JP2700267B2 - Liquid detergent composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a liquid detergent composition. For more information on clothing, plastic, floor tiles, walls, kitchens, gas stands,
Liquid detergent suitable for washing and removing dirt attached to ventilation fans, especially dirt that combines oil and carbohydrates, protein, soot, earth and sand, or those that have been left for a long time and adhered firmly. Composition.

[Conventional technology]

Various soaps, alkylbenzenesulfonates, alkylsulfonates, alkylsulfates, etc. can be used to remove simple dirt with oil, carbohydrates, earth and sand, etc.
Anionic surfactants such as alkyl ethoxy sulfate salts and alkyl phosphate salts and nonionic surfactants such as alkyl phenol ethoxylates, alkyl ethoxylates and alkyl ethanolamides, builders or, if necessary, lower alcohols, glycols and carbitols Is used.

These cleaning agents have excellent cleaning effects on simple dirt and are widely used, but they are used in conjunction with animal and vegetable oils and fats, mineral oil, grease, silicone, etc. attached to clothing, floor tiles, walls, etc., as well as carbohydrates and proteins. Soil, soot, earth and sand, etc., do not exhibit a sufficient effect of removing dirt, especially when the dirt has been adhered for a long time.

Various cleaning agents have been reported to remove such stubborn dirt. For example, a stain remover (US Pat. No. 3,374,902) in which hexylene glycol and an enzyme are blended with an anionic surfactant is used for removing protein attached to fibers, and a nonionic surfactant is used as a non-ionic surfactant for washing 3-methyl-3-anionic surfactant. Detergent containing methoxybutanol (Japanese
54-99106) or a detergent containing hexylene glycol, butyl cellosolve and the like (JP-A-51-10808).

[Problems of the prior art]

As a detergent that removes stubborn stains, detergents containing a surfactant and a solvent are used, but conventionally known detergents have poor cleaning effects on specific stains, or have drawbacks in use. It was something with

For example, when the solvent to be mixed with the surfactant is an alcohol-based solvent as described above, the cleaning effect on stains such as grease is inferior. In addition, as a solvent used in addition to the alcohol-based solvent,
Although chlorinated solvents and paraffinic solvents are known, chlorinated solvents are toxic and easy to volatilize, and are not suitable for cleaning agents used in ordinary households. The paraffin-based solvent has a poor cleaning effect on stains such as silicone and printing ink, has a poor emulsifying property, and has a drawback that it is difficult to mix as a cleaning agent. In addition, conventional cleaning agents exert cleaning effects only on limited stains, so they are used for stain removal agents for clothing, cleaners for hard surfaces such as microwave ovens, etc. according to their respective applications. Was limited.

The present invention has been devised in view of the above-mentioned problems, and it is possible to wash and remove simple stains, various oily stains, or strong stains obtained by combining these, which are attached to clothing and hard surfaces. It is an object of the present invention to provide a versatile liquid detergent composition that can be used.

[Means for solving the problem]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by using a liquid detergent composition containing a surfactant containing an alkylbenzene sulfonate and alkylbenzene in a specific ratio, clothing On products, plastics, floor tiles, walls, kitchens, gas stands, ventilation fans, etc., especially various oils and carbohydrates, proteins, smoke,
The present invention has been found that it is possible to remove dirt mixed with earth and sand or the like, or that these dirt is allowed to stand for a long time to remove solidly adhered dirt.

That is, the present invention relates to a surfactant component having an alkylbenzene sulfonate as an essential component, and an alkylbenzene containing an alkyl group having 10 to 14 carbon atoms, and 69.6 to 31.1: 30.4 to 6
It is a liquid detergent composition containing a weight ratio of 8.9 and optionally adding water, a builder, a viscosity modifier, and an abrasive, and the liquid detergent composition of the present invention dissolves well in water. It can be used in the form of a clear aqueous solution or paste by mixing with any amount of water, and by using it, it can be washed well from simple dirt attached to clothing and hard surfaces to stubborn dirt, Can be removed.

Examples of the alkylbenzene sulfonate used in the present invention include a linear alkylbenzene sulfonate and / or a branched alkylbenzene sulfonate having an alkyl group having 10 to 14 carbon atoms, and alkylbenzene sulfonates commercially available as detergent raw materials. Salt or carbon number 10 described below
Alkyl benzene having an alkyl group of ~ 14 can be sulfonated and neutralized to form a salt.

Examples of the salt constituting the alkylbenzene sulfonate include an alkali metal salt, an ammonium salt, and an amine salt. As the alkali metal salt, a sodium salt and a potassium salt are preferable, and as the amine salt, a monoethanolamine salt, a diethanolamine salt, and a triethanolamine are preferable. Amine salts,
Morpholine salts and the like are preferred.

Other surfactants used in the present invention include soaps, sulfonates, sulfate salts, anionic surfactants such as phosphate salts, alkylene glycols, nonionic surfactants such as alkanolamides, and the like. Examples include amphoteric surfactants such as betaine type and alanine type.

More specifically, the soaps include natural fatty acids such as animal and vegetable oil fatty acids, and alkali metal salts, alkylolamine salts, and ammonium salts such as synthetic fatty acids obtained by the oxidation reaction of petroleum-based raw materials. Sulfonate-based anionic surfactants include α-olefin sulfonate salts and petroleum sulfonate salts, and sulfate-based and phosphate-based anionic surfactants include coconut oil-reduced alcohol, tallow-reduced alcohol, lanolin alcohol, macaw alcohol, Synthetic primary alcohol (Dovanol: manufactured by Mitsubishi Yuka Co., Ltd., oxocol: manufactured by Mitsubishi Kasei Kogyo Co., Ltd.), synthetic secondary alcohol (Softanol:
Higher alcohols or ethoxylate sulfates and phosphates such as those manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd. These are sodium salts, potassium salts, ammonium salts, monoethanolamine salts, diethanolamine salts,
Used as salts such as triethanolamine salts.

Nonionic surfactants include natural fatty acids such as coconut oil and beef tallow and their reduced alcohols, castor oil, synthetic higher alcohols, octylphenol, nonylphenol, fatty acid sorbitan esters, fatty amines, and other ethoxylates. What is used is mentioned. Monoethanolamide and diethanolamide of coconut fatty acid and tallow fatty acid are also used as nonionic surfactants. As the amphoteric surfactant, NN
-Di (2-hydroxyethyl) N-lauryl-N-carboxymethylammonium betaine, sodium N-lauryl β-aminopropionate and the like. In addition, there is no particular limitation on other components.

The alkylbenzene used in the present invention has 10 carbon atoms.
Examples include straight-chain alkyl benzenes and / or branched-chain alkyl benzenes having up to 14 alkyl groups, and commercially available dodecyl benzene is preferred. Commercially available dodecylbenzene is supplied as a raw material for an alkylbenzene sulfonate used as a detergent, and contains as a main component a straight-chain alkylbenzene and / or a branched-chain alkylbenzene having 10 to 14 carbon atoms, mainly having 12 alkyl groups.

The liquid detergent composition of the present invention contains a surfactant component having an alkylbenzene sulfonate as an essential component and an alkylbenzene having an alkyl group having 10 to 14 carbon atoms, and the ratio of the alkylbenzene sulfonate to the alkylbenzene is:
The weight ratio is 69.6-31.1: 30.4-68.9.

Since the liquid detergent composition of the present invention contains the surfactant component and the alkylbenzene in the above proportions, the liquid detergent composition exerts a good cleaning effect on strong stains. Also, the alkylbenzene sulfonate in the surfactant component solubilizes the alkylbenzene well, and when the liquid detergent composition is diluted with water, a clear aqueous solution is obtained. In order to solubilize the alkylbenzene, it is preferable that the surfactant component contains 15% by weight or more of an alkylbenzene sulfonate.

The liquid detergent composition of the present invention can be produced by mixing each component individually, but when producing an alkylbenzene sulfonate from alkylbenzene in advance,
It is also possible to leave a predetermined amount of alkylbenzene unreacted and mix it with other components for production. For example, the alkylbenzene sulfonate conventionally used contains a small amount of unreacted alkylbenzene, and a method for producing the alkylbenzene sulfonate to minimize this amount has been studied (Oil Chemistry, 14 , P63 (196
5)) In the present invention, on the contrary, by suppressing the sulfonation rate with respect to alkylbenzene and leaving the alkylbenzene, an alkylbenzenesulfonic acid salt containing a predetermined amount of alkylbenzene can be produced and used.

Generally, the sulfonation reaction of alkylbenzene is performed using sulfuric anhydride or fuming sulfuric acid.

In the case of using sulfuric anhydride gas, a theoretical amount of sulfuric anhydride corresponding to the sulfonation rate is blown into the alkylbenzene in the reaction tank to cause a reaction, and a sample is taken out.The sample is neutralized to pH 7.0 to 7.5 with an aqueous solution of sodium hydroxide. The target alkylbenzene sulfonate is obtained by quantitatively analyzing the petroleum ether extract and confirming the content of unreacted alkylbenzene.

In addition, since the reaction of fuming sulfuric acid with alkylbenzene is slow in the reaction with fuming sulfuric acid, the reaction is carried out by increasing the proportion of fuming sulfuric acid from the theoretical molar ratio according to the sulfonation rate, and the content of unreacted alkylbenzene is determined in the same manner as above. To give the alkylbenzenesulfonate.

When the amount of unreacted alkylbenzene becomes equal to or less than a predetermined amount, it can be adjusted by adding alkylbenzene. The additional adjustment of the alkylbenzene can be performed at the time of production of the alkylbenzenesulfonic acid or even after neutralization to obtain an alkylbenzenesulfonic acid salt.

The alkylbenzene sulfonic acid containing alkylbenzene obtained as described above is neutralized with an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, ammonium, monoethanolamine, diethanolamine, triethanolamine, morpholine, etc. to form a salt thereof. .

The liquid detergent composition of the present invention contains a surfactant containing an alkylbenzene sulfonate and an alkylbenzene, and exhibits a good cleaning effect as it is. However, if necessary, water, a builder, a viscosity modifier, and a polishing agent may be used. A material can be added and used. The amount of the builder is 0 based on 100 parts by weight of the total of the surfactant component and the alkylbenzene.
~ 20 parts by weight, viscosity modifier 0 ~ 10 parts by weight, abrasive 0 ~ 100
Parts by weight are preferred, and water can be added in any amount.

As the above-mentioned builder, viscosity modifier and abrasive, those generally known can be used. For example, as a builder, sodium phosphate, sodium hydrogen phosphate,
Sodium polyphosphate, sodium carbonate, sodium sesquicarbonate, sodium borate, sodium silicate, zeolite, sodium chloride, sodium sulfate, sodium hydrogen sulfate, sodium citrate, sodium malate,
Sodium gluconate, sodium humate, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium polyacrylate, sodium polymaleate, fatty acid amide, sodium naphthalene sulfonate, urea, glycolic acid, sodium maleate styrene copolymer, sodium maleate vinyl alcohol Copolymers and the like, and as a viscosity modifier, methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Propyl ether, ethylene glycol monobutyl ether Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Examples thereof include diethylene glycol monobutyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, polyoxyethylene-polyoxypropylene copolymer, glycerin, carboxymethyl cellulose, starch and the like.

As abrasives, silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide, titanium oxide,
Zinc oxide, chromium oxide, iron oxide, silicon carbide, boron carbide, aluminosilicate, calcium carbonate, calcium phosphate, corundum, emery, quartzite, dolomite, quartz sand, sand, shellfish, etc., and these abrasives are 40 Those having a size smaller than the mesh are preferred.

The liquid detergent composition of the present invention, in addition to the above components, unless it impairs its stability, pH adjusters, fragrances, coloring agents, hydrotropes, thickeners and other commonly known detergents Auxiliaries can be added.

The liquid detergent composition of the present invention has good water dilutability in a liquid or paste state, and has a transparent appearance when converted to a low-concentration aqueous solution. When this is used, an aqueous solution of about 0.01 to 1% by weight is used as a liquid detergent for clothing, and a high-concentration solution is used as a stain remover. When cleaning hard surfaces such as plastics, gas stands and ventilation fans, dirt is removed. Depending on the degree, various uses such as using a low-concentration aqueous solution or an undiluted solution can be performed.

 Next, examples and comparative examples of the present invention will be described.

〔Example〕

 % In Examples shows% by weight.

Example 1 A sulfonation reaction was carried out using an alkylbenzene as described below, and samples A to G containing an alkylbenzene and an alkylbenzene sulfonate were produced.

Alkylbenzenes 1 of fuming sulfuric acid method alkylbenzene SAB-G (C ₁₀
2.0%, alkylbenzenes 30.7% of C _11, alkyl benzene 29.3 percent of C _12, alkyl benzene 19.3% of C _13, alkyl benzene 8.7% content of C ₁₄₎ (Mitsubishi Petrochemical Co., Ltd.) 8
0 g was placed in a 200 ml four-necked flask, and 6 g of 20% fuming sulfuric acid (special grade reagent) was added dropwise over 10 minutes while stirring at 700 rpm. During this time, the temperature was kept at 20 ± 1 ° C. After completion of the dropwise addition, the reaction was continued at a temperature of 45 to 50 ° C for 60 minutes.

The above reaction product was washed with water and then neutralized with 40% sodium hydroxide as Sample-A, the one neutralized with 40% potassium hydroxide as Sample-B, and the one further neutralized with diethanolamine as Sample-C. did.

Anhydrous sulfuric acid method Naruken N-500 (alkylbenzene 13.7% of C _10, C
₁₁ alkylbenzene 29.7 percent of alkylbenzenes C ₁₂ 2
5.8%, alkylbenzenes 18.2% of C _13, alkyl benzene 12.4% content of C ₁₄₎ (manufactured by Nissan Chemical detergents, Ltd.) 80 g
Was placed in a 200 ml four-necked flask, and while stirring at 700 rpm, sulfuric anhydride diluted with nitrogen gas to a concentration of about 10% was fed at a constant rate to carry out the reaction at a temperature of 20 ± 1 ° C.

The amount of sulfuric anhydride fed was measured by a metering pump, and when the amount became close to a predetermined charged amount, sampling was performed, and the content of unreacted alkylbenzene was measured to obtain a reactant containing 30.5% of unreacted alkylbenzene. The reaction product was neutralized with 40% sodium hydroxide as Sample-D, the one neutralized with 40% potassium hydroxide as Sample-E, and the one further neutralized with morpholine as Sample-F.

A reaction product in which unreacted alkylbenzene was 51.3% was obtained by the same reaction with sulfuric anhydride as described above, and this was neutralized with 40% sodium hydroxide to obtain Sample-G.

The water content of the obtained samples A to G (test method: JIS K3362 5.1
7) The contents of inorganic salts (test method: JIS K3362 5.13), alkylbenzene sulfonates (test method: JIS K3362 5.3) and alkylbenzenes (test method: JIS K3362 5.1) were measured, and the results are shown in Table 1. Show.

The obtained Samples A to G were blended as shown in Table 2 to obtain a liquid cleaning composition of the present invention, and a cleaning test of a stained stainless steel plate and a tile was performed using the composition. Table 2 shows the results. No. 19 in the liquid detergent composition of Table 2 is a comparative example in which no alkylbenzene was used.

1) Preparation of stained stainless steel plate and tile and cleaning test method.

B) Preparation of stained stainless steel plate Prepare a 3 cm x 6 cm test piece of stainless steel SUS 304 surface No. 4 polished plate (Nippon Stainless Steel Co., Ltd.).

Place 700 ml of soybean salad oil in an oil bath with a capacity of 1 and set the temperature to 160 ° C, set the stainless steel plate so that the surface of the stainless steel plate is horizontal at 15 cm above the oil level, and fumigate for 24 hours. A volatile stainless steel plate was attached to the plate to prepare a stainless steel plate to which heat-degraded dirt had adhered.

B) Preparation of tiles with stains 1.0 g of molybdenum grease is uniformly applied to the surface of a vinyl chloride tile (white) 5 cm x 10 cm for flooring, and is allowed to stand horizontally at 25 ° C for 6 days for tiles with grease stains. Was prepared.

C) Washing test method 2 g of the liquid detergent composition was attached to a sponge, and the surface of a test piece (stained stainless plate or tile) adjusted as shown above was rubbed up and down five times, and this was heated to 30 ° C.
Into a beaker containing 700 ml of water, stirred with a magnetic stirrer at 300 rpm for 3 minutes, and then taken out. The state of adhesion of dirt (soybean salad oil dirt or grease dirt) remaining on the surface of the test piece was visually evaluated according to the following criteria.

 A: Very good dirt removal.

 B: Good dirt removal.

 C: Soil removal property is slightly poor.

 D: Removability of dirt is considerably poor.

 E: Very poor dirt removal.

Example 2 Liquid detergent composition prepared by blending Samples A to G and sodium alkylbenzene sulfonate (Nissan Chemical Industry Co., Ltd., dehydrated 550A Soft Oarai) manufactured in Example 1 as shown in Table-3 Was used to perform a cleaning test on the contaminated cloth. Table 3 shows the state of the aqueous solution when each liquid detergent composition was diluted and the results of the cleaning test of the contaminated cloth. In the liquid detergent composition of Table 3, No. 27 is a reference example, and No. 28 is a comparative example.

2) Cleaning test method for stained cloth a) Preparation of stained cloth Add 25 g of corn starch to 500 g of water, stir at 95 ° C for 30 minutes, adjust the water reduced by evaporation to the original weight, and adjust the concentration to 5%. A corn starch solution was obtained. To this, 25 g of edible lard was added and mixed to obtain a uniform dispersion.

A rayon taffeta of 20 cm × 90 cm and a weight of 180 g was immersed in this dispersion, squeezed with a rubber roll so that the weight became 360 g, and dried in a horizontal state at 80 ° C. for 60 minutes. What was left in the room for 6 days was used as a contaminated cloth.

B) Cleaning test method Each liquid cleaning composition (No. 20-28) converted to anhydride
100 ml of a 0.5% strength aqueous solution is prepared, placed in a washing beaker, and kept at a temperature of 25 ° C. Put a 10cm x 10cm piece of contaminated cloth and 10 φ6.4mm steel balls into this round-
Washing was performed with a 0-meter for 20 minutes, and furthermore, washing with 100 ml of tap water at 25 ° C. was performed twice for 5 minutes to take out the contaminated cloth.

After washing, the cloth was taken out, dried, and subjected to Soxhlet extraction with ethanol containing 5% of water, and the residual glue residue ratio was measured.

[Effect of the Invention] As described above, the liquid detergent composition of the present invention contains a surfactant containing an alkylbenzene sulfonate and alkylbenzene in a specific ratio, and is a conventional clothing detergent or hard surface detergent. Compared to cleaning agents such as clothing, plastics, floor tiles, walls, kitchens, gas stands, dirt attached to hard surfaces such as ventilation fans, especially various oils and carbohydrates, proteins, smoke, earth and sand, etc. The present invention can be used for a composite soil or a soil to which these soils have been left for a long time and adhered firmly, and have an effect that these stains can be washed and removed well.

Claims (1)

(57) [Claims] (1) A surfactant component comprising an alkylbenzene sulfonate as an essential component and an alkylbenzene containing an alkyl group having 10 to 14 carbon atoms, comprising 69.6 to 31.1: 30.4 to 68.9.
A liquid detergent composition comprising, as required, water, a builder, a viscosity modifier, and an abrasive.