JPS6254840B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a low-foaming detergent composition. More specifically, the present invention relates to a detergent composition that has low foaming properties and strong detergency. Low-foaming cleaning compositions include, for example, scouring cleaning agents for textiles, cleaning agents for machinery and metals, deinking agents (deinking agents) for waste paper recycling, felt cleaning agents, depitching agents (resin removal agents) for pulp, etc. It is used as an industrial cleaning agent, as well as a household cleaning agent such as a dishwashing agent and a cleaning agent for electric washing machines. Conventionally, nonionic surfactants such as Pluronik type and Tetronic type surfactants, which are condensation types of polyoxyethylene and holoxypropylene, and fatty acid polyethylene glycol ester type, have been known as such low-foaming detergent compositions. However, although these products do not foam well, they do not have sufficient cleaning power. Furthermore, the alkylphenol EO-PO block adduct (EO is ethylene oxide, PO is propylene oxide, hereinafter referred to in the same manner) described in Japanese Patent Publication No. 36-4373 has low foaming properties, but has low detergency. Not enough.
Also, alkylphenol (EO/PO) random adducts described in Japanese Patent Publication No. 40-22250,
EO adducts, which are random adducts of (EO/PO) of monohydric aliphatic alcohols described in Publication No. 33-2798, have excellent detergency, but have high foaming properties, and have low foaming properties. No product with excellent detergency has been obtained. The present inventors have conducted extensive research in order to obtain a detergent composition with low foaming properties and strong detergency, and as a result, they have arrived at the present invention. That is, the present invention is based on the general formula () (In the formula, R is an alkyl group having 6 to 12 carbon atoms, phenyl group, phenylethyl group, α-dimethylbenzyl group, A is an alkylene group having 3 to 4 carbon atoms, and l is 1 to
10, m is 1-8, n is 1-8, p is 1-3, and

[Formula] The average molecular weight of the chain portion is 1500 or less, and the content of polyoxyethylene chains is 25 to 65% by weight in the compound. ) is a low-foaming detergent composition containing a compound represented by the following as a main component. In the general formula (), R is an alkyl group having 6 to 12 carbon atoms, (hexyl group, octyl group, nonyl group,
dodecyl group, etc.) phenyl group, phenylethyl group, α-dimethylbenzyl group. If the number of carbon atoms in the alkyl group is less than 6, the cleaning power will be insufficient, which is not preferable. Further, l is 1 to 10, m is 1 to 8, and n is 1 to 8, considering low foaming properties and strong detergency. If l is less than 1, the product will have high foaming properties or the detergency will be weak, and if it exceeds 10, the product will have high foaming properties or the detergency will be weak. Further, when m is less than 1, the foaming property is high, and when it exceeds 8, only the effect as a foam suppressing agent can be obtained, resulting in weak cleaning properties. n is 1 to 8
Outside this range, the foaming property will be high or the cleaning performance will be weak. Also, if p is less than 1,

[Formula] The molecular weight of the chain portion (hydrophobic group) is insufficient, resulting in weak detergency. If it exceeds 3

[Formula] The molecular weight of the chain portion becomes too large and the detergency becomes weak. Also

[Formula] The average molecular weight of the chain portion is 1500 or less. If the average molecular weight exceeds 1500, the foaming property will be high or the detergency will be weak. The content of polyoxyethylene chains in the compound of general formula () is usually 25 to 65% by weight, preferably 35 to 60% by weight. When this content is less than 25% by weight, the water solubility is insufficient and the effect only as a foam suppressor can be obtained. If it exceeds 65% by weight, the product becomes hard, difficult to handle, and highly foamable. In addition, the content of terminal polyoxyethylene chains in the compound of general formula () is usually 3 to 55
% by weight, preferably from 3 to 45% by weight. If the content is less than 3% by weight, the detergency will be insufficient and the effect will only be achieved as a foam suppressor, making it unsuitable as a main ingredient in detergents. Moreover, if it exceeds 55% by weight, a product with low foaming properties cannot be obtained, and the object of the present application cannot be achieved due to high foaming properties. The compound represented by the general formula () is the starting material

The compound represented by the formula is added to EO, AO (alkylene oxide having 3 to 4 carbon atoms, such as propylene oxide, 1,2-, 1,3-, 2,3-, 1,4-butylene oxide, etc.) by a conventional method. It can be produced by adding blocks to the order of ) and then adding EO. However, although a compound with similar EO and AO contents can be obtained by random addition, the structure is completely different, and it is not possible to obtain a compound with low foaming properties and good detergency as obtained with the patented product. The compound represented by the above general formula () is (1) alkylphenol (EO)l(AO)m
(EO)n adduct, nonylphenol (EO) _{4
Nonylphenol _ _ _ _} EO) ₇ (PO) ₄ (EO) ₃ , octylphenol (EO) ₅ (PO) ₃ (EO) ₂ , etc. (2) Phenylphenol (EO) l (AO) m
(EO)n adduct. Orthophenylphenol (EO) ₄ (PO) ₅ (EO) ₄ etc. (3) Phenylethylphenol (EO) _l − (AO) −
_n (EO)n adduct. Styrenated phenol (EO) l (AO) m (EO) n adduct such as styrenated phenol (EO) ₇ (PO) ₃
(EO) ₄ (4) α-dimethylbenzylphenol (EO)l
(AO)m(EO)n adduct. For example, α-methylstyrene (1 mol) phenol (EO) ₆
(PO) ₃ (EO) ₃ , particularly preferred are nonylphenol (EO) ₄ (PO) ₂ (EO) ₂ , nonylphenol (EO) ₇ (PO) ₄ (EO) ₃ , and octylphenol (EO) ₅ (PO) ₃ (EO) ₂ , orthophenylphenol (EO) ₆ (PO) ₅ (EO) ₄ , styrenated phenol (EO) ₇ (PO) ₃ (EO) ₄
It is. In the cleaning composition of the present invention, in addition to the compound represented by the general formula (), l,
A compound in which at least one of m and n is outside the range and other surfactants may be contained in combination. Other surfactants mentioned above include nonionic surfactants listed in Surfactant Handbook (published by Sangyo Tosho Co., Ltd., July 5, 1960), pages 36 to 45, and pages 10 to 21.
The anionic activators described on page 1 can be mentioned.
For example, nonionic surfactants include alkyl ether type, alkylaryl ether type, alkyl ester type, polyoxyethylene alkylamine type, polyoxyethylene alkylamide type, polyoxyethylene polyoxypropylene type, sorbitan alkyl ester type, and fatty acid ethanol. Examples of the amide type and anion activator include carboxylate type, polyethylene glycol ether sulfate type, ester bonded sulfonate type, ether bonded alkylaryl sulfonate type, and phosphate type. The amount of active agent that can be contained in combination in the cleaning composition of the present invention is usually 50% of the total active agent.
It is less than 30% by weight, preferably less than 30% by weight. If the amount of the compound represented by the general formula () in the active agent is less than 50%, a sufficient effect cannot be obtained to satisfy both the objectives of the present invention, low foaming property and strong detergency. The present detergent composition may also contain an alkali builder, a solvent, a bleaching agent, a fluorescent dye, a coloring agent, a fragrance, etc., if necessary. This cleaning composition can be used as a cleaning agent without reducing workability due to foaming or causing various troubles, such as a scouring cleaning agent for textiles, a cleaning agent for machinery and metals, a deinking agent (deinking agent) for waste paper recycling, and a felt cleaning agent. Used for industrial purposes such as cleaning agents, pulp de-pitching agents (resin-removal agents), and other agricultural chemicals and photography industries. It can also be used as a dishwashing detergent, an electric washing machine detergent, a household detergent, and the like. This cleaning composition is usually used as an aqueous solution. Typical concentrations used are 0.01-20%, preferably 0.05-10%. The method of use may be the same as for general nonionic surfactants. For example, in the case of textile scouring detergents, it may be used in combination with agents such as alkaline agents (e.g. caustic soda, soda charcoal, sodium tribolyphosphate, etc.) or oxidizing agents under high temperature and high pressure. Scour and wash under normal pressure. In the case of cleaning agents for machinery and metals, immersion cleaning and spray cleaning can be used, but spray cleaning is preferable because the present cleaning composition has low foaming properties. Specifically, Surfactant Handbook (Sangyo Tosho Co., Ltd., published on July 5, 1960) No. 627-628
You can use the method described on the page. When used as a deinking agent for recycling waste paper, the waste paper is steamed in a pulper together with an alkaline agent, the present composition, etc. at high temperature and pressure (or at room temperature to 80°C and normal pressure). It is effective to then use the steamed product for a scouring method in which ink particles are removed using a wire mesh or the like. The composition also has low foaming properties, making it suitable for automatic dishwashers. Note that cedar is easy to use in a household washing machine. Some conventionally known detergents of this kind have sufficiently low foaming properties, but they have poor detergency, which is the main purpose of surfactants, and conversely, those with strong detergency have sufficiently low foaming properties. The cleaning composition of the present invention satisfies both low foaming properties and strong cleaning properties, although only one of them was satisfied. In addition, other properties necessary for a detergent, such as penetrating power and ease of rinsing, are equal to or higher than those of conventionally known polyoxyalkylene ether type nonionic surfactants. The cleaning composition of the present invention will be described in detail with reference to Examples below, but the present invention is not limited thereto. (% in examples is weight%
Example 1 The foaming properties and detergency of the cleaning compositions Nos. 1 to 20 of the present invention and comparative products A to J shown in Table 1 were evaluated.

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【table】 Foaming property and detergency test results of the product of the present invention

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[Table] The above results table-2 shows that the compositions of the present invention are comparative products A to
When compared with J, it shows that both low foaming properties and strong cleaning properties are satisfied. Examples regarding various uses of the cleaning composition of the present invention are shown below. Example 2 Example of scouring cotton knitted fabric using the composition of the present invention (A) Scouring conditions Sample cloth Cotton knitted fabric Bath ratio 1:15 Temperature, time 60 minutes 120°C Bath composition {Activator 0.5% owf Caustic soda 3.0% owf} (B) result

[Table] Amount of residual fat: Extracted with alcohol and benzene using a Soxhlet extractor. Whiteness: Measure reflectance using an AKA photoelectric colorimeter.Wettability: Drop water onto the stockinette after scouring.
The time taken for the water droplet to disappear was measured. As shown in the results below, the present invention showed an excellent scouring effect. Example 3 Low foaming cleaning agent for alkali metals (A) Cleaning agent

[Table] The powder type cleaning agent shown above was prepared and a cleaning test was conducted on steel plates and aluminum plates. As a comparative product, the activator components in Table 5 were replaced with Newpol.
PE ₆₄ (Pluronic type manufactured by Sanyo Chemical Co., Ltd.) was used, and the other ingredients were the same. (B) Test method 1 Creation of standard contaminated plate The following contaminated sample was applied to the steel plate and aluminum plate.
After being immersed for a second, it was washed with water and dried. Contaminated sample: spindle oil, oleic acid, carbon black dispersed with carbon tetrachloride. 2 Cleaning conditions Cleaning method: Use of spray Concentration of cleaning agent (Table 5): 0.5% Temperature: 30°C Time: 20 seconds 3 Judgment method: Attach contaminants remaining on the cleaned steel plate or aluminum plate to Sellotape and peel it off. Transfer it to the sellotape side. This sellotape was attached to a white paper, and the reflectance of the contaminated surface was measured using an AKA photoelectric colorimeter and calculated using the following formula. Cleaning rate (%) = RW-RS/RO-RS×100 RO: Reflectance of original white paper RS: Reflectance of standard contaminated plate (before cleaning) RW: Reflectance of contaminated plate after cleaning (C) Results

[Table] As shown above, the product of the present invention showed superior cleaning effects compared to the conventional Bruronik type. Example 4 Example of use as a low foaming deinking agent (deinking agent) for waste paper recycling (A) Test method 1 Disintegration conditions Test paper: Asahi Shimbun waste paper Waste paper concentration: 5% Processing temperature: 60°C Processing time: 20 Separation solution composition: As shown in Table-7

[Table] Comparative product A in Table 1 was replaced with No. 11 activator and the other ingredients were the same. 2 Deinking method After disintegration, the waste paper was filtered through an 80-mesh sieve at a concentration of 1% ( 2 times) to remove carbon particles. Next, a sheet was created using a paper machine. (B) Results

[Table] was measured.
As shown in the above results, the product of the present invention was found to have excellent effects as a deinking agent. Table 1 Comparative product A had poor cutting performance and decreased efficiency due to bubbling. Example 5 Low foaming detergent for washing dishes (A) Detergent

[Table] (B) Test method 1 c.c. (0.9 g) of edible lard in an anodized aluminum plate
Apply evenly. Dissolve 30 g of the above cleaning agent in 10 ml of warm water (40°C) and soak 5 plates as a set for 10 minutes. Take out one sheet at a time and wash gently with water. The residual fat was extracted with ether, and the cleaning efficiency was calculated from the amount of residual fat. (C) Results

[Table] Oxide adduct system As shown in the above results, the product of the present invention showed superior effects compared to commercial product B. Example 6 Low foaming detergent for electric washing machines (A) Detergent

【table】

[Table] (B) Test method The above cleaning agent was prepared, and a carbon black standard contaminated cloth was washed with a 2 g solution at 40°C for 30 minutes using a rounder-o-meter according to the provisional method of the Japan Oil and Fat Chemistry Association.
The detergency was determined by measuring the reflectance using an AKA photoelectric colorimeter. (C) Results

[Table] Acid Sodium Type As described above, the product of the present invention was found to be easier to rinse and to be more effective as a cleaning agent than commercially available product C.

Claims (1)

[Claims] 1 General formula () (In the formula, R is an alkyl group having 6 to 12 carbon atoms, phenyl group, phenylethyl group, α-dimethylbenzyl group, A is an alkylene group having 3 to 4 carbon atoms, and l is 1 to
10, m is 1 to 8, n is 1 to 8, P is 1 to 3, [Formula] The average molecular weight of the chain portion is 1500 or less, and the content of polyoxyethylene chains in general formula () is Middle school 25~
It is 65% by weight. ) A low-foaming detergent composition comprising a compound represented by the following as a main component. 2. The cleaning composition according to claim 1, wherein the content of the terminal polyoxyethylene chain is 3 to 55% by weight in the compound.