JP2015010141A - Tableware washing detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tableware washing detergent which is not only excellent in detergency, foaming and rinsibility at low temperatures but good in aromatic smelling and has reduced temperature variation of the smelling.SOLUTION: A detergent comprises α-sulfo fatty acid ester salt, α-sulfo fatty acid di-salt, a specified semi-polar surfactant, at least one of compounds of formulae (4) and (5) and a perfume, with the ratio of the individual ingredients controlled specifically. In the formulae (4) and (5), Z is a phenyl group, a benzyl group or a specified alkyl group; AO is a specified oxyalkylene group; m is 1-5; Ris a hydrogen atom or a specified hydrocarbon group; Ris a hydrogen atom or a methyl group; X is -COOor -SO; and Mis H, Na, etc.

Description

  The present invention relates to a dishwashing detergent.

In recent years, there has been an increasing demand for CO ₂ emission reduction, such as numerical targets for carbon dioxide emission reduction. Among them, from the viewpoint of carbon neutral, it is strongly desired to use natural raw materials (such as linear higher alcohols) in dishwashing detergents. More recently, consumers have become more energy-saving not only using detergents that use natural ingredients but also using dishwashing without using hot water. It has increased.

  For example, Patent Document 1 discloses α-sulfo fatty acid methyl ester salts, α-sulfo fatty acid di-salts, alkylamine oxides and the like using natural raw materials as detergents having excellent detergency against foaming and oil stains even at room temperature (25 ° C). A combination is disclosed.

JP 2012-172051 A

  However, the detergent described in Patent Document 1 is excellent in the detergency of foaming and oil stains at room temperature, but at low temperatures (10 ° C), the detergency and foaming are reduced, and the tableware is null during rinsing. There was a problem that the decrease in rinsing properties and the decrease in fragrance became noticeable. In order to improve the fragrance at low temperatures, it is conceivable to increase the blending amount of the fragrance in the detergent, but in that case, when the detergent is used at room temperature, the fragrance is too strong. Occurs.

  The present invention has been made in view of the above circumstances, and not only has excellent cleaning power, foaming and rinsing properties at low temperatures, but also has good scenting at low temperatures and normal temperatures, and there is little difference depending on the temperature of scenting. The issue is to provide dishwashing detergent.

（式（１）中、Ｒ^１は炭素数１０〜１２のアルキル基、Ｒ^２は炭素数１〜２のアルキル基、Ｍ^１は水溶性塩を形成しうる陽イオンである。）

（式（２）中、Ｒ^３は炭素数１０〜１２のアルキル基、Ｍ^２およびＭ^３はそれぞれ独立に水溶性塩を形成しうる陽イオンである。）

（式（３）中、Ｒ^４は炭素数１２〜１４のアルキル基、Ｒ^５およびＲ^６はそれぞれ独立に炭素数１〜３のアルキル基である。）

（式（４）中、Ｚはフェニル基、ベンジル基または炭素数４〜６のアルキル基である。ＡＯは炭素数２〜４のオキシアルキレン基であり、ｍは１〜５の整数である。）

（式（５）中、Ｒ^７は水素原子または炭素数１〜４の炭化水素基、Ｒ^８は水素原子またはメチル基である。Ｘは、−ＣＯＯ⁻または−ＳＯ_３ ⁻、Ｍ^４はＨ^＋、アルカリ金属イオンまたはアルカリ土類金属イオンである。
［２］前記（Ｄ）成分がジエチレングリコールモノブチルエーテルであることを特徴とする［１］に記載の食器洗い洗浄剤。 The present invention has the following configuration.
[1] (A) an α-sulfo fatty acid ester salt represented by the following general formula (1);
(B) an α-sulfo fatty acid di-salt represented by the following general formula (2);
(C) a semipolar surfactant represented by the following general formula (3);
(D) at least one of a compound represented by the following general formula (4) and a compound represented by the following general formula (5);
(E) containing a fragrance,
The mass ratio represented by (A) / (B) is 0.5 to 8,
The mass ratio represented by (B) / (D) is 0.6-30,
The mass ratio represented by ((A) + (B)) / (C) is 1 to 10,
The dishwashing detergent characterized by mass ratio represented by (D) / (E) being 0.5-50.

(In formula (1), R ¹ is an alkyl group having 10 to 12 carbon atoms, R ² is an alkyl group having 1 to ² carbon atoms, and M ¹ is a cation capable of forming a water-soluble salt.)

(In formula (2), R ³ is an alkyl group having 10 to 12 carbon atoms, and M ² and M ³ are each a cation capable of independently forming a water-soluble salt.)

(In Formula (3), R ⁴ is an alkyl group having 12 to 14 carbon atoms, and R ⁵ and R ⁶ are each independently an alkyl group having 1 to 3 carbon atoms.)

(In Formula (4), Z is a phenyl group, a benzyl group, or a C4-C6 alkyl group. AO is a C2-C4 oxyalkylene group, and m is an integer of 1-5. )

(In Formula (5), R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, R ⁸ is a hydrogen atom or a methyl group, X is —COO ^— or —SO ₃ ^— , and M ⁴ is H. ⁺ , An alkali metal ion or an alkaline earth metal ion.
[2] The dishwashing detergent according to [1], wherein the component (D) is diethylene glycol monobutyl ether.

  ADVANTAGE OF THE INVENTION According to this invention, the dishwashing detergent which not only is excellent in the detergency at the time of low temperature, foaming, and a rinse property but is good in both fragrance at the time of low temperature and normal temperature, and there are few differences with the temperature of fragrance.

Hereinafter, the present invention will be described in detail.
[(A) α-sulfo fatty acid ester salt]
The dishwashing detergent of the present invention (hereinafter also simply referred to as “cleaning agent”) is a liquid detergent and contains (A) an α-sulfo fatty acid ester salt as a main active agent.
(A) α-sulfo fatty acid ester salt (hereinafter also referred to as “component (A)”) is represented by the following general formula (1).

In formula (1), R ¹ is an alkyl group having 10 to 12 carbon atoms, R ² is an alkyl group having 1 to ² carbon atoms, and M ¹ is a cation capable of forming a water-soluble salt.

The alkyl group for R ¹ may be linear or branched.
The component (A) may be a mixture of plural kinds of α-sulfo fatty acid ester salts having different R ¹ and R ² . Component (A), a compound wherein R ¹ is a linear alkyl group of 10 carbon atoms, or, R ¹ is a compound 12 carbon atoms is a linear alkyl group of 10 carbon atoms linear Mixtures with compounds that are alkyl groups are preferred. (A) R ² of the component is preferably an alkyl group having 1 carbon atom.

M ¹ may be anything as long as the general formula (1) forms a water-soluble salt.
Specific examples of M ¹ include alkali metal cations such as sodium and potassium, alkaline earth metal cations such as calcium and magnesium, ammonium ions, and ethanolamine. The component (A) may be a mixture of a plurality of types of α-sulfo fatty acid ester salts having different M ¹ . M ¹ is preferably a sodium ion.

  Preferable specific examples of the component (A) include α-sulfolauric acid methyl ester salt and α-sulfomyristic acid methyl ester salt, and one or more kinds can be used. Examples of the mixture include α-sulfococonut oil fatty acid methyl ester salt.

  The content of the component (A) in 100% by mass of the cleaning agent is preferably 5 to 35% by mass and more preferably 10 to 25% by mass from the viewpoint of the cleaning power and foaming of the cleaning agent at a low temperature. When it is at least the lower limit of the above range, sufficient detergency and foaming are easily obtained, and when it is at most the upper limit, sufficient rinsing properties are easily obtained.

[(B) α-sulfo fatty acid di-salt]
The cleaning agent of the present invention contains (B) α-sulfo fatty acid di-salt (hereinafter also referred to as “component (B)”). The component (B) contributes to foaming at a low temperature, and particularly contributes to an improvement in rinsing properties and an improvement in aroma at a low temperature of the component (E) described later.
The component (B) is represented by the following general formula (2).

In Formula (2), R ³ is an alkyl group having 10 to 12 carbon atoms, and M ² and M ³ are cations that can independently form a water-soluble salt.
The alkyl group for R ³ may be linear or branched.
M ² and M ³ may be any ones as long as the general formula (2) forms a water-soluble salt. Specifically, alkali metal cations such as sodium and potassium, and alkaline earth metals such as calcium and magnesium A cation, an ammonium ion, ethanolamine, etc. are mentioned. M ² and M ³ may be the same or different. Both M ² and M ³ are preferably sodium ions.

  2-20 mass% is preferable and, as for content of (B) component in 100 mass% of cleaning agents, 5-10 mass% is more preferable. When it is in the above range, more excellent foaming at low temperature, rinsing properties, and later-described (E) component fragrance at low temperature can be easily obtained.

[Mass ratio of (A) / (B)]
The mass ratio ((A) / (B)) between the component (A) and the component (B) in the cleaning agent is 0.5 to 8, preferably 2 to 6. When the mass ratio is outside the above range, foaming at low temperatures becomes insufficient.

[(C) Semipolar surfactant]
The cleaning agent of the present invention contains (C) a semipolar surfactant (hereinafter also referred to as “component (C)”). (C) component has the effect | action which improves detergency and foaming.
Examples of the semipolar surfactant include a compound represented by the following general formula (3).

In formula (3), R ⁴ is an alkyl group having 12 to 14 carbon atoms, and R ⁵ and R ⁶ are each independently an alkyl group having 1 to 3 carbon atoms. R ⁴ , R ⁵ and R ⁶ may all be linear or branched.
The component (C) may be a mixture of a plurality of types of semipolar surfactants having different R ⁴ , R ⁵ and R ⁶ . R ⁵ and R ⁶ are preferably methyl groups. A preferred specific example of the component (C) is dimethyl lauryl amine oxide.

  3-10 mass% is preferable and, as for content of (C) component in 100 mass% of cleaning agents, 4-9 mass% is more preferable. When it is at least the lower limit of the above range, sufficient detergency and foaming at low temperatures can be easily obtained, and when it is at most the upper limit, sufficient rinsing properties at low temperatures can be easily obtained.

[Mass ratio of ((A) + (B)) / (C)]
The mass ratio ((A) + (B)) / (C) of the sum of the components (A) and (B) and the component (C) in the cleaning agent is 1 to 10, preferably 1 to 5. . When the mass ratio is less than the lower limit of the above range, foaming at low temperatures is reduced, and when it exceeds the upper limit, detergency at low temperatures is reduced. When the components (A) to (C) satisfy the mass ratio, a high detergency is exhibited by the interaction of these components.

[(D) Compound]
The cleaning agent of the present invention comprises a compound represented by the following general formula (4) and a compound represented by the following general formula (5) as the compound (D) (hereinafter also referred to as “component (D)”). Including at least one of them. In addition to improving foaming at low temperatures, the component (D) also acts as an agent for improving fragrance at low temperatures of the component (E) described below.

In formula (4), Z is a phenyl group, a benzyl group or an alkyl group having 4 to 6 carbon atoms. AO is an oxyalkylene group having 2 to 4 carbon atoms, m is a repeating number, and is 1 to 5.
Specific examples of the compound represented by the formula (4) include diethylene glycol monobutyl ether, phenoxyethanol, phenoxy-2-propanol, and benzyl diglycol, and diethylene glycol monobutyl ether is preferable.

In Formula (5), R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may be linear or branched, and R ⁸ is a hydrogen atom or a methyl group. X is, -COO ^- or _-SO ³ -, ^{M 4} is ^{H +,} an alkali metal ion or alkaline earth metal ions.
Specific examples of the compound represented by the formula (5) include metaxylenesulfonic acid, paratoluenesulfonic acid, cumenesulfonic acid, and benzoic acid, and paratoluenesulfonic acid and cumenesulfonic acid are preferable.

Among such components (D), the compound represented by the formula (4) is preferable. In particular, in addition to the improvement of foaming and rinsing properties at low temperatures, the later described component (E) has a fragrance at low temperatures. It is preferable to use diethylene glycol monobutyl ether from the point that the effect of improving becomes remarkable. Diethylene glycol monobutyl ether, the above general formula _(4), is _{Z = -C 4 H 9, AO} = CH 2 CH 2 O, the compounds of m = 2.

  0.1-7 mass% is preferable and, as for content of (D) component in 100 mass% of cleaning agents, 0.5-5 mass% is more preferable. If the mass ratio is less than the lower limit of the above range, foaming and fragrance tend to be reduced at low temperatures, and if it exceeds the upper limit, detergency at low temperatures tends to be reduced.

[Mass ratio of (B) / (D)]
The mass ratio ((B) / (D)) between the component (B) and the component (D) in the cleaning agent is a parameter that affects the low-temperature foaming and rinsing properties of the cleaning agent, and is 0.6. ˜30, preferably 1-15, and more preferably 1-4. When the mass ratio is less than the lower limit of the above range, foaming at low temperatures is reduced, and when it exceeds the upper limit, rinsing properties at low temperatures are reduced. When the mass ratio is within the range, the effect of achieving both foaming and rinsing properties at low temperatures can be sufficiently obtained.

[(E) Fragrance]
The cleaning agent of the present invention contains (E) a fragrance (hereinafter also referred to as “(E) component”). In general, a fragrance tends to have a lower fragrance when used at a low temperature (for example, 10 ° C.) than when used at a normal temperature (for example, 25 ° C.). Therefore, if the amount of the fragrance added to the cleaning agent is increased in order to improve the fragrance formation at a low temperature, the fragrance becomes too strong at room temperature. The present inventor blends the above-mentioned components (A) to (D) together with the fragrance that is the component (E), and particularly makes the components (D) and (E) have a specific ratio as described later. Thus, it was found that the scenting at low temperature can be improved and the difference from the scenting at normal temperature can be reduced. Thereby, even if it does not mix | blend many fragrance | flavors, fragrance standing at low temperature can be improved. Therefore, even when used at room temperature, the scent does not become too strong.

(E) As a fragrance | flavor of a component, well-known fragrance | flavors, such as a synthetic | combination fragrance | flavor and a natural fragrance | flavor from plants, can be used. 1969 MONTCLAIR, N.C. J. et al. Fragrances described in the publication “STEFEN Arctander” “Perfume and Flavor Chemicals” can be used. As natural fragrances, the fragrances described in “Scent Encyclopedia” edited by Japan Fragrance Association can be used.
Synthetic fragrances include hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons and aromatic hydrocarbons, alcohols such as aliphatic alcohols, terpene alcohols and aromatic alcohols, ethers such as aliphatic ethers and aromatic ethers , Oxides such as aliphatic oxides, terpene oxides, aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes, thioaldehydes, aldehydes such as aromatic aldehydes, aliphatic ketones, terpene ketones, hydrogenated aromatics Ketones, ketones such as aliphatic cyclic ketones, non-benzene aromatic ketones, aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, hydrogenated aromatic carboxylic acids, aromatics Acids such as aromatic carboxylic acids, acid amides, aliphatic lactones, large Lactic acid lactone, terpene lactone, hydrogenated aromatic lactone, lactone such as aromatic lactone, aliphatic ester, furan carboxylic acid ester, aliphatic cyclic carboxylic acid ester, cyclohexyl carboxylic acid ester, terpene carboxylic acid ester, Synthetic fragrances such as esters such as aromatic carboxylic acid esters, nitrogen-containing compounds such as nitromusks, nitriles, amines, pyridines, quinolines, pyrrole and indole.
(E) 1 or more types can be used for a component and 2 or more types are used together normally.
The content of the component (E) in 100% by mass of the cleaning agent is preferably from 0.1 to 1% by mass, and more preferably from 0.1 to 0.5% by mass, from the point of fragrance strength.

  In addition, the fragrance | flavor may be diluted with the solvent for fragrance | flavors previously. As a solvent for a fragrance, a solvent generally used for dilution of a fragrance can be used. For example, ethanol, acetin (triacetin), MMB acetate (3-methoxy-3-methylbutyl acetate), ethylene glycol dibutyrate, hexylene glycol , Dibutyl sebacate, deltile extra (isopropyl myristate), methyl carbitol (diethylene glycol monomethyl ether), carbitol (diethylene glycol monoethyl ether), TEG (triethylene glycol), benzyl benzoate, propylene glycol, diethyl phthalate, Tripropylene glycol, Aborin (dimethyl phthalate), Deltyl prime (isopropyl palmitate), Dipropylene glycol DPG-FC (Dipropylene glycol) ), Farnesene, dioctyl adipate, tributyrin (glyceryl tributanoate), hydrolite-5 (1,2-pentanediol), propylene glycol diacetate, cetyl acetate (hexadecyl acetate), ethyl abiate, avaline (methyl abiate) ), Citroflex A-2 (acetyltriethyl citrate), Citroflex A-4 (tributylacetyl citrate), Citroflex No. 2 (triethyl citrate), Citroflex No. 4 (tributyl citrate), Durafix (methyl dihydroabietate), MITD (isotridecyl myristate), polylimonene (limonene polymer), propylene glycol, 1,3-butylene glycol and the like can be used. Moreover, the above-mentioned (D) component can also be used as a fragrance | flavor solvent.

[Mass ratio of (D) / (E)]
The mass ratio ((D) / (E)) between the component (D) and the component (E) in the cleaning agent of the present invention is a parameter that affects the fragrance of the component (E). E) Even when the concentrations of the components are the same, the fragrance varies depending on the mass ratio ((D) / (E)). The mass ratio ((D) / (E)) in the cleaning agent of the present invention is 0.5 to 50, preferably 1 to 15, and more preferably 1 to 10. If the mass ratio is less than the lower limit of the above range, the scenting at low temperatures decreases, and if it exceeds the upper limit, the scenting at room temperature becomes too strong. As a result, the difference due to the temperature of fragrance increases. On the other hand, when the mass ratio is within the range, the strength of scenting at low temperature is improved, and the strength of scenting at normal temperature is approached. As a result, both the scenting at low temperatures and normal temperatures are good, and the difference due to the scenting temperature is reduced.

[Optional ingredients]
The cleaning agent of the present invention usually contains water as a dispersion medium in addition to the above components. Moreover, the component conventionally used for a liquid detergent can be contained as an arbitrary component in the range which does not impair the effect of this invention. Examples of optional components include various surfactants excluding the components (A) to (C), hydrotropes, metal ion scavengers, antioxidants, preservatives, coloring agents, emulsifying agents, natural product extracts, Examples include pH adjusters (sodium hydroxide, sulfuric acid, hydrochloric acid, glycolic acid, etc.).

  The pH of the cleaning agent of the present invention is not particularly limited, but 4 to 8 is preferable. Within this range, it is gentle against tableware, cooking utensils and hand skin.

[Production method]
The detergent of the present invention can be produced by a conventionally known method for producing a liquid detergent. For example, the manufacturing method which adds and stirs each component to the water which is a dispersion medium is mentioned.

As explained above, the cleaning agent of the present invention contains the components (A) to (E) at a specific ratio. Therefore, not only is it excellent in detergency, foaming, and rinsing properties at low temperatures, but it also has good fragrance at low temperatures and normal temperatures, and there is little difference due to the temperature of the fragrance.
In particular, the mass ratio ((B) / (D)) is important for the expression of foaming and rinsing properties at low temperatures of the cleaning agent, and the mass ratio ((D) / (E)) It is important in terms of improving the fragrance of time together.

Hereinafter, the present invention will be specifically described with reference to examples.
Each evaluation method in the examples is as follows.
[Evaluation method]
(1) Evaluation of detergency at low temperature 1 g of beef tallow (manufactured by Wako Pure Chemical Industries, Ltd.) colored with 1% by mass of Sudan IV (manufactured by Kanto Chemical Co., Ltd.) is 10 cm long × 15 cm wide × 5 cm high. It was applied uniformly on the entire inner surface of a plastic container (trade name: Neokeeper, manufactured by Iwasaki Kogyo Co., Ltd.) to make a hydrophobic surface stain model that was heavily soiled.
In a temperature-controlled room at 10 ° C, a dishwashing sponge (product name: Scotch Bright, manufactured by Sumitomo 3M) with a length of 11.5cm x width 7.5cm x height 3cm, 38g of tap water at 10 ° C and the cleaning agent of each example After taking 2 g each and rubbing by hand 10 times, rubbing the bottom surface of the plastic container 10 times, 10 times the side surface, 5 times each corner, and then rinsing with tap water at 10 ° C. According to the following evaluation criteria, the degree of oil stain removal on the inner surface of the plastic container was evaluated (4-step evaluation).
(Evaluation criteria)
A: There is no stain residue of colored beef tallow, and the plastic container is not null.
○: The colored beef tallow has no dirt residue, but the plastic container is slightly null.
Δ: Colored beef tallow remains and the plastic container is null.
X: There is considerable dirt residue of colored beef tallow.

(2) Evaluation of foaming at low temperature In a temperature-controlled room at 10 ° C, tap water at 10 ° C is placed on a dishwashing sponge (product name: Scotch Bright, manufactured by Sumitomo 3M) with a length of 11.5cm x width 7.5cm x height 3cm. 38 g and 2 g of each example of the cleaning agent were taken, and the foaming after the hand was rubbed five times was evaluated according to the following criteria.
(Evaluation criteria)
(Double-circle): Covers the range where the foam exceeded 80% of the surface area of the sponge.
○: Foam covers a range of more than 50% and less than 80% of the surface area of the sponge.
(Triangle | delta): Foam covers the range of 50% or less exceeding 30% of the surface area of sponge.
X: Foam covers a range of 30% or less of the surface area of the sponge.
XX: No bubbles at all.

(3) Rinsing evaluation at low temperature In a constant temperature room at 10 ° C, a dishwashing sponge (product name: Scotch Bright, manufactured by Sumitomo 3M) with a length of 11.5cm × width 7.5cm × height 3cm Take 38 g of water and 2 g of the cleaning agent in each example, rub it 5 times by hand, and then wash the circular ceramic dish (φ = 23 cm) while rubbing with a sponge. Rinse water adjusted to 10 ° C. at a flow rate of 100 ml / second, and rinse five dishes one by one. The time required for all of the null plates on the five plates to completely disappear was measured and evaluated as a rinse property.
(Evaluation criteria)
(Double-circle): Null luck disappears completely within 60 seconds.
○: Nullness disappears completely within 60 seconds to 80 seconds.
Δ: Nullness disappears completely within 80 seconds to 100 seconds.
X: It takes more than 100 seconds to completely eliminate null tack.

(4) Fragrance (i) Fragrance intensity In a temperature-controlled room at 25 ° C. and 10 ° C., a dishwashing sponge (product name: Scotch Bright, manufactured by Sumitomo 3M) having a length of 11.5 cm × width of 7.5 cm × height of 3 cm Next, after taking 38 g of tap water and 2 g of the cleaning agent of each example and squeezing it by hand five times, the evaluation of the strength of the scent by 30 female panelists in their 20s to 40s Evaluation based on the criteria. And the average value of the score was calculated in each of 25 degreeC and 10 degreeC.
The tap water and sponge were stored in a temperature-controlled room for over 1 hour, and it was confirmed that each temperature was the same as the temperature in the temperature-controlled room.
The breakdown according to the age of 30 evaluation panelists was 20 years: 10 people, 30s: 10 people, 40s: 10 people.
(Evaluation criteria)
Rating 5 points: The fragrance is too strong.
4 points: Slightly strong scent.
3 points: The fragrance is just right.
2 points: Slightly weak scent.
1 point: The fragrance is too weak.

  In addition, the fragrance intensity | strength intensity | strength in each temperature is 1.5 points or more and less than 2.5 points | pieces as an average value of a rating, or 3.5 points or more and less than 4.5 points | pieces are favorable, and 2.5 A value of ~ 3.5 points is particularly good. On the other hand, less than 1.5 points or 4.5 points or more is not good.

(Ii) Temperature difference in fragrance intensity (fragrance evaluation)
The difference between the average value at 25 ° C. calculated in (i) above and the average value at 10 ° C. was obtained (= average value at 25 ° C.−average value at 10 ° C.). The smaller the difference between the temperatures, the better.
(Evaluation criteria)
◎: Difference in fragrance is less than 0.5 point ○: Difference in fragrance is 0.5 or more and less than 1 point △: Difference in fragrance is 1 or more and less than 1.5 point ×: Difference in fragrance is 1. 5 points or more

[Examples 1 to 25, Comparative Examples 1 to 15]
According to the compounding composition shown in Tables 1-4, the cleaning agent (liquid cleaning composition) of each example was prepared with the manufacturing method shown below, respectively.
In addition, the unit of the compounding quantity in a table | surface is the mass%, and all components show the amount of pure content conversion. Moreover, the cleaning agent of each example adjusted (balanced) the compounding quantity of water so that the sum total of each component of Tables 1-4 might be 100 mass%. Each component used was kept at 50 ° C.

(Production method)
Components (A) to (E) were placed in a 200 mL beaker and stirred with a magnetic stirrer. Next, water was added and stirred so that the total amount (the total amount was 100 parts by mass) was 93 parts by mass. Thereafter, the pH was adjusted, and the remaining water was added and balanced so that the total amount became 100 parts by mass. To adjust the pH, glycolic acid and 0.1N aqueous sodium hydroxide solution were used as pH adjusting agents, and appropriate amounts thereof were added so that the pH at 25 ° C. of the cleaning agents in each example was 6.5. It was. Specifically, after adding a predetermined amount of glycolic acid, an aqueous sodium hydroxide solution was added so that the pH was 6.5 as described above.
The pH was measured by adjusting the cleaning agent to 25 ° C. and using a glass electrode type pH meter (product name: Horiba F-22, manufactured by Horiba, Ltd.). The measuring method was performed based on JIS K3362-1998.

The following components were used for the preparation of the cleaning agents in each example.
Component (A): α-sulfolauric acid methyl ester sodium salt (synthetic product)
The synthesis method will be described below.
1 kg (4.7 mol) of lauric acid methyl ester (Lion Corporation “Pastel M-12”) was placed in a reactor having a capacity of 3 L, and anhydrous sulfuric acid (Nisso Metal Chemical Co., Ltd. ”) 449 g (5.6 mol) was heated to gasify, and sulfonated by pouring with a nitrogen flow in an open system. The reaction temperature was 80 ° C., and the sulfuric acid anhydride feed rate was 10 g / min. Thereafter, an aging reaction was performed at 80 ° C. for 30 minutes to obtain α-sulfo fatty acid methyl ester (sulfonic acid). Methanol (Kanto Chemical Co., Ltd.) 20% by weight, based on the addition obtained acid (290 _g), 2 wt% of H 2 _{O 2} as a pure component (35 _wt% H 2 _{O 2} (Kanto Chemical ( After adding 83 g), esterification and bleaching were carried out by reacting at 80 ° C. for 60 minutes. The obtained bleaching acid was adjusted to pH 7.0 with an aqueous NaOH solution, and the reaction solvent was distilled off under reduced pressure. Since foaming occurred midway, water was distilled off while isopropanol was added and azeotroped. The residue was dissolved by heating at 60 ° C. with ethanol / water = 9/1 (v / v) to remove insoluble matters. The filtrate was cooled to 5 ° C. and recrystallized, and then the precipitate was separated by filtration and vacuum dried to obtain α-sulfolauric acid methyl ester sodium salt.

Component (B): α-sulfolauric acid disodium salt (synthetic product)
The synthesis method will be described below.
100 g (0.32 mol) of α-sulfolauric acid methyl ester sodium salt obtained above was put into a reactor having a capacity of 500 mL, 200 mL of 7 mass% NaOH aqueous solution (NaOH 14 g, 0.35 mol) was added, and 6 ° C. at 90 ° C. Reacted for hours. Thereafter, the mixture was allowed to stand at room temperature for 2 days, and the obtained crystals were separated by filtration, washed with MeOH, and vacuum-dried to obtain α-sulfolauric acid disodium salt.

(C) Component (C-1) N, N-dimethyllaurylamine oxide (“ALOMOX DM-12D-W” manufactured by Lion Akzo)

(D) Component (D-1): p-toluenesulfonic acid (“pTSH” manufactured by Kyowa Hakko Chemical Co., Ltd.)
(D-2): Cumene sulfonate Na (“Taikatox N5040” manufactured by Teika Co., Ltd.)
(D-3): m-xylene sulfonic acid (“Taikatox 110” manufactured by Teika Co., Ltd.)
(D-4): Diethylene glycol monobutyl ether (Kyowa Hakko Kogyo, butyl carbitol (90-5P))
(D-5): 2-phenoxyethanol (manufactured by Yokkaichi Synthesis Co., Ltd.)
(D-6): benzyl diglycol (manufactured by Nippon Emulsifier)

(D ') component (comparative substance)
(D′-1): 1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd.)
(D'-2): Diethylene glycol monoethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
(D′-3): Diethylene glycol 2-ethylhexyl ether (“BLUAUNON EH-2” manufactured by Aoki Yushi Co., Ltd.)

(E) component: Fragrance | flavor The fragrance | flavor A and the fragrance | flavor B of the composition shown in Tables 5-14 were used as a fragrance | flavor. In the table, perfume A is (E-1) and perfume B is (E-2). Both fragrance | flavor A and fragrance | flavor B will be 100 mass%, if the content of each component shown to Tables 5-14 is added together. Moreover, all the components described in these tables are fragrance | flavors, and the solvent for fragrance | flavors is not contained in these.

(Other ingredients)
Glycolic acid: DuPont's trade name “Grip Pure 70”.
Sodium hydroxide: Sodium hydroxide, manufactured by Tsurumi Soda Co., Ltd.
Water: tap water

The cleaning agents of each Example described in Tables 1 and 2 were superior in cleaning power, foaming and rinsing properties at low temperatures as compared with the cleaning agents of Comparative Examples described in Tables 3 and 4. The fragrance was good both at low temperature and at normal temperature, and there was little difference depending on the temperature of the degree of fragrance.
For example, from the results of Examples 5 to 10, etc.
(I) The mass ratio ((D) / (E)) affects the fragrance, and if the mass ratio is in a more appropriate range, both the fragrance at low temperature and normal temperature are excellent, and these differences are Very little.
(Ii) The mass ratio ((B) / (D)) affects the foaming and rinsing properties of the cleaning agent at a low temperature. When the mass ratio is in a more appropriate range, the foaming and rinsing properties at a low temperature are affected. Sufficient effects can be obtained.
I understood.
In addition, from the results of Examples 20 to 25, particularly when diethylene glycol monobutyl ether is used as the component (D), the detergency at low temperatures, foaming, rinsing properties, and fragrance at both low and normal temperatures are well balanced. I understood that it was excellent.

Claims (2)

(A) an α-sulfo fatty acid ester salt represented by the following general formula (1);
(B) an α-sulfo fatty acid di-salt represented by the following general formula (2);
(C) a semipolar surfactant represented by the following general formula (3);
(D) at least one of a compound represented by the following general formula (4) and a compound represented by the following general formula (5);
(E) containing a fragrance,
The mass ratio represented by (A) / (B) is 0.5 to 8,
The mass ratio represented by (B) / (D) is 0.6-30,
The mass ratio represented by ((A) + (B)) / (C) is 1 to 10,
The dishwashing detergent characterized by mass ratio represented by (D) / (E) being 0.5-50.

(In formula (1), R ¹ is an alkyl group having 10 to 12 carbon atoms, R ² is an alkyl group having 1 to ² carbon atoms, and M ¹ is a cation capable of forming a water-soluble salt.)

(In formula (2), R ³ is an alkyl group having 10 to 12 carbon atoms, and M ² and M ³ are each a cation capable of independently forming a water-soluble salt.)

(In Formula (3), R ⁴ is an alkyl group having 12 to 14 carbon atoms, and R ⁵ and R ⁶ are each independently an alkyl group having 1 to 3 carbon atoms.)

(In Formula (4), Z is a phenyl group, a benzyl group, or a C4-C6 alkyl group. AO is a C2-C4 oxyalkylene group, and m is 1-5.)

(In Formula (5), R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, R ⁸ is a hydrogen atom or a methyl group, X is —COO ^— or —SO ₃ ^— , and M ⁴ is H. ⁺ , An alkali metal ion or an alkaline earth metal ion.   The dishwashing detergent according to claim 1, wherein the component (D) is diethylene glycol monobutyl ether.