JP2660590B2 - Detergent composition for automatic dishwashers - Google Patents

Description

The present invention relates to a detergent composition for an automatic dishwasher, and more particularly, to a low-foaming, excellent detergency against oil stains and an oil at the time of cleaning. The present invention relates to a detergent composition for an automatic dishwashing machine, which has an effect of preventing tableware and the inside of the dishwasher from being recontaminated by dirt.

[Conventional technology and its problems]

BACKGROUND ART In recent years, automatic dishwashers have rapidly spread, and have been actively used not only for business purposes but also for general households. At present, automatic dishwashers are of a type in which a heated detergent solution is sprayed onto dishes to wash the dishes, and the detergent solution is circulated for use. When the detergent is used, there has been a problem that the detergent solution overflows from the washing tank due to remarkable foaming, or the pump runs idle, so that the pump operation of the washing machine itself becomes impossible.

In the case of an automatic dishwasher of the type described above, since the detergent aqueous solution and the rinsing water are circulated and used, if oil stains adhere to the washing machine in the washing process, the rinse water is contaminated by the oil stains, and the rinse water is further contaminated. There is a problem in that the oil stains re-adhere to the dishes and the washing machine. Further, if oil stains remain in the washing machine, leaving them unattended may cause a bad smell, which is not preferable in terms of hygiene. In order to solve such a problem, a rinsing aid is added in the rinsing step,
Means such as regularly performing empty cleaning are taken. However, the addition of the rinsing aid has a safety problem because the components of the rinsing aid remain on the tableware after washing.In the case of empty washing, it is effective for removing accumulated dirt by long-term use, It cannot be a means of resolving the contamination of the washing machine in the washing.

From the above circumstances, the detergent composition for an automatic dishwasher satisfies the low performance and high detergency, which are the basic performances, and in the washing process, the dishes and the inside of the washer are contaminated with oil stains. There has been a strong demand for a detergent composition that has the effect of preventing the occurrence of water.

[Means for solving the problem]

Under such circumstances, the present inventors have developed a cleaning agent for an automatic dishwashing machine which has low foaming property and high washing power, and does not contaminate dishes and the inside of the washing machine with oil stains in the washing process. As a result of intensive studies, they have found that a desired detergent composition can be obtained by using an amine oxide and a specific polyoxyalkylene derivative in combination, and completed the present invention.

That is, the present invention provides the following components (a) and (b) (a) (Wherein, R ₁ represents an alkyl or alkenyl group having 6 to 18 carbon atoms, R ₂ represents an alkyl or alkenyl group having 1 to 18 carbon atoms, provided that the sum of the carbon atoms of R ₁ and R ₂ is 16 That's it, R ₃
-CH ₂ CH ₂ -O is _{-, - CH 2 CH 2 CH} 2 -O- and -CH ₂ CH (CH
One or two or more groups selected from ₃₎ -O- represents those bonded 0-20 pieces in any combination, R ₄ is 1 to carbon atoms
An alkyl or hydroxyalkyl group, a benzyl group or a hydrogen atom of (b) (b) an alkylene oxide adduct of a monohydric alcohol, an alkylphenol or a monovalent mercaptan (hereinafter referred to as "compound A"); A polyoxyalkylene derivative obtained by reacting a diepoxide compound, wherein the weight ratio of the component (a) to the component (b) (a) /
(B) 0.1 to 10 is provided, it is providing the detergent composition for automatic dishwashers.

The amine oxide of the component (a) used in the present invention is an amine oxide represented by the general formula (I), and has an effect of preventing oil stains from re-adhering. Formula (I)
In the formula, R ₁ and R ₂ have 6 to 18 and 1 to 18, respectively, and preferably 8 to 12 and 1 to 12, respectively. Also
The sum of the carbon numbers of R ₁ and R ₂ is 12 or more, but if it is less than 12, the effect of preventing re-adhesion is weak, and if the carbon number of either R ₁ or R ₂ exceeds 18, it is water-soluble. Is significantly reduced and the detergency decreases, which is not preferable. R ₃ is -CH ₂ CH ₂ -O-,
One or two or more groups selected from —CH ₂ CH ₂ CH ₂ —O— and —CH ₂ CH (CH ₃ ) —O— are bonded to each other in an optional combination. If it exceeds, the effect of preventing re-adhesion decreases, which is not preferable.

Although the component (a) has the effect of preventing oil stains from re-adhering as described above, the use of the component (a) alone is not preferable because of its high foaming property, which impairs the operation of an automatic dishwasher. .

The polyoxyalkylene derivative of the component (b) itself has good detergency as a detergent component, but when used in combination with the amine oxide of the component (a), exhibits a remarkable foam-suppressing effect. Suppresses foaming and removes adverse effects on the washing machine. For this reason, very good detergency is exhibited in combination with the effect of preventing the re-adhesion of oil stains of amine oxide.

Examples of the compound A, which is a raw material of the polyoxyalkylene derivative as the component (b) in the present invention, include compounds represented by the following general formulas (II) to (IV).

R ₅ —O—R ₆ H (II) wherein R ₅ represents an alkyl or alkenyl group having 10 to 24 carbon atoms, and R ₆ represents —CH ₂ CH ₂ —O—, —CH ₂ CH ₂ CH ₂ -O- and -CH ₂ CH (CH ₃₎ one or more groups selected from -O- indicates those bonded average of 20 or more in any combination] [Wherein, R ₇ represents an alkyl or alkenyl group having 4 to 18 carbon atoms, and R ₆ represents the same as above] R ₅ -S-R ₆ -H (IV) [wherein R ₅ and R ₆ represents the same as above. Compound A is a random or block addition of a monohydric alcohol, an alkylphenol or a monohydric mercaptan, alone or in a mixture of ethylene oxide and propylene oxide, in the presence of an alkali catalyst, in a conventional manner. Manufactured by running.

The total carbon number of the monohydric alcohol, alkylphenol or monohydric mercaptan is preferably from 10 to 24, particularly preferably from 12 to 18. When the total number of carbon atoms is less than 10, not only is the synthesized component (b) foamable, but also the foaming effect of the component (a) is reduced. b) the solubility of the components in water is reduced,
If the cleaning power of the entire cleaning composition is impaired, or if the cleaning composition is in a liquid form, the stability of the solution deteriorates, which is not preferable.

R ₆ of these compounds A is —CH ₂ CH ₂ —O—, —CH ₂ C
One or two or more groups selected from H ₂ CH ₂ —O— and —CH ₂ CH (CH ₃ ) —O— are bonded in an arbitrary combination on average of 20 or more. Number is 100-2
00 range.

Compound A can be used alone or as a mixture of two or more kinds as the raw material of component (b).

Examples of the diepoxide compound as the other raw material of the component (b) include the following (1) to (10).

(1) β, γ-epoxypropyl ether (2) 1,2-bis (β, γ-epoxypropoxy) ethane (3) 1,3-bis (β, γ-epoxypropoxy) propane (4) 1,4-bis (β, γ-epoxypropoxy) butane (5) 1,2-bis (β-ethyl-β, γ-epoxypropoxy) ethane (6) 1,2-bis (α, β-epoxy-γ-methoxypropyl) ethane (7) 1.6-bis (epoxyethyl) hexane (8) 1,4-bis (β, γ-epoxypropoxy) benzene (9) 2,2-bis [p- (β, γ-epoxypropoxy) phenyl] propane (10) 1-epoxyethyl-3,4-epoxycyclohexane (common name: vinylcyclohexene diepoxide) The diepoxide compounds can be used alone or in combination of two or more.

When the compound A and the diepoxide compound are reacted in the presence of an alkali catalyst, a polyoxyalkylene derivative as the component (b) is obtained. The reaction ratio between the compound A and the diepoxide compound is appropriately selected depending on the molecular weight of the compound A to be added and the type of the diepoxide compound. Generally, 0.5 to 5 equivalents of the diepoxide compound is added to 1 equivalent of the hydroxyl group of the compound A. Is appropriate. The reaction temperature is 50-200 ° C, especially 100-150 ° C, and the reaction time is 10 minutes-1.
0 hours, especially 30 minutes to 3 hours, is preferred. In this case, the reaction proceeds easily, and the viscosity of the aqueous solution gradually increases as the reaction proceeds, and finally the viscosity reaches a maximum. This point is defined as the end point of the reaction.

The weight ratio (a) / (b) of the component (a) and the component (b) is 0.
When (a) / (b) is less than 0.1, the effect of preventing oil stains from re-adhering is insufficient, and when (a) / (b) exceeds 10, foamability is increased due to component (a). It is undesirably high.

The cleaning composition of the present invention can be in any form of liquid, powder, or solid state, but is preferably liquid or powder from the viewpoint of ease of use.

Further, the cleaning composition of the present invention, in addition to the above essential components,
Known additives can be added as needed as long as the desired performance is not impaired. Examples of such additives include non-ionic surfactants such as polyoxyalkylene alkyl ethers and polyoxyethylene-polyoxypropylene block polymers; amylase, protease,
Enzymes such as cellulase and lipase; alkaline agents such as sodium hydroxide, potassium hydroxide, sodium metasilicate, sodium tripolyphosphate, sodium pyrophosphate, sodium carbonate, sodium hydrogencarbonate; ethylenediaminetetraacetate, gluconate, nitrilotriacetate , Polyacrylates, polymaleates, citrates and other chelating agents; polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose and other anti-soiling agents; ethanol, propylene glycol, glycerin and other hydrotropes; Pigment,
Preservatives, fungicides and the like can be mentioned.

When the detergent composition of the present invention is actually used for washing dishes, the total amount of the components (a) and (b) is 0.005% by weight.
It is preferable to dilute with water so as to have a concentration of (abbreviated simply as%) or more in order to obtain a good detergency.

〔Example〕

Hereinafter, the present invention will be further described with reference to Synthesis Examples and Examples of the polyoxyalkylene derivative as the component (b), but the present invention is not limited thereto.

Synthesis Examples 1 to 7 Synthesis of component (b): A predetermined equivalent ratio of a diepoxide compound was added to compound A as shown in Table 1, and the mixture was stirred at 150 ° C. for about 3 hours to react to obtain a polyoxyalkylene derivative. Was. In the reaction, the viscosity of a 10% aqueous solution of the reaction product at 40 ° C. was measured, and the end point was determined when the viscosity no longer increased.

In each of the synthesis examples, a combination of the compound A and the diepoxide compound shown in Table 1 below was synthesized at the equivalent ratio shown in Table 1.

Example 1 A liquid detergent composition for an automatic dishwasher having the composition shown in Table 2 below was prepared and tested for its detergency, low-foaming property and re-adhesion property by the following test methods.

 Table 2 shows the results.

Detergency test method Tallow (Japanese Pharmacopoeia) is melted in a warm bath at 80 ° C and the diameter is 25cm.
5 g was applied to a magnetic white dish, and then left in a constant temperature room at 25 ° C. for 24 hours to coagulate tallow. A set of four contaminated dishes prepared in this manner was subjected to washing. The washing conditions and evaluation method are as follows.

Cleaning conditions Model used: Fully automatic dishwasher manufactured by Matsushita Electric Co., Ltd. (Model name: NP-600) Cleaning temperature: The cleaning start temperature is 5 ° C, which is gradually heated in the cleaning process and eventually rises to 55 ° C. I do.

Water used: Hard water with a hardness of 3.5 ゜ DH Detergent concentration: 5 g of detergent composition used (concentration: about 0.2%) Washing time: 20 minutes for washing → 20 minutes for rinsing Amount of circulating water for washing: about 2.5 Evaluation method After washing The number of oil reds was applied to the dish, the reaction area (S ₁ ) on the dish was measured by photographic judgment, and the washing rate was determined from the initial reaction area (S ₀ ) by the following equation.

The average cleaning rate of the four dishes determined by the above equation was indicated by the following criteria.

○ 100% Completely washed △ 80-90% Partially soiled × Less than 80% Not washed Low-foaming test method Put 5 g of detergent into a clean washing machine and test for cleaning power Cleaning conditions similar to the method (detergent concentration 0.2% during cleaning)
To start driving. 1 minute, 5 minutes, 10 minutes, 15 minutes, 20 minutes after start
The number of revolutions of the spray arm nozzles of the washer after a minute was visually measured to evaluate whether or not the number of revolutions (mechanical force) of the nozzle of the washer decreased due to foaming.

 The evaluation at this time was performed as follows.

_{(R 1, R 5, R} 10, R 15, R 20 after the start of operation, respectively 1
Minutes, 5 minutes, 10 minutes, 15 minutes and 20 minutes are shown.

 The criteria are as follows.

○ R ≧ 38: There is little foaming and mechanical force works sufficiently.

Δ38> R ≧ 30: foaming, and the mechanical power is slightly lowered. × R <30: foaming is remarkable, and little mechanical force acts.

Reattachment test 1 ml of 80% aqueous detergent composition (0.2%, 60 ° C, 35 ° DH)
Take in a 00 ml beaker and add 0.8 tallow. Stir with a constant mechanical force for 4.5 minutes to melt and disperse the beef tallow. Stir for 30 seconds after stopping the stirring, and use a stainless steel test piece (7.5 cm
× 2.5 cm) for 5 seconds. Test piece 60 after immersion
Rinse in 3.5 ° DH, 3.5 ° DH water for 10 seconds and dry in 105 ° C electric drying for 2 hours. From the weight change of the test piece before and after the test, the amount of tallow adhering was determined and evaluated according to the following criteria.

○ Adhesion amount less than 5 mg: low re-adhesiveness △ Adhesion amount of 5 mg or more and less than 20 mg: slight re-adhesion is observed × Adhesion amount of 20 mg or more: remarkable re-adhesion is observed.

Example 2 A detergent composition having the following composition was prepared, and a detergency test, a low-bubble test, and a re-adhesion test were performed in the same manner as in Example 1. The results are shown in Table 3.

Example 3 A detergent composition having the following composition was prepared, and a detergency test, a low-bubble test, and a re-adhesion test were performed in the same manner as in Example 1. The results are shown in Table 4.

Claims (3)

(57) [Claims] 1. The following components (a) and (b): (a) the following general formula (I) (Wherein, R ₁ represents an alkyl or alkenyl group having 6 to 18 carbon atoms, R ₂ represents an alkyl or alkenyl group having 1 to 18 carbon atoms, provided that the sum of the carbon atoms of R ₁ and R ₂ is 16 That's it, R ₃
-CH ₂ CH ₂ -O is _{-, - CH 2 CH 2 CH} 2 -O- and -CH ₂ CH (CH
One or two or more groups selected from ₃₎ -O- represents those bonded 0-20 pieces in any combination, R ₄ is 1 to carbon atoms
(B) an alkyl or hydroxyalkyl group, a benzyl group or a hydrogen atom) (b) a polyhydric alcohol, an alkylphenol or an alkylene oxide adduct of a monohydric mercaptan with a diepoxide compound, An oxyalkylene derivative, and the weight ratio of the component (a) to the component (b) (a) /
(B) 0.1 to 10 is a detergent composition for automatic dishwashers. 2. An alkylene oxide adduct of a monohydric alcohol, alkylphenol or monohydric mercaptan is represented by the following general formulas (II) to (IV): R ₅ —O—R ₆ H (II) wherein R ₅ is Represents an alkyl or alkenyl group having 10 to 24 carbon atoms, and R ₆ is selected from —CH ₂ CH ₂ —O—, —CH ₂ CH ₂ CH ₂ —O— and —CH ₂ CH (CH ₃ ) —O— One or two or more groups combined with an average of 20 or more in any combination.) (Wherein, R ₇ represents an alkyl or alkenyl group having 4 to 18 carbon atoms, and R ₆ represents the same as above.) R ₅ -S-R ₆ -H (IV) (wherein R ₅ and R _The cleaning composition for an automatic dishwasher according to claim 1, wherein the cleaning composition is one or a mixture of two or more selected from the group consisting of: 3. The method of claim 1, wherein the diepoxide compound is β, γ-epoxypropyl ether, 1,2-bis (β, γ-epoxypropoxy) ethane, 1,3-bis (β, γ-epoxypropoxy) propane, Bis (β, γ-epoxypropoxy) butane, 1,2-bis (β-methyl-β, γ-epoxypropoxy) ethane, 1,2-bis (α, β-epoxy-γ-methoxypropyl) ethane, 1 1,6-bis (epoxyethyl) hexane, 1,4-bis (β, γ-epoxypropoxy) benzene, 2,2-bis [p- (β, γ-epoxypropoxy) phenyl] propane, 1-epoxyethyl 3. The composition according to claim 1, which is one or a mixture of two or more kinds selected from the group consisting of 3,4-epoxycyclohexane.
The cleaning composition for an automatic dishwasher according to the above.