JPH0684509B2 - Cleaning composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a detergent composition having low odor and having extremely little odor due to aging.

More specifically, a detergent composition comprising a stabilized phenol ethoxylate obtained by reacting an improved phenol with an ethylene oxide, which is obtained by adding a specific neutralizing agent to the phenol ethoxylate obtained with a very small change with time, The present invention relates to use as a base material of

The phenol ethoxylates are used in a wide range of fields as the main cleaning active ingredient of cleaning compositions. Fiber, for example
It can be used for various cleaning agents for metals, leather, automobiles, houses, etc.

Various fragrances are generally added to these detergents depending on their use. However, if there is a problem with the odor of the phenolic ethoxylates, which are the main active ingredients for cleaning, the original effect of the fragrance may not be exhibited.
The present invention provides a high-quality detergent having a low odor and having very little odor due to aging by using a phenol ethoxylate containing lactic acid and / or lactate as a raw material for the detergent.

(Prior art) As a detergent raw material, especially in terms of detergency, easy non-adhesiveness, hard water resistance, compatibility, easy solubility, low temperature stability (cold resistance) defoaming and rinsing properties, phenol ethoxylates Is used. Generally, ethoxylates of phenols are present in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium alkoxide or the like, or an acid catalyst such as boron trifluoride, boron trifluoride-complex, antimony pentachloride, tin tetrachloride, etc. It is produced by adding ethylene oxide to phenols.

In addition to containing unreacted phenols, the phenols ethoxylates obtained by such a method may cause catalysts, aldehydes, free acids, esters, peroxides and other malodors or coloration. Contains a small amount of impurities. These aldehydes, free acids, esters,
Impurities such as peroxides are purified by washing with an aqueous alkali solution, saponification and distillation, and the alkaline catalyst is usually neutralized by adding a mineral acid such as sulfuric acid and phosphoric acid or acetic acid. The phenol ethoxylate obtained in this manner has other impurities that cause malodor and coloration, and thus has a problem of producing malodor with aging. Further, when the phenol ethoxylates that have changed over time are sulfated with a sulfating agent such as sulfur trioxide or chlorosulfonic acid, there is a problem that the hue of the sulfated product is significantly deteriorated. As described above, when a detergent product is prepared using the phenol ethoxylate obtained by the conventional technique, there are problems that cause odor of the product, product quality and deterioration, which is not preferable.

In particular, alkali catalysts such as sodium hydroxide, potassium hydroxide and sodium alkoxide used in the production of phenol ethoxylates by reacting phenols with ethylene oxide are usually mineral acids such as sulfuric acid and phosphoric acid or acetic acid such as phosphoric acid. It is purified by neutralizing by adding a neutralizing agent like this, but when using a phenolic ethoxylate using this conventional neutralizing agent as a detergent raw material, there is already an odor at the time of compounding. However, an odor is generated due to a change with time, which is a big problem in producing a cleaning agent having a small odor.

(Problems to be Solved by the Invention) An object of the present invention is to prepare a detergent at the time of blending the detergent when a phenol ethoxylate obtained by reacting a phenol with ethylene oxide is used as a detergent active ingredient. The purpose of the present invention is to provide a cleaning agent which has a low odor and a very low odor due to aging.

(Means for Solving the Problems) The present invention relates to a detergent composition containing a phenol ethoxylate as a cleaning active ingredient, wherein lactic acid and / or lactate is a phenol ethoxylate in which a phenol and an ethylene oxide are alkali-catalyzed. Is a phenol ethoxylate obtained by adding lactic acid and / or lactate to an unneutralized phenol ethoxylate obtained by reacting the phenol with an ethylene oxide in the presence of an alkali catalyst. A phenol ethoxylate obtained by adding lactic acid and / or lactate to a phenol ethoxylate obtained by reacting an unneutralized phenol ethoxylate obtained by neutralizing the catalyst or by removing the catalyst by filtration. The present invention relates to a cleaning composition containing the same.

The lactic acid used in the present invention may be one produced by either a fermentation method or a synthetic method, and the purity of lactic acid is not particularly limited, but is usually commercially available for industrial use, for brewing, and for food addition. Can also be used for

The lactate used in the present invention is an alkali metal salt of lactic acid such as sodium lactate, potassium lactate or lithium lactate, an alkaline earth metal salt of lactic acid such as calcium lactate, magnesium lactate or barium lactate, aluminum lactate, zinc lactate or silver lactate. , Copper lactate, iron lactate, manganese lactate, ammonium lactate, etc., and sodium lactate and potassium lactate are particularly preferred.

The addition amount of lactic acid and / or lactate used in the present invention is 1 to 0.001 part by weight, preferably 1 to 0.001 part by weight based on 100 parts by weight of phenol ethoxylate phenol ethoxylate.
05 parts by weight. Upon addition, the pH of the aqueous solution is preferably 4-9, and more preferably 5-7.

The method for adding lactic acid and / or lactate of the present invention is an unneutralized phenol ethoxylate obtained by reacting a phenol with ethylene oxide in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide and sodium alkoxide. There is a method of adding lactic acid to the phenol, or a method of adding lactic acid to the phenol ethoxylate from which the catalyst is removed by a known method such as filtration. Regarding the addition of lactic acid and / or lactate, it is preferable to add lactic acid and / or lactate to the phenol ethoxylate as it is or as a solution, and stir for about 30 minutes to completely dissolve it.

The phenol ethoxylates used in the present invention include alkali catalysts such as sodium hydroxide, potassium hydroxide and sodium alkoxide, or boron trifluoride, boron trifluoride-complex, antimony pentachloride, tin tetrachloride and the like in the phenols. Those obtained by the addition reaction of ethylene oxide in the presence of the acidic catalyst of.

The reaction temperature of the phenol ethoxylate obtained by reacting the phenol of the present invention with ethylene oxide is
A temperature range of 50 to 200 ° C, particularly 120 to 180 ° C is preferred.

The reaction pressure of the phenol ethoxylate obtained by reacting the phenol of the present invention with ethylene oxide is
A pressure range of 0 to 30 kg / cm ² G, especially 0.5 to 20 kg / cm ² G is preferred.

The addition of ethylene oxide to phenols is in the range of 0.1 to 100 mol, preferably 1 to 50 mol of ethylene oxide per mol of phenol.

Examples of phenols include phenol, bisphenol,
Ortho-cresol, meta-cresol, para-cresol,
2,4-dialkylphenol, 2,5-dialkylphenol, 2,6-dialkylphenol, nonylphenol,
Octylphenol, orthochlorophenol, metachlorophenol, parachlorophenol, paramethoxyphenol, paraaminophenol, orthophenylphenol, t-butyl-paracresol, hydroquinone, catechol, resorcinol, pyrogallol, 1-naphthol, 2-naphthol, 4-chloro-2-nitrophenol, para-t-butylphenol, orthoaminophenol, dodecylphenol, octylcresol,
Examples include dioctyl cresol, dinonylphenol, and 2,5-dichlorophenol.

In the detergent composition containing the phenol ethoxylate of the present invention as a cleaning active ingredient, in addition to the phenol ethoxylate containing lactic acid and / or lactate, various additives to be added according to various uses, for example, Activator, hydrotrope, foaming agent, foam stabilizer, antifoaming agent, thickener, low viscosity agent, builder, anti-staining agent, bleaching agent, fragrance, fluorescent whitening agent, fragrance, dye whitening agent It has been found that a detergent composition having extremely good performance can be obtained by combining the above ingredients and the like, thus completing the present invention.

In the detergent composition containing the phenol ethoxylate of the present invention as a detergent active ingredient, the content of the phenol ethoxylate detergent composition containing lactic acid and / or lactate is preferably 1 to 90% by weight.

Characteristics of the liquid detergent composition of the present invention depending on its use, for example, alkylbenzene sulfonates, alkyl ether carboxylates, fatty acid soaps, α-olefin sulfonates as effective activators having a synergistic effect of foaming, foam control, and cleaning. , Higher alcohol sulfate ester salts, alkyl ether sulfate salts, fatty acid alkylol amide sulfate ester salts, alkyl ether phosphate ester salts, alkyl phosphate ester salts, N-acylmethyl taurine, N-
Acyl amino acid salts, acylated peptides, alkyl alkanol amides, aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, imidazolinium salts, carboxybetaine type, aminocarboxylic acid salts, imidazolinium betaines It is preferable to add 0 to 30% by weight of one kind or a mixture of two or more kinds of alkylamine oxides, polyoxyethylene alkylamines, fatty acid alkanolamides and the like.

Further, as a solubilizing agent (hydrotrobe) for the liquid cleaning agent, lower alcohols, ethylene glycols, propylene glycols, glycerin, cellosolves, ethanolamines, toluene sulfonates, xylene sulphonate, urea One or a mixture of two or more selected from the above can be used in an amount of 0 to 10% by weight.

As the viscosity modifier, 0 to 5% by weight of inorganic salts such as one or a mixture of two or more selected from sodium chloride, potassium chloride, magnesium chloride, sodium sulfate, sodium carbonate and potassium pyrophosphate can be used.

The balance is water, but deionized water or distilled water is particularly preferable.

An antiseptic agent, a bactericidal agent, etc. may be added to prevent spoilage. Further, additives such as builders, anti-redeposition agents, bleaching agents, fluorescent agents, coloring agents, fragrances and antioxidants can also be used.

(Function) When a phenol ethoxylate obtained by reacting a phenol with ethylene oxide contains lactic acid and / or a lactate and the obtained phenol ethoxylate is used as a base material for a detergent, odor is aged. It was found that the effect of reducing the change was extremely small.

(Examples) Hereinafter, the embodiments of the present invention will be specifically described by way of examples. The invention is not limited to the examples that follow.

The test methods used in the examples are as follows.

(1) Odor 100 ml of odorless distilled water treated with activated carbon was added to 0.1 ml of the sample, and the temperature was determined at 50 ° C by the paired comparison method with the standard product. The odor was judged as follows.

5: Same as standard product 4: Slight odor than standard product 3: Slight odor than standard product 2: Clearly odor than standard product 1: Very strong odor than standard product Standard product (A) Example 1 3 to Comparative Examples 1 to 3, the cleaning agent of Example 1 which did not change with time was used as a standard product.

(2) Detergency test (Method A) Put 3 × 10 × 10 cm artificially contaminated cloth 65% polyester 35% cotton broad cloth into the cleaning solution 1 at the specified concentration, and use a tergotometer (rotation speed: 100 rpm). Washed.

(1) Cleaning conditions Cleaning agent concentration: 0.067wt% Water used: Tap water temperature: 25 ° C Cleaning time: 5 minutes Rinse: 5 minutes with tap water Fouling composition of artificially contaminated cloth A Organic matter (wt%) Myristic acid 16.7 Oleic acid 16.7 Tristearin 16.7 Triolein 16.7 Cholesterol 8.8 Cholesterol stearate 2.2 Paraffin wax (mp50-52 ° C) 11.1 Squalene 11.1 B inorganic clay (Kanto loam 250 mesh) C carbon carbon black (250 mesh) Organic 49.75% by weight, Inorganic 49.75% by weight, carbon 0.5
% Of the mixture was mixed into dirt, and the purified white cloth was contaminated so that the reflectance was 45% ± 2%.

(3) Calculation of cleaning rate of artificially contaminated cloth The reflectance at 530 μm of the original cloth before cleaning and the artificially contaminated cloth before and after cleaning was measured with a reflectometer (Hiranuma SPR-3 type), and the cleaning rate was calculated by the following formula. (%) Was calculated.

Example 1 200 g of nonylphenol (molecular weight 221), 0.6 g of sodium hydroxide as a catalyst, and 400 g of ethylene oxide were charged into a reactor made of stainless steel having a thermometer, a pressure gauge, and a stirrer and having a capacity of 1000 ml, and the temperature was 150 ° C. and the pressure was 6.0 kg /. The reaction was carried out at cm ² G. 2.7 g of a 50% by weight aqueous lactic acid solution was added to the obtained nonylphenol ethylene oxide average addition product of 10 mol, and well stirred. Ethylene oxide average of the obtained nonylphenol
A detergent composition of Table 1 containing 10.0 mol adduct (Sample-1) as a main washing active ingredient was prepared and tested for odor and detergency. The results are as shown in Table 1.

Comparative Example 1 200 g of nonylphenol (molecular weight 221), 0.6 g of sodium hydroxide as a catalyst, and 400 g of ethylene oxide were charged into a 1000 ml stainless reactor equipped with a thermometer, a pressure gauge, and a stirrer, and the temperature was 150 ° C. and the pressure was 6.0 kg /. The reaction was carried out at cm ² G. 0.9 g of acetic acid was added to the resulting 10-mol addition product of ethylene oxide on nonylphenol, and the mixture was stirred well. A cleaning composition of Table 1 containing the obtained 10.0 mol of ethylene oxide adduct of nonylphenol (Comparative Sample-1) as a main cleaning active ingredient was prepared and tested for odor and cleaning power. The results are as shown in Table 1.

Example 2 A 1000 ml stainless reactor equipped with a thermometer, a pressure gauge and a stirrer was charged with 143 g of nonylphenol (molecular weight 221), 0.6 g of potassium hydroxide as a catalyst and 457 g of ethylene oxide, and the temperature was 150 ° C. and the pressure was 6.0 kg /. The reaction was carried out at cm ² G. 1.9 g of a 50 wt% aqueous lactic acid solution was added to the obtained 16.0 mol average ethylene oxide adduct of nonylphenol and stirred well.

The average ethylene oxide of the obtained nonylphenol was 16.0.
A cleaning composition of Table 1 containing a molar adduct aqueous solution (Sample-2) as a main cleaning active ingredient was prepared and tested for odor and cleaning power. The results are as shown in Table 1.

Comparative Example 2 143 g of nonylphenol (molecular weight 221), 0.6 g of potassium hydroxide and 457 g of ethylene oxide as a catalyst were charged into a 1000 ml stainless steel reactor equipped with a thermometer, a pressure gauge, and a stirrer, and the temperature was 150 ° C. and the pressure was 6.0 kg /. The reaction was carried out at cm ² G. 1.0 g of a 50 wt% sulfuric acid aqueous solution was added to the resulting 16.0 mol ethylene oxide average adduct of nonylphenol, and the mixture was stirred well. A detergent composition of Table 1 containing the resulting aqueous solution of nonylphenol with an average of 16.0 mol of ethylene oxide adduct (Comparative Sample-2) was prepared and tested for odor and detergency. The results are as shown in Table 1.

Example 3 A 1000 ml stainless reactor equipped with a thermometer, a pressure gauge, and a stirrer was provided with 191 g of octylphenol (molecular weight 206), 0.6 g of sodium hydroxide as a catalyst, and 409 g of ethylene oxide.
Was charged and reacted at a temperature of 150 ° C. and a pressure of 6.0 kg / cm ² G.
The obtained octylphenol has an ethylene oxide average of 10
2.7 g of a 50 wt% lactic acid aqueous solution was added to the mole adduct, and the mixture was stirred well. A detergent composition of Table 1 containing the obtained ethylene oxide average 10.0 mol adduct of octylphenol (Sample-3) as a main washing active ingredient was prepared.
A detergency test was performed. The results are as shown in Table 1.

Comparative Example 3 In a stainless steel reactor equipped with a thermometer, a pressure gauge, and a stirrer, a capacity of 1000 ml, 191 g of octylphenol (molecular weight 206), 0.6 g of sodium hydroxide as a catalyst, and 409 g of ethylene oxide were used.
Was charged and reacted at a temperature of 150 ° C. and a pressure of 6.0 kg / cm ² G.
The obtained octylphenol has an ethylene oxide average of 10
0.9 g of 85 wt% phosphoric acid aqueous solution was added to the mole adduct, and well stirred. A detergent composition of Table 1 containing the obtained ethylene oxide average 10.0 mol adduct of octylphenol (Comparative Sample-3) as a main detergent active ingredient was prepared,
The odor and detergency were tested. The results are as shown in Table 1.

Example 4 Stainless steel with a capacity of 1000 ml equipped with a thermometer, a pressure gauge, and a stirrer
200 g of nonylphenol (molecular weight 221), catalyst in the reactor
As sodium hydroxide 0.6g, ethylene oxide 400g
Charge, temperature 150 ℃, pressure 6.0kg / cm²Reacted with G. Profit
Ethylene oxide on average 10 mol of nonylphenol
KYOWARD as an adjunct 600BUPS (manufactured by Kyowa Chemical Industry Co., Ltd.
Adsorbent) 7.5g and stirred at 80 ℃ for 30 minutes
Kyo which was transferred to a filter pre-coated with soil and adsorbed the catalyst
word 600 BUPS was removed. Then ethylene was filtered
Add 3.5 g of 50 wt% lactic acid aqueous solution to the oxide adduct, and
Stir well. The resulting nonylphenol ethylene oxide
Sid average 10.0 mol adduct (Sample-4)
The cleaning composition of Table 1 is prepared as
And a detergency test was performed. The results are shown in Table 1.
It was Ri.

Comparative Example 4 Stainless steel with a capacity of 1000 ml equipped with a thermometer, a pressure gauge and a stirrer
200 g of nonylphenol (molecular weight 221), catalyst in the reactor
As sodium hydroxide 0.6g, ethylene oxide 400g
Charge, temperature 150 ℃, pressure 6.0kg / cm²Reacted with G. Profit
Ethylene oxide on average 10 mol of nonylphenol
KYOWARD as an adjunct 600BUPS (manufactured by Kyowa Chemical Industry Co., Ltd.
Adsorbent) 7.5g and stirred at 80 ℃ for 30 minutes
Kyo which was transferred to a filter pre-coated with soil and adsorbed the catalyst
word 600 BUPS was removed. Obtained nonylpheno
Ethylene oxide average 10.0 mol adduct (comparative sample-
Detergent of Table 1 containing 4) as the main cleaning active ingredient
The composition was prepared and tested for odor and detergency.
The results are as shown in Table 1.

(Effect of the invention) The phenol ethoxylate obtained by reacting the phenol ethoxylate obtained by reacting the phenol with ethylene oxide contains lactic acid and / or lactate, and has an effect that the change of odor with time is extremely small. It turned out to exert. Further, the obtained phenol ethoxylate can be used in a wide range of fields as a surfactant.

Claims (1)

[Claims] 1. A liquid cleaning composition containing phenol ethoxylate as a cleaning active ingredient, wherein the cleaning active ingredient contains lactic acid and / or lactate in an amount of 1 to 0.001 part by weight per 100 parts by weight of phenol ethoxylate. A cleaning composition comprising a phenolic ethoxylate.