JPS593514B2 - Low foaming cleaning agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention comprises at least one fatty acid of polyoxyethylene ether or fatty acid of polyoxyethylene/polyoxypropylene ether and their salts, and has particularly good product decomposition, and usually The present invention relates to a low-foaming cleaning agent with excellent cleaning properties that can be easily removed even through wastewater treatment.

Conventionally, cleaning agents generally include anionic surfactants such as alkylbenzene sulfonates, alkyl sulfates, alkyl sulfonates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl allyl sulfates, polyoxyethylene alkyl ethers, polyoxyethylene 5-alkyl sulfates, etc. Nonionic surfactants such as phenyl ether and polyoxyethylene alkylamine are used.

Both of these anionic and nonionic surfactants have excellent cleaning effects, but they are all characterized by extremely good foaming properties.

In recent years, there has been a desire to speed up work processes to improve productivity, and as a result, foaming is extremely low, and at the same time, it can be easily removed after use through normal primary wastewater treatment such as pressurized flotation or coagulation and sedimentation. 15 There is a strong demand for cleaning agents with good biodegradability.

Pluronic-type activators and fatty acid soaps are examples of products that simply produce less foam, but pluronic-type activators can hardly be removed in the primary wastewater treatment, and soaps cannot be removed in the primary wastewater treatment. Although it can remove almost 100% of the fluoride during primary wastewater treatment and produces less foaming, it may not be as effective as other nonionic activators for stains that are difficult to remove, or it may generate gas and cause stains to re-adhere. It has some drawbacks. Like this,
Each of them has advantages and disadvantages, and it is important to obtain a detergent that has excellent cleaning effects, good biodegradability, and at the same time satisfies the requirements of a low-foaming detergent that can be removed extremely easily in normal primary wastewater treatment. Have difficulty. In view of the current situation, the present inventors have found that the present invention has excellent cleaning effects and good biodegradability, and that it can be removed extremely easily by the primary treatment of wastewater using the usual pressure flotation method or coagulation sedimentation method. Furthermore, as a result of extensive research into a cleaning composition with extremely low foaming properties, the present invention was arrived at. In the present invention, ethylene oxide or ethylene oxide 35 is added to hydroxy fatty acid ester having 8 or more carbon atoms.
At least one type of fatty acid of polyoxyethylene ether or fatty acid of polyoxyethylene polyoxy-propylene ether obtained by addition reaction of 5 to 100 moles of polyoxyethylene oxide and propylene oxide, and then hydrolyzed with an acid or alkali. It is a low-foaming cleaning agent characterized by containing: In the present invention, carbon number 8
The above esters of hydroxy fatty acids (hereinafter referred to as specified fatty acids) are esters of specified fatty acids and lower alcohols, polyhydric alcohols, or alkylene glycols, and in practical terms, castor oil fatty acids and glycerin, and 12-hydroxy fatty acids and ethyl Alcohol is easy to use ~ The specified fatty acids include 2,10-dioxytridecanoic acid, 3,11-dioxytetradecanoic acid, 11-dioxypentadecanoic acid, 2,15-dioxypentadecanoic acid,
11-oxyhexadecanoic acid, 15,16-dioxyhexadecanoic acid, 2,15,16-trioxyhexadecanoic acid, 8,9,16-trioxyhexadecanoic acid, 9,
10,16-trioxyhexadecanoic acid, tetraoxy9,10hexadecanoic acid, 16-oxyΔ゛ hexadecanoic acid, 9,10-dioxyoctadecanoic acid, 9,
1012-oxyΔ゛ Octadecanoic acid (castor oil fatty acid), 12-oxy9,10-stearolic acid, 2
-Oxidodecanoic acid, 2-oxytetradecanoic acid, 2-
These include oxyhexadecanoic acid and those in which the unsaturated bonds of these oxyfatty acids are removed by hydrogenation.

Examples of commonly available predetermined fatty acids include castor oil fatty acids and 12-hydroxystearic acid, which is a hydrogenated product thereof. The production of an ester of a given fatty acid, the addition reaction of a given fatty acid ester with ethylene oxide or ethylene oxide and propylene oxide, and the hydrolysis of the reaction product with an acid or alkali can be carried out by known methods.

The number of moles of addition reaction of ethylene oxide or ethylene oxide and propylene oxide to the ester of a given fatty acid is determined depending on the purpose of cleaning. As a pre-scouring cleaning agent, 15 to 30 moles in the case of ethylene oxide alone, 20 to 45 moles in the case of ethylene oxide and propylene oxide (among them, propylene oxide is preferably less than the Z weight of ethylene oxide), and dyeing. As the subsequent soaping agent, in the case of ethylene oxide only, 25 to 60 mol;
In the case of ethylene oxide and propylene oxide, the amount is 35 to 80 moles (of which, propylene oxide is preferably less than Z weight of ethylene oxide). As a pre-scouring detergent for mineral oils and waxes for natural fibers and synthetic fibers, if only ethylene oxide is used, 15 to 30
moles, 20 to 45 moles in the case of ethylene oxide and propylene oxide (of which, propylene oxide is preferably less than % weight of ethylene oxide), 25 to 60 moles in the case of only ethylene oxide as a soaping agent after dyeing, In the case of ethylene oxide and propylene oxide, it is 35 to 80 moles (of which, propylene oxide is preferably less than Z weight of ethylene oxide), and in the case of only ethylene oxide, it is 10 moles for cleaning metals with mineral oils attached. ~30 mol, 15~ in case of ethylene oxide and propylene oxide
45 mol (of which propylene oxide is preferably less than % weight of ethylene oxide).

Products obtained by addition-reacting propylene oxide to ethylene oxide adducts of predetermined fatty acids exhibit even lower foaming properties. Examples of the salt of the predetermined compound in the present invention include monovalent salts such as lithium, potassium, sodium, and ammonium, monoethanolamine, diethanolamine,
triethanolamine, monoisopropanolamine,
There are alkanolamine salts such as diisopropanolamine and triisopropanolamine.

Among these, sodium salts and potassium salts are economically preferred. If necessary, other active agents,
Inorganic salts, sequestering agents, antifoaming agents, etc. may be added and used freely, but they do not affect the cleaning properties, biodegradability, and
Care must be taken not to impede the characteristics of wastewater treatment and low bubbles. The following examples further illustrate the invention.

In the description, parts or % simply refer to parts by weight or % by weight. Example 1 Add 2 parts of caustic potash to 930 parts of castor oil, and pressurize with nitrogen for 2~
After reacting 1,320 parts (30 moles) of ethylene oxide at a temperature of 150 to 170° C. for 4 hours under three conditions, a reaction product 2,2407 which was transparently soluble in water was obtained.

54 parts of a 25% aqueous potassium hydroxide solution was added to 550 parts of the reaction product, and after hydrolysis at a temperature of 90 to 95°C for 2 hours, 18 parts of water was added and a brown product (1% aqueous solution pH 9.8) became liquid at room temperature. ) was obtained.

This product was subjected to the tests described below. Example 2 In the same manner as in Example 1, 930 parts of castor oil was reacted with 660 parts (15 moles) of ethylene oxide, and then 50 parts of ethylene oxide was reacted.
Add 270 parts of aqueous solution of caustic potassium and add 8 parts of water after hydrolysis.
0 parts was added, and a brown product (1% aqueous solution of P
H9.7) was obtained.

This product was subjected to the tests described below. Example 3 In the same manner as in Example 1, castor oil was reacted with 2,200 parts (50 moles) of ethylene oxide, 270 parts of a 50% caustic potassium aqueous solution was added, and after hydrolysis, 225 parts of water was added, and the mixture was heated to room temperature. A pasty, brown product (1% aqueous solution, pH 9.8) was obtained.

The following tests were conducted on this product. A. A 0.1% aqueous solution of the products of Foaming Examples 1-3 was prepared and the loss
Foaming properties were measured at a temperature of 20° C. using the Miles method, and the results shown in Table 1 were obtained.

B. Wastewater treatment properties 0.1% water solubility of the products of Examples 1 to 3 (active ingredient 1,
000P Den), sulfuric acid band 300PI] [l (in terms of anhydrous sulfuric acid band) and polymer flocculant UNIFROTSKA-1 101 (
(manufactured by Unitika) was added, and P. After adjusting the temperature to H4 to 4.5, the mixture was stirred for 5 minutes and left at room temperature overnight, and the BOD (biological oxygen demand) was measured using the supernatant liquid as a treatment waste liquid according to JlSKOlO2.

The BOD of the untreated liquid was measured in the same manner, and the removal rate was determined using the following formula, and the results shown in the table were obtained. Example 4 An unrefined polyester chassis and a processed polyester yarn fabric were mixed in a beaker with 17/t of the product of Example 2 and 17/t of soda ash at a bath ratio of 1:30 and a temperature of 95 to 100°C. After washing for minutes, the water-washed cloth was extracted with ether for 4 hours and the residual fat percentage was measured.

The residual fat percentage of the water-treated cloth was measured in the same manner, and the residual fat percentage was calculated using the following formula, and the results shown in Table I were obtained.

Example 5 15 parts of each of the products of Examples 1 and 3 (active ingredients) and 70 parts of water were added to obtain a 30% detergent composition.

C. I. Using Acid Blue 78 for 3 (!) pairs of fibers, a nylon processed yarn fabric was dyed in a conventional manner, and then treated with tannin. Soaping was performed for 10 minutes.

The abrasion fastness of the dyed product was measured using a Gakushin type abrasion fastness tester, and as shown in the table, the soaping effect was good. Example
6 In the same manner as in Example 1, 930 parts of castor oil was reacted with 1,760 parts (40 moles) of ethylene oxide, then 5 parts of para-toluenesulfonic acid and 60 parts of water were added, and the temperature was 95-95.
Hydrolysis was carried out at 100° C. to obtain 40 mole ethylene oxide-added hardened castor oil fatty acid containing 90% of the active ingredient.

C. I. Reactive Bull 13 30y/t and Glauber's Salt 1
After soaking cotton muslin in a solution of 00 t/t for 30 minutes at room temperature, 20 y/l of soda ash was added and dyed for 50 minutes at a temperature of 85°C, followed by 57/t of glacial acetic acid and 1 vol of the product of Example 6.
Soaping was performed for 20 minutes at a temperature of 55 to 60°C with a solution of /t (pure content).

The dyed product obtained is clear and has a washing fastness of 5th grade staining.
It showed good soaping effect at grade. Example 7 Degree of biodegradability of the product of Example 1 hydrolyzed with caustic potash BOD after 5 days according to JISKOlO2 (hereinafter referred to as B
It was determined as a percentage of TOD (denoted as OD5) to TOD (total oxygen demand).

When biodegradability is good (BOD5/T?0D) x 100
The value (hereinafter referred to as biodegradation rate) shows a large value. Generally, when the value of the biodegradability rate exceeds 40%, it can be judged that the biodegradability is extremely good. 0 of the product of Example 1
．． BOD5 of 1% aqueous solution (active ingredient 1,000PF),
The TOD and biodegradation rate were determined and the results shown in Table V were obtained. The table shows that the product of Example 1 has an extremely high biodegradability rate compared to the comparative product Choran 2, indicating that it has good biodegradability.

Example 8 In the same manner as in Example 1, 314 parts of methyl 12-hydroxystearate was reacted with 440 parts (10 moles) of ethylene oxide, and then 116 parts of propylene oxide. 865 parts of a 10 mole ethylene oxide and 2 mole propylene oxide adduct of methyl acid were obtained.

20 parts of caustic soda and 43 parts of water were added to 435 parts of the reaction product and hydrolyzed, resulting in a liquid brown product (1% aqueous solution of P.HlO.2). This product is used as an active ingredient at 1V/t1 soda ash 17/t, liquid ratio 1:30, temperature 9
The nylon spandex was washed at 5-100°C for 30 minutes. Cleaning compositions made from this product had extremely low foaming properties. The residual fat percentage for the fabric determined by ether extraction after washing was 0.32%.

The results of a similar test using an 8 mol nonylphenol ethylene oxide adduct showed high foaming and a residual fat percentage of 3.10%, and 3.2% for unwashed products. Example 9 In the same manner as in Example 1, 1 part of ethylene oxide was added to 328 parts of ethyl 12-hydroxystearate.
, 760 parts (40 moles) of propylene oxide were reacted, and then 3 parts of caustic potassium was added and 1,160 parts (20 moles) of propylene oxide were reacted at 120 to 130°C for 6 hours under nitrogen pressure for 3 to 4 hours. A pale yellow viscous liquid product 3,2
Got 50 copies.

34 parts of a 50% caustic potassium solution was added to 325 parts of the above product for hydrolysis, and then 21 parts of ice was added to the PHlO. 3) 90% product was obtained.
The products of Example 2 and Example 9 were each purified at 17/t.
The raw wool was washed at 40°C for 30 minutes and then washed with water.
After extraction with an ether extractor for 4 hours, the residual fat percentage with respect to the raw hair was determined to be 0.2%. Similarly, a comparison product of nonyl phenol 8 mol ethylene oxide adduct was added at 27/t.
The residual fat percentage when the raw wool was washed with a concentration of 0.2% was 0.2%, and the residual fat percentage when washed with water was 2.1%. Cleaning using the comparative products resulted in significant foaming, requiring a considerable amount of time to rinse and resulting in poor workability, whereas cleaning using the products of Examples 2 and 9 resulted in low foaming.

Claims (1)

[Claims] 1 Fatty acid or polyoxyethylene ether of polyoxyethylene ether obtained by adding 5 to 100 moles of ethylene oxide or ethylene oxide and propylene oxide to a hydroxy fatty acid ester having 8 or more carbon atoms, and then hydrolyzing with acid or alkali. A low-foaming detergent characterized by containing at least one polyoxypropylene ether fatty acid and a salt thereof.