JPS5947000B2 - additives for detergents - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an additive used in powdered or granular detergents (hereinafter collectively referred to as granular detergents), particularly in granular detergents containing anionic activators. It's hot,
More specifically, the present invention relates to a detergent additive that can be used in combination with a granular detergent to impart excellent flexibility and antistatic properties to washed fabrics during washing.

In ordinary households, when washing clothes and adding flexibility to the washed fabric, wash the clothes with a detergent solution, rinse off the detergent components with a large amount of water, and then wash the clothes with a detergent solution. A commonly used procedure is to treat the fabric to be washed with a fabric softener whose main component is a di-long-chain alkyl type quaternary ammonium salt that is sparingly soluble in water.

This is because if the quaternary ammonium salt coexists with the detergent in the solution, sufficient flexibility and antistatic ability cannot be imparted to the cloth to be washed. In other words, the above-mentioned di-long-chain alkyl-type quaternary ammonium salt inherently has the property of adsorbing to fibers and imparting flexibility and antistatic properties; This is thought to be due to its cationic and hydrophobic properties.

However, when it coexists with detergents in liquid, it loses its cationic and hydrophobic properties under attack by the active ingredients in the detergent (which are usually anionic and/or nonionic activators). Therefore, it becomes difficult for the quaternary ammonium salt to be adsorbed onto the cloth being washed, and as a result, the quaternary ammonium salt cannot fully exert its original function. Therefore, when imparting flexibility and antistatic properties to washed fabrics, the procedure generally adopted is to first wash the clothes with a detergent and then treat the washed fabrics with a soft finishing agent. There is. however,
Since carrying out the washing process and the softening process separately in this way requires extra time and effort, consumers are looking forward to detergents that can perform washing and softening processes at the same time. By the way, there are ways to make quaternary ammonium salts function even when they coexist with detergents in liquids, such as mixing poorly water-soluble organic dispersion inhibitors such as paraffin wax or higher alcohols with quaternary ammonium salts, or using special A method of delaying the swelling and dispersion of a quaternary ammonium salt by coating with a film is known (US Pat. No. 3,936).
No. 537, JP-A-49-98403, JP-A-50-J
(See Mo V406, etc.)

However, although these methods are effective to some extent under washing conditions, especially when the temperature of the water used is within a specific range, there is a problem in that the softening effect varies when the temperature of the washing water changes. To explain this point in more detail, as can be seen from the example where the water temperature is different in summer and winter, it is almost impossible for the temperature of washing water to always be constant. Therefore, in some cases, the swelling and dispersion of the quaternary ammonium salt is not delayed sufficiently, and in other cases, it is delayed too much, which tends to cause the quaternary ammonium salt particles to adhere to the cloth being washed. This causes variations in the softening effect of the cloth to be washed. Alternatively, sodium pyrophosphate,
A method of adding and mixing an inorganic salt such as sodium tripolyphosphate to form a composite salt (Japanese Patent Publication No. 36-8927) and a method of melt-mixing quaternary ammonium salt and hexametaphosphate (Japanese Patent Publication No. 160098-1982) Proposed.

However, as phosphates in detergents become regulated due to environmental concerns, phosphates such as sodium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate are also regulated as granulation base materials used in detergent additives. in the direction.
As a result of intensive research into detergent additives that do not use phosphates and are less susceptible to attack by detergent components in washing liquids, the present inventors have developed a method for melt-mixing quaternary ammonium salts and water-soluble aluminum compounds. The inventors have discovered that superior effects can be obtained by this method, and have completed the present invention based on this knowledge. That is, the present invention consists of a cationic activator represented by the following general formula and a water-soluble aluminum compound, and the weight ratio of the cationic activator to the aluminum compound is 1/5 to 1/5.
Provides additives for detergents in the range of 5/1.

(However, Rl and R2 represent an alkyl group having 12 to 20 carbon atoms, R3 and R4 represent a hydroxyalkyl group or a polyoxyalkylene group having 2 to 4 carbon atoms, and X represents a halogen CH3SO4 or C2 SO4.

) The cationic activator used in the detergent additive of the present invention is a quaternary ammonium salt represented by the above general formula, and specific examples thereof include distearyldimethylammonium salt, dicured tallow alkyl Dimethylammonium salt, dicured beef tallow alkylbenzylmethylammonium salt,
Distearylmethylbenzylammonium salt, distearylmethylhydroxyethylammonium salt, distearylmethylhydroxypropylammonium salt, distearyldihydroxyethylammonium salt, etc. are included, and counter ions thereof include chloride ion, bromine ion, etc.

Commercially available quaternary ammonium salts usually contain lower alcohols such as ethanol and isopropanol, and water, but these lower alcohols and water are removed in advance so that the water content is 5% by weight or less and the volatile content is 10% by weight or less, preferably. must have a moisture content of 3% by weight or less and a volatile content of 5% by weight or less. If the water content and volatile content are high, not only may a complex salt be formed when mixing a quaternary ammonium salt and a water-soluble aluminum compound with a negative softening effect, but also the detergent additive of the present invention may not be used in granular products. This is because if this happens, the free-flowing property or storage stability will be adversely affected. On the other hand, specific examples of the water-soluble aluminum compound used in the present invention include aluminum sulfate, aluminum chloride, alum, and sodium aluminate. The mixing ratio of the above-mentioned quaternary ammonium salt and water-soluble aluminum compound is extremely important for the present invention, and the weight ratio of the former to the latter must be in the range of 1/5 to 5/1.

If the weight ratio during mixing deviates from this range,
The softening effect and antistatic effect on the cloth to be washed deteriorate. Further, the quaternary ammonium salt and the water-soluble aluminum compound must be uniformly mixed. Therefore, in the present invention, when preparing a detergent additive, a method is adopted in which a quaternary ammonium salt is heated and melted, and a water-soluble aluminum compound is added thereto. The detergent additive of the present invention is used by being mixed into a granular detergent. In this case, the average particle size of the additive particles is preferably in the range of 50 to 250 microns. If the particle size is too large, it may not be possible to evenly impart flexibility to the items to be washed, and there is a risk that the additive particles will adhere to the items to be washed, and if the particle size is too small, particles may not be imparted evenly to the items to be washed. is not preferable because it becomes too dispersed and becomes difficult to be adsorbed onto the items to be washed. The amount of additives added to the granular detergent may range from 0.5 to 5% by weight based on the quaternary ammonium salt. If it is less than 0.5, the softening effect will be insufficient, and if it exceeds 5%, the detergency and foaming of the detergent will be impaired.

The present invention will now be described in more detail by way of examples.

Example 1 Using the quaternary ammonium salt and inorganic salt shown in Table 1, 9
300y of quaternary ammonium salt heated and melted at 0-95℃
Add 300 ft of inorganic salt with a particle size of 50 to 150 μm to the mixture, mix uniformly, cool and solidify at a cooling rate of 4 to 5°C/min, and then crush it to form an additive with a particle size distribution of 60 to 100 mesh. Obtained.

Next, using each of these additives, a granular detergent was prepared with the following composition. The flexibility imparting effect was tested.

The flexibility imparting effect was evaluated by the following method. The test fabric was pretreated by washing it for 15 minutes using the above granular detergent and tap water at 60°C, and then rinsing it three times for 3 minutes each using tap water at 60°C.

Next, this test cloth was placed in a jet-type household electric washing machine, and washed using the above-mentioned granular detergent, each additive composition, and tap water at 25°C under conditions of a detergent concentration of 0.13% and a bath ratio of 30 times. 10 to
After washing for 1 minute, dehydrating for 1 minute, rinsing with tap water at 25° C. for 3 minutes, and dehydrating for 1 minute, the procedure was repeated twice. Afterwards, the test fabric was air-dried for 24 hours, then 25°C, 65% R
The air-dried test fabric was conditioned under H conditions. A nylon tricot cloth was taken out of the test fabrics thus obtained, and its feel was judged by 10 judges, and the flexibility imparting effect of the additive composition was evaluated based on the average of the 10 judges. still. The feel was evaluated based on the following criteria in comparison with the feel of a nylon tricot cloth obtained by the same procedure as above except that no additive composition was used. Example NQl~4 showed good flexibility.

Example 2 An additive was prepared in the same manner as in Example 1, and this additive was used to create the same granular detergent composition as in Example 1 (however, the amount of additive was 1 wt% in terms of quaternary ammonium salt). The flexibility imparting effect was evaluated in the same manner as in Example 1.

The results are shown in Table-2. An example of IS! Q7-9 are
It can be seen that it exhibits better flexibility than the comparative example NQlO,ll.

Example 3 The granular detergent having the composition shown in Table 3 was tested for its softening effect in the same manner as in Example 1.
All were good with a score of 3.7 or higher.

Claims (1)

[Claims] 1. An additive for detergents consisting of a cationic activator represented by the following general formula and a water-soluble aluminum compound, the weight ratio of the cationic activator to the aluminum compound being in the range of 1/5 to 5/1. agent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R_1 and R_2 represent alkyl groups with 12 to 20 carbon atoms, R_3 and R_4 represent hydroxyalkyl groups or polyoxyalkylene groups with 2 to 4 carbon atoms, and X is Halogen, CH_3SO_4 or C_2H_4SO_
4 is shown. )2 The water-soluble aluminum compound is aluminum sulfate,
The detergent additive according to claim 1, which is aluminum chloride, alum or sodium aluminate.