JPH0357158B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a liquid detergent composition, and more particularly, to an improvement in a liquid detergent composition containing an alkyl ethoxy sulfate salt as an active ingredient, which does not form a film even when left in the atmosphere. It does not gel or gel.
The present invention also relates to a liquid cleaning composition that can maintain fluidity. [Prior art and its problems] Conventionally, various anionic activators have been used as active ingredients in liquid detergents, and among them, alkali metal salts or alkaline earth metal salts of alkyl ethoxy sulfate esters have been used as active ingredients in liquid cleaning agents. These salts are frequently used because they have better cleaning performance than anionic activators and do not cause color deterioration unlike alkanolamine salts. However, while alkali metal salts or alkaline earth metal salts of alkyl ethoxy sulfate esters have such excellent properties, when liquid cleaning agents containing them as active ingredients are left in the atmosphere, water evaporates and the liquid level drops. There are problems in that a liquid film is formed and gelation occurs. This gelation phenomenon occurs when the liquid cleaning agent is collected into a measuring cup or when the cap of the cleaning agent container is forgotten to close, so it not only reduces the commercial value of the liquid cleaning agent, but also damages the cleaning agent. This made quality control during drug manufacturing difficult. And such a problem is that the total active agent component is 15 to 70
This was particularly noticeable in liquid detergents containing 5% by weight or more of alkali metal salts or alkaline earth metal salts of alkyl ethoxy sulfates. In order to solve these problems, various improvement methods have already been proposed. For example, products characterized by blending polyethylene glycol and water-soluble inorganic chloride to prevent film formation (Japanese Patent Laid-Open No.
No. 53-92809), which is characterized by blending a water-soluble salt of mono- and/or disulfate of polyalkylene ether glycol with polyalkylene ether glycol in order to improve the fluidity of a concentrated aqueous solution of surfactant (Unexamined Japanese Patent Publication No. (Sho 56-36596)
Examples include. However, although these methods achieve the desired effects to some extent, they have the disadvantage that the foaming power and rinsability, which are the original important functions of detergents, are impaired. [Means for Solving the Problems] Under these circumstances, the inventors of the present invention have conducted intensive research to solve the above problems, and have found that an alkali metal salt or alkaline earth salt of alkyl ethoxy sulfate, which is an active ingredient, When a polyalkylene oxide adduct of a specific polyhydric alcohol is used in combination with a metal salt, film formation and gelation do not occur, fluidity can be maintained, and it has excellent foaming power, rinsability,
The present invention was completed based on the discovery that a stable liquid cleaning composition can be obtained. That is, the present invention provides the following formula () RO (C ₂ H ₄ O) nSO ₃ M () (wherein, R is a straight chain or branched alkyl group having 7 to 18 carbon atoms, and n is an average of 1 to 5 and M represents an alkali metal or alkaline earth metal);
Sulfate ester salt of neopentyl glycol or polyalkylene oxide adduct (average molecular weight 300-5000) of trivalent or higher polyhydric alcohol 0.3-10% by weight
The present invention provides a liquid cleaning composition characterized by containing the following. In the liquid detergent composition of the present invention, the alkyl ethoxy sulfate salt () used as the active ingredient decreases in solubility in water as the number of carbon atoms in the alkyl group R increases, and the average number of moles of added ethylene oxide (n) decreases. As it increases, the foaming power decreases. Therefore, in general, the number of carbon atoms in the alkyl group R is 7 to 18, and the average number of added moles n of ethylene oxide is 1 to 5.
are used. The alkyl ethoxy sulfate ester () is blended in the total composition in an amount of 5 to 60% by weight (hereinafter expressed as %). In addition, sulfate ester salts of polyalkylene oxide adducts of neopentyl glycol or trihydric or higher polyhydric alcohols (hereinafter both may be collectively referred to as polyhydric alcohols) are used in combination with the alkyl ethoxy sulfate salts (). as,
A polyalkylene oxide adduct of polyhydric alcohol having an average molecular weight of 300 to 5,000 is used.
If it deviates from this range, the effects of the present invention will not be achieved. Suitable examples of the trihydric or higher polyhydric alcohol include glycerin, polyglycerin, trimethylolpropane, pentaerythritol, and sorbitol. The polyalkylene oxide is preferably one obtained by addition polymerizing one or both of ethylene oxide (EO) and propylene oxide (PO), and the addition state of PO and EO can be either block-like or random. It's okay. The sulfuric acid ester salt of the polyalkylene oxide adduct of polyhydric alcohol is produced according to a conventional method (for example, JP-A-57-5796). Further, as the salt, alkali metal salts, alkaline earth metal salts, alkanolamine salts, ammonium salts, etc. are preferable, and among them, alkali metal salts and alkaline earth metal salts are particularly preferable. These salts can be used alone or in combination of two or more. In addition,
It is possible to introduce sulfate groups in the number corresponding to the valence of the polyhydric alcohol into the sulfate ester salt, but in order to fully exhibit the desired effect, the number of sulfate groups in one molecule must be It is preferably 4 or less. The sulfate ester salt of polyalkylene oxide adduct of polyhydric alcohol is blended in an amount of 0.3 to 10% in the total composition. If the amount is less than 0.3%,
The effects of the present invention cannot be achieved, and if it exceeds 10%, the foaming power of the composition decreases, which is not preferable. In addition to the above-mentioned essential components, the liquid detergent composition of the present invention may contain known active agents for liquid detergents, if necessary. Examples of such activators include polyoxyethylene (average number of added moles of 4 to 20) alkyl (C ₇ to _{C 18} linear or branched) ethers, C ₈ to _{C 22} higher fatty acid mono- or dialkanols (C ₂ ~ _C3 ) amide, alkyl ( _C8 ~
_C20 ) Nonionic surfactants such as dimethylamine oxide; α-olefin ( _C8 - _C20 ) sulfonates [Na, K, Mg, triethanolamine (TEA),
NH ₄ ], α-sulfo fatty acid ester salt (

[Effect]

As is clear from the detailed description above, the present invention prevents film formation and gelation caused by alkyl ethoxy sulfate salts by using a sulfate salt of a polyalkylene oxide adduct of a polyhydric alcohol. However, the rationale for this is not entirely clear at present. However, it is estimated as follows. That is,
The film formed on the liquid surface of the cleaning agent is considered to be a higher-order structure (so-called lamellar liquid crystal) of alkyl ethoxy sulfate ester salt, which is formed by concentrating and changing the composition of the liquid as water evaporates. As this phenomenon progresses further, the fluidity of the entire liquid is impaired and gelation occurs. The sulfate ester salt of the polyalkylene oxide adduct of polyhydric alcohol used in the present invention has a molecular structure suitable for entering into the above-mentioned higher-order structure, so it does not penetrate into the higher-order structure. It is presumed that the structure is destroyed by its hydration power. [Effects of the Invention] According to the present invention, the performance of a liquid detergent using an alkyl ethoxy sulfate salt as an active ingredient, such as foaming power, rinsability, and stability, can be improved.
Film formation and gelation, which were conventional problems, can be prevented. [Example] Next, the present invention will be explained with reference to Examples. In addition,
Various performance evaluations described in the Examples were performed by the following methods. (1) Film formation test Collect 20ml of liquid cleaning agent into a 30ml sample beaker, leave it at 20℃ and 60%RH for 3 days, observe the surface condition of the liquid, and evaluate according to the following criteria. do. A: No film on the surface B: Film formed on part of the surface C: Thin film formed on the entire surface D: Thick film formed on the entire surface (2) Gelation test The sample used in the film formation test above was tested under the same conditions. After leaving the solution for another 7 days, the fluidity of the entire solution was observed with the naked eye, and the degree of gelation progress was judged according to the following criteria. A: No gelation at all and extremely good fluidity. B: Slightly gelled, but fairly fluid. C: Considerably gelled and slightly fluid. D: Almost gelled, with no fluidity at all. (3) Foaming power test Commercially available butter was used as a stain ingredient at a cleaning concentration of 0.5.
Measure the foaming power when adding 0.1% to a cleaning solution of 0.1%. The measurement method is to place 40 c.c. of the above detergent solution to which butter has been added into a glass cylinder with a diameter of 5 cm, rotate and stir for 10 minutes, and measure the foam height at the stop diameter. (4) Low-temperature stability test Evaluate the sample after storing it in a constant temperature room at -5℃ for 10 days. Evaluation details ○: No change △: Slightly cloudy ×: Separation or precipitation Example 1 Cleaning compositions containing sulfate ester salts of EO adducts or PO adducts of various polyhydric alcohols shown in Table 1 were prepared. Then, a film formation test, a gelling test, and a foaming power test were conducted on this product. The results are shown in Table 1. In addition, the abbreviations of components in the table indicate the following compounds (the same applies hereinafter). Furthermore, the number in parentheses after the abbreviation indicates the average molecular weight of the EO or PO adduct of the polyhydric alcohol. PEG-DS (Na): Disulfate salt of polyethylene glycol (Na salt) PPG-DS (Na): Disulfate salt of polypropylene glycol (Na salt) GLY-EO-MS (Na): EO adduct of glycerin Monosulfate salt (Na salt) GLY-EO-DS (Na): Disulfate salt (Na salt) of EO adduct of glycerin GLY-EO-TS (Na): Trisulfate salt of EO adduct of glycerin (Na salt) GLY-PO-TS (K): Trisulfate salt of PO adduct of glycerin (K salt) TGL-EO-TS (Na): Trisulfate salt of EO adduct of triglycerin (Na salt) ) TMP-EO-TS(Na): Disulfate salt (Na salt) of EO adduct of trimethylolpropane PET-EO-TeS(Na): Pentaerythritol
Tetrasulfate salt (Na salt) of EO adduct SOB-EO-TS (Na): Trisulfate salt (Na salt) of EO adduct of sorbitol NPG-EO-DS (Na): EO addition of neopentyl glycol Disulfate salts of substances (Na salts)

[Table] Example 2 A cleaning composition containing the sulfate ester salt of the EO adduct of trimethylolpropane shown in Table 2 was prepared, and its film formation test, gelation test, foaming power test, and low temperature stability were conducted. A sex test was conducted. Second result
Shown in the table.

[Table] Example 3 Cleaning compositions containing sulfate ester salts of PO/EO adducts of various polyhydric alcohols shown in Table 3 were prepared and subjected to film formation tests, gelling tests, and foaming power tests. , conducted low temperature stability tests. 3rd result
Shown in the table. In addition, the abbreviations of components in the table indicate the following compounds (the same applies hereinafter). Also, the numbers in [ ] in the abbreviations are
The molar ratio of PO/EO is indicated, and the number in parentheses after the abbreviation indicates the average molecular weight of the PO/EO adduct of the polyhydric alcohol. GLY-PE-TS (Na): Trisulfate salt (Na salt) of PO/EO adduct of glycerin TMP-PE-TS (Na): Trisulfate salt (Na salt) of PO/EO adduct of trimethylolpropane
salt) PET-PE-TeS (Na): pentaerythritol
Pentasulfate salt of PO/EO adduct (Na
Salt) SOB-PE-TS (Na): Sorbitol PO/EO
Adduct trisulfate salt (Na salt)

【table】

[Table] Example 4 Cleaning compositions having the compositions shown in Table 4 were prepared and subjected to film formation tests, gelling tests, foaming power tests, and low temperature stability tests. The results are shown in Table 4.

【table】

【table】

Claims (1)

[Claims] Primary formula () RO (C ₂ H ₄ O) nSO ₃ M () (wherein, R is a straight or branched alkyl group having 7 to 18 carbon atoms, and n is 1 on average. 5, M represents an alkali metal or alkaline earth metal) and a polyalkylene oxide adduct of neopentyl glycol or a trihydric or higher polyhydric alcohol (with an average molecular weight of 300 or more) 5000) and 0.3 to 10% by weight of a sulfuric ester salt thereof. 2. The liquid cleaning according to claim 1, wherein the trivalent or higher polyhydric alcohol is one or more selected from the group consisting of glycerin, polyglycerin, trimethylolpropane, pentaerythritol, and sorbitol. agent composition. 3. The liquid cleaning composition according to claim 1, wherein the number of sulfate groups in one molecule of the sulfate ester salt of a polyalkylene oxide adduct of a trivalent or higher polyhydric alcohol is 4 or less. 4. The total amount of active ingredients in the liquid cleaning composition is
15 to 70% by weight, and the amount of alkyl ethoxy sulfate salt () among the active ingredients is 5% by weight.
60% by weight of the liquid cleaning composition of claim 1.