JP2000160190A - Low foamable detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a low foamable detergent capable of exhibiting an excellent washing effect and a good biodegrading property and low in fish toxicity by adding a specific (poly)glycerol monoalkyl ether. SOLUTION: This low foamable detergent contains a (poly)glycerol monoalkyl ether of the formula [R1 is a 1-24C alkyl, a 1-24C alkenyl or a 3-8C cycloalkyl; and (n) is 1-4]. The glycerol monoalkyl ether can be obtained, for example, by hydrolyzing an alkyl glycidyl ether in the presence of an acid or alkali catalyst. The diglycerol monoalkyl ether can also be obtained by opening the ring of the alkyl glycidyl ether with glycerol, and the tridiglycerol monoalkyl ether can also be obtained by opening the ring of the alkyl glycidyl ether with diglycerol. The content of the ether compound of the formula in the detergent is preferably 0.01-10 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-foaming detergent which is suitably used in a cleaning step requiring low-foaming.

[0002]

2. Description of the Related Art For cleaning of hard surfaces used for home or industry such as washing dishes, washing cans and bottles, washing glass, etc., when there is foaming, a low-foaming detergent is used. There are places that are required. Examples of the low-bubble detergent include a copolymer of ethylene oxide and propylene oxide or an alkylene oxide adduct obtained by adding ethylene oxide to an aliphatic alcohol and then further adding propylene oxide or butylene oxide or a methyl etherified product thereof. Things are known. However, these compounds contain an oxypropylene group or an oxybutylene group, which is a unit having poor biodegradability and fish toxicity, and have insufficient biodegradability and fish toxicity.

Further, West German Patent No. 3,315,951 discloses that polyethylene glycol dialkyl ether exhibits sufficient biodegradability, and has high detergency and low foamability. However, when the terminal alkyl group or alkenyl group of the polyethylene glycol dialkyl ether has a low carbon number (for example, 4 carbon atoms), it does not sufficiently satisfy both the low foaming property and the wettability and emulsifying property required for the washing step. Those having high carbon number (for example, carbon number 8) have high detergency and low foaming property, but are difficult to be economically manufactured because they are manufactured using higher alkyl halides. Coloring problems occur in the resulting product.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a low-foaming material, excellent cleaning effect, good biodegradability, low fish toxicity,
Another object of the present invention is to provide a low-foaming detergent which can be produced by an economical production method.

[0005]

The present invention relates to a compound represented by the general formula (I) R ^1- (OCH ₂ -CHOH-CH ₂ ) _n -OH (I) wherein R ¹ is a straight-chain having 1 to 24 carbon atoms. A glycerin monoalkyl ether or polyglycerin monoalkyl ether represented by a chain or branched alkyl group or alkenyl group, or a cycloalkyl group having 3 to 8 carbon atoms, and n represents a number of 1 to 4) A low-foaming detergent containing an ether compound (I) is provided below.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the ether compound (I) of the present invention, R ¹ is a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms. Having 6 or more carbon atoms of a straight or branched chain
An alkyl group of 18 is preferable, and an alkyl group having 8 to 12 carbon atoms is particularly preferable. Specifically, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group,
Linear alkyl groups such as dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylhexyl, 2-ethylhexyl,
Examples include a branched-chain alkyl group such as a methylheptyl group, a 2-methylnonyl group, a 2-octyldecyl group, a 3,5,5-trimethylhexyl group, an isostearyl group, and an alkenyl group such as an oleyl group. N is 1 to 4, and 1 or 2
Is particularly preferable, and 1 is particularly preferable.

The ether compound (I) of the present invention can be produced, for example, according to the following reaction scheme.

[0008]

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(Wherein, R ¹ has the same meaning as described above.) Glycerin monoalkyl ether (I-1) can be obtained by hydrolyzing alkyl glycidyl ether (II). In addition, diglycerin monoalkyl ether (I-2) is opened by opening the alkyl glycidyl ether (II) with glycerin, and triglycerin monoalkyl ether (I-3) is opened by opening the ring with diglycerin. Obtainable. The ring opening reaction of the alkyl glycidyl ether (II) is performed in the presence of an acid catalyst or an alkali catalyst.

The alkyl glycidyl ether (II) can be prepared by a known method. For example, it is obtained by reacting an alcohol represented by the formula (III) R ¹ -OH (III) (wherein R ¹ has the above-mentioned meaning) with epichlorohydrin in the presence of an alkali catalyst and a phase transfer catalyst. The chlorohydrin compound can be obtained using a mineral acid such as sulfuric acid or a Lewis acid catalyst such as BF ₃ O (CH ₂ CH ₃ ) ₂ and then closed with an alkali to obtain the alkyl glycidyl ether (II). it can.

The ether compound (I) can be directly obtained by reacting the alcohol (III) with glycerin at a high temperature in the presence of an acid or alkali catalyst. In this case, a glycerin having a degree of condensation of 5 or more may be obtained.
A polyglycerin monoalkyl ether having a degree of condensation of 5 or more may be contained. However, from the viewpoint of performance, the degree of condensation of glycerin is preferably small.

The low-foaming detergent of the present invention containing the ether compound (I) is low-foaming, has excellent wettability and emulsifying properties required for the washing step, has good biodegradability, and has good biodegradability. Low toxicity. The content of the ether compound (I) in the low-foaming detergent of the present invention is preferably 0.01 to 10% by weight, and 0.1 to 5% by weight.
% By weight is more preferred.

[0013] The low-foaming detergent of the present invention contains, in addition to the ether compound (I), components usually used in detergents, such as wetting agents, builders, complexing agents, alkalis, acids, preservatives, antimicrobial agents, and organic solvents. And the like. Examples of the humectant include nonionic surfactants such as aliphatic alcohols, alkylphenols, aliphatic amines or fatty acid amides and ethylene oxide adducts thereof, and alkali metal salts of acids such as fatty acids, alkyl sulfates, alkyl sulfonic acids and alkyl benzene sulfonic acids. And an anionic activator such as an amine salt or an alkylolamine salt.

The builders and complexing agents include alkali metal orthophosphates, polymer phosphates,
Examples include silicate, borate, carbonate, polyacrylate, gluconate, citric acid, ethylenediaminetetraacetic acid and the like. The content of the builder and the complexing agent is 1 to
It is preferably 50% by weight, more preferably 2 to 40% by weight.

Examples of the alkali include sodium hydroxide, sodium carbonate, sodium hydrogen carbonate and the like. The alkali content is preferably from 10 to 70% by weight, more preferably from 20 to 50% by weight.

The low-foaming detergent of the present invention is low-foaming and excellent in detergency, and can be used for washing with an automatic dishwasher, cans and bottles, and the like.
It is particularly useful as a cleaning agent requiring low foaming properties such as glass cleaning.

[0017]

EXAMPLES In the examples,% is% by weight unless otherwise specified.

Examples 1 to 4 and Comparative Examples 1 to 3 For the ether compounds of the present invention and comparative ether compounds shown in Table 1, low foamability, wettability, emulsifiability,
Biodegradability and fish toxicity were evaluated. Table 1 shows the results.

<Low-foaming property> A 0.1% aqueous solution of various ether compounds was prepared and subjected to the JIS synthetic detergent test method (JIS K3362).
6.5 The foam amount was measured by the method described in 6.5 Foaming power and foam stability. However, the measurement of the foam height was performed after 1 minute instead of 5 minutes. If the foam height after 1 minute is less than 3 cm, ○ 3 cm
The above was evaluated as x.

<Wetability> A 200 mL beaker was used to prepare 150 mL of a 0.1% aqueous solution of various ether compounds, a 2 cm × 2 cm felt was dropped, and the time until the felt began to sink was measured. A sample of less than 5 seconds was rated as ○, a sample of 5 seconds or more and less than 10 seconds was rated as Δ, and a sample of 10 seconds or longer was rated as ×.

<Emulsifying Property> 8 mL of olive oil, 11 mL of water and 1 mL of an ether compound were placed in a test tube having a diameter of 1.5 cm and a length of 17.5 cm, and allowed to soak for 2 minutes. Then, the emulsification ratio after 10 minutes was measured. And the ratio is shown. ○: emulsification rate of 80% or more, Δ: less than 80%, 60% or more, ×: less than 60%
And

<Biodegradability> The biodegradability was measured by the method under the Chemical Substances Control Law except that 30 ppm of sludge from a sewage treatment plant and 30 ppm of an ether compound were used. If the BOD is more than 80% on day 28,
% And less than 60% were rated as △, and less than 60% were rated as x. <Fish toxicity> 71. of JIS factory drainage test method (JIS K 0102)
According to the method described in the acute toxicity test with fish, LC50 of 96 hours was measured using 8 medaka in each aquarium. 30
Those with mg / L or more were rated as 、, those with less than 30 mg / L and 5 mg / L were rated as Δ, and those with less than 5 mg / L were rated as x.

[0023]

[Table 1]

Example 5 and Comparative Examples 4 to 6 Using the ether compound of the present invention and the comparative ether compound shown in Table 2, a low-foaming detergent for powdery dishwashing was prepared by mechanically mixing the following components. Prepared. The detergency of the obtained low-bubble detergent was evaluated by the following method. Table 2 shows the results.

<Composition of low-foaming detergent> Ether compound 1% Sodium hydroxide 40% Sodium tripolyphosphate 20% Sodium sulfate 39% The above-prepared powdery detergent is put into a cartridge container for supplying detergent. And an automatic dishwasher DW-230L manufactured by Sanyo Electric Co., Ltd. A cleaning agent was supplied from this supply machine, and a cleaning test was performed under the following conditions, and the cleaning performance was evaluated based on the following criteria.

<Test conditions> Washing temperature: 80 ± 2 ° C. Washing time: 45 seconds Detergent concentration: 0.15% Rinsing time: 15 seconds Rinsing temperature: 80 ± 2 ° C. Washing object: Diameter stained by dipping in commercial salad oil 20 dishes of 20 cm ceramic dishes <Washability> The remaining spots of salad oil are visually judged and
The average of the sheets was evaluated according to the following criteria. ：: 0 to 5 spots per dish Δ: 6 to 19 spots per dish ×: 20 or more spots per dish

[0027]

[Table 2]

[0028]

The low-foaming detergent of the present invention has a sufficiently low foaming property, is excellent in wettability and emulsifying properties, and has a biodegradability of B.
OD: 80% or more, good biodegradability, fish toxicity evaluated by the above method is 30 mg / L or more, low fish toxicity, and excellent cleaning effect.

Claims (1)

[Claims] 1. A compound of the general formula (I) R ^1- (OCH ₂ -CHOH-CH ₂ ) _n -OH (I) wherein R ¹ is a linear or branched alkyl group having 1 to 24 carbon atoms or A low-foaming detergent containing a glycerin monoalkyl ether or a polyglycerin monoalkyl ether represented by an alkenyl group or a cycloalkyl group having 3 to 8 carbon atoms, and n represents a number of 1 to 4.