JPH0631410B2 - Detergent formulations - Google Patents

Description

The present invention relates to novel detergent formulations, in particular for anionic, nonionic or amphoteric surfactants, as general formula (I) as builders. Polypropylene glycol represented by (where n is 1
0-40) and the general formula (MSO ₃ ) ₂ NM ′ (II)
(In the formula, M represents a cation selected from sodium, potassium, lithium and ammonium, and M ′ represents hydrogen or a cation selected from sodium / potassium lithium and ammonium). The present invention relates to a novel cleaning composition that is inexpensive and has low toxicity and excellent cleaning power.

[Prior Art] A builder is defined as having an effect of increasing the surface activity of the surfactant or improving the physical properties of the powder when blended with the surfactant, and its properties are detergency, chelating effect and dispersion. It is required to be excellent in strength, emulsifying power, hard water resistance, corrosion prevention power, economical efficiency, etc. and be non-polluting.

[Industrial field of application] Conventionally known builders include nantrium tripolyphosphate, various phosphates, sodium metasilicate / Glauber's salt, sodium carbonate, etc., but those satisfying all of the above required properties are Therefore, it cannot be said that a builder has been developed that is practically satisfactory. For example, in the case of phosphate, there is a problem in drainage, and in the case of ordinary silicate, there are difficulties in terms of hard water resistance, etc. It is inferior to Of these, phosphates are generally most widely used due to their excellent inherent properties such as detergency, and therefore, they solve the environmental problems that are the drawbacks of these, and also synergize the inherent properties of builders. It would be very convenient if it could be improved.

[Problems to be Solved by the Invention] From this point of view, the present inventor overcomes the above-mentioned drawbacks of phosphate-based detergents, and in addition to performance and economic efficiency, particularly from the viewpoint of pollution. As a result of repeated intensive research to develop an improved detergent composition,
The inventors have found that the object can be achieved by using the polypropylene glycol as a builder and further appropriately mixing imidebissulfate or the like, and have completed the present invention. Each of these builders is inexpensive and has low toxicity, and has the remarkable technical effect of simultaneously achieving detergency, safety, and economy.

[Means for Solving Problems] Polypropylene glycol, which is an essential component of the present invention, has the general formula (I) It is represented by. Although n ranges from 3 to several hundreds, about 13 or less is easily soluble in water, about 30 or less is difficult to dissolve, and more is insoluble in water. It is easily soluble in organic solvents such as alcohols, ketones, ethers, chlorinated hydrocarbons and hydrocarbons. It is a colorless or slightly yellow nonvolatile liquid and has a flash point of 198.9.
It is as high as ~ 226.7 ° C and has little toxicity.

The detergent formulation according to the invention is intended to incorporate polypropylene glycol into the surfactant as described above and to achieve an imidobissulfate synergistic builder effect.

As the anionic surfactant, for example, conventional ones such as sodium alkyl sulfate ester, sodium alkylbenzenesulfonate, sodium long-chain α-olefinsulfonate, and alkyl polyoxyalkylene ether sulfate ester salt can be used alone or in combination. . As the nonionic surfactant, for example, polyoxyethylene alkyl ether, polyoxyethylene long chain fatty acid ester, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene nonylphenyl ether, long chain fatty acid alkylolamide, and the like,
As the amphoteric surfactant, a conventional one such as alkylaminoaminopropionate, alkyldimethylbetaine, alkyldihydroxyethylbetaine, and alkylimidazoline type may be used alone or in combination, as appropriate.

Further, cationic surfactants such as trialkylammonium halides and alkylpyridinium halides can be appropriately used together for the purpose of sterilization and antistatic.

Imidobissulfate (II), which is an essential component of the detergent composition of the present invention, is extremely inexpensive because it can be easily produced from sulfur and ammonia as raw materials and can be obtained by treating waste NO _X gas. Sulfur content is 1 of that of borax
It is much higher than 0% and can be said to be excellent in terms of effective use of sulfur.

Further, this compound does not structurally contain phosphorus which is said to be involved in the eutrophication problem, and the content of nitrogen is particularly low in alkali metal salts. The aqueous solution of this compound is neutral to weakly alkaline, and has a pH suitable as a builder.
The range is maintained. Water solubility is also an essential factor for the builder, but this compound has sufficient water solubility for use as a builder.

PH 1 for trisodium imidobissulfate (monohydrate)
0.9, solubility 19.7 (30 ° C) and 68.8 (40
C.), phosphorus content 0%, nitrogen content 5.4%.

In addition, crystallinity, powder stability, fluidity, granulation property, anti-caking property, etc. are indispensable as secondary properties of powder cleaning builders, but imide bissulfates generally have satisfactory performance. have.

In addition, trisodium imidobissulfate has extremely low acute oral toxicity, skin irritation, fish toxicity, hemolytic activity, etc., and other salts are considered similarly, and therefore the practical value is extremely high.

Examples of the imide sulfate include (NH ₄ SO ₃ ) ₂ N
H, (NaSO ₃ ) ₂ NH.2H ₂ O and other imidobissulfates (neutral), (NH ₄ SO ₃ ) ₂ NNH ₄ H ₂ O,
(NaSO ₃ ) ₂ NNa · H ₂ O, (NaSO ₃ ) ₂ N
Imidobissulfate (basic) such as Na.12H ₂ O can be used.

Next, the compounding ratio of each builder in the present invention is shown.

A remarkable effect can be seen when the blending ratio (weight) of the surfactant and polypropylene glycol is in the range of 1: 0.1-4, preferably 1: 0.2-2. The mixing ratio of the surfactant to polypropylene glycol and trisodium imidobissulfate is the same as the previous example, and the ratio of the surfactant to the total of both builders is 7: 1 to 1: 7, preferably 3: 1 to 1: 1. A remarkable result of 1: 3 is obtained. It is considered that the effect of polypropylene glycol is due to the effect of alkalinity and chelating power of trisodium imidebissulfate added to the calcium chelating power of polypropylene glycol and the improvement of the surfactant by polypropylene glycol or the mixing of polypropylene glycol and the surfactant.

It should be understood, of course, that various builders, ie sodium carbonate, sodium silicate, sodium aluminosilicate, E
DTA, NTA, sodium citrate and the like can be added.

〔The invention's effect〕

As is clear from the above, the composition of the present invention is a substance of low pollution, which has almost no toxicity or irritancy, does not cause eutrophication, is economical, and exhibits an excellent cleaning effect.

In addition, the surface activity is not limited to washing, but may be permeation, emulsification,
It can also be used for various purposes such as dispersion and solubilization.

EXAMPLES Next, the present invention will be described in more detail with reference to examples.

Test method The artificial soil was tested according to Japan Sunhome (1971) formula, and the detergency test method was carried out according to the Japan Oil Chemistry Association method.

(1) Formation of artificially contaminated cloth (momen) From 8 parts of oil, 0.40 to 0.45 parts of carbon black, and 800 parts of perkren, the momen cloth was immersed in a contaminated bath for 1 minute, and then air-dried to form an artificially contaminated cloth. did. The oil composition was 15 parts oleic acid, 7.5 parts palmitic acid, 7.5 parts myristic acid, 15 parts triolein, 15 parts tripalmitin, 10 parts cholesterin, 5 parts squalene, 10 parts liquid paraffin, and cetanol. It was composed of 10 parts and 5 parts of cholesterol palmite.

(2) Washing test Artificial contaminated cloth (size 5 × 10 cm) 4 obtained as described above 4
The sheet was put into a washing bottle having an internal volume of 400 m having 10 steel balls (diameter 6.5 mm) inside, and washed under the following conditions using a Launder odometer.

(3) Method of calculating cleaning efficiency (%) and cleaning index (%) The cleaning power was calculated by the following formula.

In the formula, R: reflectance of the contaminated cloth after washing R ′: reflectance of the base cloth R ₀ : reflectance of the contaminated cloth before washing The reflectance was measured through a green filter.
In addition, the cleaning index is the cleaning efficiency in the case of cleaning under the same conditions using a standard detergent close to practical use shown in Table 2,
It is expressed as a percentage of the measured cleaning efficiency.

Reference Example Polypropylene glycol (PPG) having various molecular weights was added to anionic and nonionic surfactants, and the detergency was determined. It shows in 1-9. Molecular weight 400
It is clear that a remarkable builder effect appears at about 2000, especially around 1000 to 1200.

Example 1 FIG. 1 shows the detergency when anionic and nonionic surfactants were blended with polypropylene glycols of various molecular weights 400, 1000 and 1200 and trisodium imidebisbissulfate (TSIS) at various ratios. Polypropylene glycol and trisodium imidobissulfate 3: 1 to 1
A remarkable synergistic effect was observed in the range of 1: 3.

Example 2 Further, in comparison with the example of the reference example, a case where a part of PPG was replaced with TSIS and a case where a nonionic surfactant was used were determined as No. 3 in Table 3. It shows in 10-13. It is clear that the detergency is further improved and the compounding effect is remarkably obtained (for example, No. 10 for No. 6 and N for No. 7).
o. 11 cleaning effect).

[Brief description of drawings]

FIG. 1 is a diagram showing the relationship between the cleaning efficiency and the compounding ratio when TSIS and PPG are compounded in LAS at various ratios.
It is shown that a significant synergistic effect is exhibited in each of the formulations in between.

Claims (1)

[Claims] 1. An anionic, nonionic or amphoteric surfactant as a builder, represented by the general formula (I): Polypropylene glycol represented by (where n is 1
0-40) and the general formula (MSO ₃ ) ₂ NM ′ (II)
(In the formula, M represents a cation selected from sodium, potassium, lithium and ammonium, and M ′ represents hydrogen or a cation selected from sodium, potassium, lithium and ammonium). A detergent composition prepared by blending.