of EO and 2 mol of PO were added. random addition (x = 12, y = 5 ) and a non-ionic surfactant were obtained _{(C 9~11 -3PO- (12EO / 2PO} ) -H)
-(C-a2): In general formula (2), octanol (Kyowa Hakko Chemical Co., Ltd., 2-ethylhexanol) was used as the raw material alcohol, and PO 3 mol and EO 7 mol were sequentially added thereto (x = 7, y = 3 ) to nonionic surfactant obtained _{(C 8 -3PO-7EO-H} )
-(C-a3): In general formula (2), tridecanol (Kyowa Hakko Chemical Co., Ltd., isotridecyl alcohol) is used as the raw material alcohol, 3 mol of EO is added thereto, and then 12 mol of EO and 3 mol of PO are randomly added. (x = 15, y = 3 ) to nonionic surfactant obtained _{(iso-C 13 -3EO- (12EO} / 3PO) -H)
-(C-a4): In the general formula (2), as a raw material, SOFTANOL 120 (Nippon Shokubai Co., Ltd., EO12 mol adduct of sec-C _12-14 alcohol) was used, and 1.5 mol of PO was added thereto = 12, y = 1.5) nonionic surfactant obtained (sec-C _12-14 -12EO-1.5PO-H)
(C-b1): Nonionic surfactant (80EO-30PO-80EO represented by the above formula (3) obtained by adding 160 mol of EO to polypropylene glycol of 30 mol of PO. 3), p = 80, q = 30, r = 80)
· (C'-1): Rineporu 911 (Shell Chemicals Japan _{Ltd., C 9 to 11} alcohol), a nonionic surfactant and 8 mols of EO _(C 9~11 -8EO)
-(C'-2): Softanol 120 (Nippon Shokubai Co., Ltd., EO 12 mol adduct of sec-C _12-14 alcohol)
Here, (C′-1) and (C′-2) are not the nonionic surfactant (C) according to the present embodiment.

<Evaluation of cleaning composition>
A detergent composition for a dishwasher having the composition shown in the examples and comparative examples of Table 1 and Table 2 below was prepared, and stability, low foamability, and cleanability were evaluated by the following methods. The content of the composition shown in the table is a pure value unless otherwise specified.

[1] Stability:
The appearance immediately after the preparation of each cleaning composition was observed and visually judged as “during blending”. In addition, each cleaning composition was put in a 100 mL glass bottle, covered, stored in a thermostatic bath at 50 ° C. and 0 ° C. for 30 days, and the appearance was visually determined. The judgment criteria are as follows.
○: Transparent and uniform with no foreign matter ×: Turbidity, separation, suspended matter or sediment is observed

[2] Low foam property:
6 g of each detergent composition was put into a dishwasher (Matsushita Electric Industrial Co., Ltd., model NP-40SX2), and cleaning was started on a standard course. The state of foaming 1 minute after the start of washing was visually determined. The judgment criteria are as follows.
◎: Almost not foamed ○: Slightly foamed ×: Foamed

[3] Detergency:
Load a polypropylene lunch box (inner dimensions: 156mm x 105mm x 41mm, without lid) coated with 2g of beef tallow into a dishwasher (Matsushita Electric Industrial Co., Ltd., model NP-40SX2), and put 6g of each detergent composition The standard course was washed and the residual oil level of the polypropylene lunch box was sensoryly evaluated. The evaluation criteria are as follows.
◎: No oil remains and no stickiness is felt ○: No oil residue is observed, but a slight amount of sliminess is felt ×: Oil residue is observed

The results are as shown in Tables 1 and 2, and the three components of the compound (A) represented by the above formula (1), the alkali agent (B) and the specific nonionic surfactant (C). In the cleaning composition of Examples 1 to 8 using A, it was possible to achieve both cleanability and low foamability, and excellent storage stability. From the comparison between Examples 2 and 3 and the other examples, the alkyl group is superior in terms of detergency and low foaming properties compared to the case where R ¹ of the compound (A) is a phenyl group or an alkylphenyl group. I understand. In addition, it is thought that the presence or absence of AO in a compound (A) does not have big difference in performance.

  On the other hand, in Comparative Example 1, since the compound (A) was not blended, the stability of the cleaning composition was poor, and therefore the evaluation of low foamability and cleanability was not performed. In Comparative Example 2 in which the alkaline agent (B) was not blended and in Comparative Example 3 in which the nonionic surfactant (C) was not blended, the detergency was poor. Moreover, when using compounds other than the compound (A) represented by the said Formula (1) like the comparative examples 4 and 5, it was inferior to low-bubble property. Furthermore, as in Comparative Examples 6 and 7, when a nonionic surfactant other than the nonionic surfactant (C) specific to this embodiment was used, the low foaming property was poor. As described above, if any one of the three components is missing, the desired effect cannot be obtained.

  The liquid cleaning composition according to the present invention can be suitably used as a cleaning agent for various dishwashers for home use and business use, and also for various uses such as various hard surface cleaning agents. Can do.

Claims (3)

Containing a compound (A) represented by the following general formula (1), an alkali agent (B), and a nonionic surfactant (C);
The nonionic surfactant (C) is at least one selected from a polyoxyalkylene alkyl ether (Ca) represented by the following general formula (2) and a polyoxyethylene polyoxypropylene block polymer (Cb). A liquid detergent composition that is a seed.
^{_{R 1 O- (AO) n -CH}} 2 CH (OH) CH 2 -SO 3 Na ... (1)
[Wherein, R ¹ is a linear or branched alkyl group having 4 to 8 carbon atoms, a phenyl group, or an alkylphenyl group having an alkyl group having 1 to 4 carbon atoms, and AO has 2 to 4 carbon atoms. It is an oxyalkylene group, n represents an average added mole number and is a number of 0-5. ]
_{^{R 2 O - [(EO)}} x / (PO) y] -H ... (2)
[Wherein, R ² represents a linear or branched alkyl group having 8 to 14 carbon atoms, EO represents an oxyethylene group, and PO represents an oxypropylene group. x and y each represent an average addition mole number, and are x = 5-15 and y = 1-6. The addition form of EO and PO may be random addition, block addition, or a combination thereof. ]   The compounding ratio of the above compound (A), alkali agent (B) and nonionic surfactant (C) is a mass ratio of compound (A) / alkali agent (B) / nonionic surfactant (C). = 1 / 0.1 to 30 / 0.1 to 10. The liquid detergent composition according to claim 1.   The liquid detergent composition according to claim 1 or 2, which is a detergent for a dishwasher.