JPS606399B2 - 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. There it is,
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 is present in the liquid with the detergent, it is not possible to impart sufficient flexibility and antistatic ability to the cloth to be washed. In other words, the di-long-chain alkyl-type quaternary ammonium salt described above has the property of adsorbing to fibers and imparting flexibility and antistatic properties; This is thought to be due to its moderate cationic and hydrophobic properties.

However, when it coexists with a detergent in a solution, it is attacked by the active ingredients in the detergent (which are usually anionic and/or nonionic activators) and loses its cationic and hydrophobic properties. Because it is stored away, it becomes difficult to be absorbed by the cloth being washed.
As a result, the quaternary ammonium salt cannot fully exhibit its original function. Therefore, when imparting flexibility and antistatic properties to washed fabrics, the procedure generally adopted is to first wash the clothes using a detergent and then treat the washed fabrics again with a fabric softener. . However, performing the washing process and softening process separately in this way requires extra time and effort, so consumers are looking forward to detergents that can perform washing and softening 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 water-soluble organic dispersion inhibitors such as paraffin wax or higher alcohols with quaternary ammonium salts, or using special A method is known in which the swelling and dispersion of a quaternary ammonium salt is delayed by coating the quaternary ammonium salt with a film (US Pat. No. 393).
No. 6537, Special Seki No. 49-98403, Japanese Patent Application Publication No. 1973-
77406 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 be always 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, and the quaternary ammonium salt particles tend to adhere to the cloth being washed. This causes variations in the softening effect of the washed fabric. Another known method is to form a composite salt by adding and mixing an inorganic salt such as sodium carbonate to an alcoholic or aqueous solution of a quaternary ammonium salt (Japanese Patent Publication No. 36-8927).

This complex salt is less likely to be attacked by detergent components in the washing solution and can provide a certain degree of softening effect. The adhesion to washing cloth is weak, and the softening effect and antistatic effect are still insufficient. As a result of intensive research into detergent additives that do not lose the cationic and hydrophobic properties of quaternary ammonium salts and are less susceptible to attack by detergent components in washing liquids, the present inventors found that they have low moisture and volatile content. Discovered the fact that superior effects can be obtained by melt-mixing quaternary ammonium salt and hexametaphosphate,
Based on this knowledge, we have completed the present invention.

That is, the present invention is represented by the following general formula, in which a quaternary ammonium salt having a water content of 5% by weight or less and a volatile content including water of 1% by weight or less is heated and melted, and hexametaphosphate is added to the quaternary ammonium salt. A detergent additive is provided by adding the quaternary ammonium salt to the hexametaphosphate at a weight ratio of 1/5 to 10/1, uniformly mixing, and then cooling and solidifying. However, R,,
R2 represents a C, 2-C4 alkyl group, R3, R4 represents a C,-C4 alkyl group, benzyl group, C2-C4 hydroxyalkyl group or polyoxyalkylene group,
X is halogen, CH3S04, C3S04 or the quaternary ammonium used in the detergent additive of the present invention has a melting point of 30 to 100q○, preferably 40 to 9000
Quaternary ammonium salts that decompose or change in quality at high temperatures cannot be used in the present invention.

Specific examples of quaternary ammonium salts that can be used include distearyldimethylammonium salt, dicured tallow alkyldimethylammonium salt, dicured tallow alkylbenzylmethylammonium salt, distearylmethylbenzylammonium salt, and distearylmethylhydroxyethylammonium salt. , distearylmethylhydroxypropylammonium salt, distearyldihydroxyethylammonium salt, etc., and counter ions thereof include chloride ion, bromide 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 to reduce the water content to 5% by weight or less and the volatile content to 1% by weight. Hereinafter, preferably the water content should be 3% by weight or less and the volatile content should be 5% by weight or less. If there is a large amount of moisture and volatile content, not only may the quaternary ammonium salt and hexametaphosphate form a complex salt which has a negative softening effect when mixed, but also when the detergent additive of the present invention is used as a granular product. This is because it has an adverse effect on its free-flowing properties and storage stability. On the other hand, the hexametaphosphate used in the present invention is a cyclic polyphosphate represented by (MP03)6, where M is sodium or potassium. The mixing ratio of the above-mentioned quaternary ammonium salt and hexametaphosphate is very important for the present invention, and the weight of the former to the latter should be in the range of 1/5 to 10/1.

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 hexametaphosphate must be uniformly mixed. Therefore, in the present invention, when preparing detergent additives, quaternary ammonium salts are heated and melted.
A method is adopted in which hexametaphosphate is added to this.
In the powder temperature mixing method, the mixing state of the quaternary ammonium salt and hexametaphosphate tends to be non-uniform, so the desired effect may not be obtained. The molten mixture of quaternary ammonium salt and hexametaphosphate obtained in the present invention is not only a mixture of quaternary ammonium salt and hexametaphosphate, but also a type of chain state with very weak bonds due to interaction. It is thought that there is.

Therefore, when particles of this molten mixture are added to the washing liquid, the ionicity and hydrophobicity inherent to the quaternary ammonium salt are maintained within the particles without much loss, whereas the surface layer of the particles maintains this property. As a result, it becomes less susceptible to attack by anionic activators and nonionic activators that coexist in the washing liquid, and its adsorption to the items to be washed is not substantially inhibited. It is presumed that excellent flexibility and antistatic properties are imparted to the material. 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 250A. If the particle size is too large, it may not be possible to evenly impart flexibility to the items to be washed, and the additive particles may adhere to the items to be washed, and if the particle size is too small, the particles may not be able to impart flexibility 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, the quaternary ammonium salt heated and melted had an average particle size of 5.
Add 0 to 150 particles of inorganic salt, mix uniformly, cool and solidify, and then crush to obtain an average particle size of 60 to 100.
A mesh additive composition was obtained.

However, No. 5 to 16 are comparative examples. Table-1 1) Na20/Si02 = 1/2.2 Aqueous dispersion of quaternary ammonium salt (3) Powder of only quaternary ammonium salt Next, add each of the above additive compositions to the composition below. The additive compositions were added to a granular detergent and washed, and the effects of each additive composition on imparting flexibility to washed items, antistatic properties, and detergency were examined.

Composition of granular detergent Linear sodium alkylbenzenesulfonate 10wt% Sodium Q-olefin sulfonate 1 volume t% Sodium alkylsulfate 5wt% Sodium pyrophosphate
2 skin t% soda carbonate (anhydrous salt)
5wt% sodium sulfate (anhydrous salt)
37wt% moisture l
OWt% Other Fine t% (i
) Flexibility and antistatic note imparting effect testing method Nylon tricot cloth (30 denier) 30 mm x 4 pieces Acrylic jersey cloth 90 mm x 2 pieces Cotton towel
80 evenings x 2 pieces of bleached cotton cloth
50 pieces x 4 pieces of cotton stockinette cloth 8
A test cloth consisting of 5 sheets x 4 sheets was mixed with the above granular detergent at 6,000 ml.
The test fabric is pretreated by washing with tap water for 15 minutes and then rinsing three times for 3 minutes each with 60 qo of tap water.

Next, this test cloth was placed in a jet-type domestic electric washing machine, and was washed with the above granular detergent, each additive composition, and 2,500 ml of tap water under the conditions of a detergent concentration of 0.13% and a pressure of 300 ml. After washing for 1 minute and dehydrating for 1 minute, rinsing with 2500 ml tap water for 3 minutes and dehydrating for 1 minute was repeated twice. After that, the test fabric was air-dried for 24 hours, then 2500, 65
The air-dried test fabrics were conditioned under conditions of %RH. A nylon tricot cloth was taken out of the test cloths obtained in this way, and five judges judged its feel.
The softening effect of the additive composition was evaluated based on the average of five judges.

The feel was evaluated using 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. The results are shown in Table-2. noticeably soft
5 points: Quite soft 4 points: Soft 3 points: Slightly soft 2 points: Slightly soft 1 point: In addition, the same kind of nantricot cloth used for tactile evaluation was cut into 3.5 squares and measured using an honest meter (manufactured by Kikusui Denki). After adjusting the amplitude of the charged voltage on the cloth by applying a voltage of 10,000 volts from an electrode 2 skin high while rotating it at a constant speed, the applied voltage is turned off and the charged voltage on the cloth is halved. The time "half-life" was measured under conditions of 280 and 65% RH.

This operation was repeated three times for the same sample, and the antistatic effect of the additive composition was evaluated based on the average value. The results are shown in Table-2. (ii) Attach the detergent test method (Test Cloth Makihata Broad) to the collar of the shirt.
After being worn for ~7 days, the test fabric was removed and two symmetrically cut pieces were prepared.

A skin shirt (cotton knitted) worn in the same way for 2 to 3 days
Divide symmetrically. Next, using a jet-type household electric washing machine, one of the test cloths and skin shirts (Group A), which was divided into two halves, was treated with a mixture of the additive composition and granular detergent, and the other (Group B)
was washed using only granular detergent. 2500 for both groups for washing
The following conditions were used: tap water, detergent concentration 0.13%, and Yuhi 3M sound. After washing for 110 minutes, the items to be washed were dehydrated and dried by rinsing twice for 3 minutes each.

After that, each washed cloth of A and B's sheep was visually observed, and each washed cloth was evaluated on a five-point scale, with 5 points being given to those with completely clean dirt and 1 point being given to those with almost no dirt removed. Give a rating to the cloth,
The detergency was evaluated based on the following criteria based on the value obtained by dividing the total score of Group A by the total score of Group B and making 10 needle sounds. The results are shown in Table-2. 97 or more ○ 94-96 △ 93 or less were used at a weight ratio of 1:1, various additive compositions were prepared by changing the mixing method of both and the granulation method of the mixture, and the same experiment as in Example 1 was conducted for each additive composition. I did it.

However, the average particle size of the additive composition blended into the granular detergent is
In each case, the mesh size was 60 to 100, and the blending amount was 1wt% based on the granular detergent based on the quaternary ammonium salt. The experimental results are shown in Table 3.

However, No. 5 to 8 are comparative examples. Table 3 Example 3 Using the granular detergent and additive composition shown in Table 4, the same experiment as in Example 1 was conducted, and the results shown in the following table were obtained.

Table-4 Note '1) Linear alkylbenzene sulfonic acid soda (2
) Sodium o-olefin sulfonate (3) Sodium alkyl sulfate (R ○, 2) ○, 5) (4) Alcohol ethoxy sulfate (R = 0, 2Y 0, 5, Day 06 = 3)
(5) Alcohol ethoxylate (R=0,2Y0,
5, Sun 06 Ni 10) (6) Sodium tripolyphosphate (7
) Sodium hyrophosphate shelf A=Aqueous dispersion of distearyldimethylammonium chloride.

Claims (1)

[Claims] 1 A quaternary ammonium salt represented by the general formula below, containing 5% by weight or less of water and 10% by weight or less of volatile matter containing water is heated and melted, and hexametaphosphate is added to the quaternary ammonium salt. The weight ratio of hexametaphosphate is 1/5 to 1
Additives for detergents obtained by adding at a ratio of 0/1 and cooling and solidifying after uniform mixing ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, R_1 and R_2 represent alkyl groups of C_1_2 to C_2_6, R_3, R_4 represents an alkyl group of C_1 to C_4, a benzyl group, a hydroxyalkyl group of C_2 to C_4, or a polyoxyalkylene group, X is a halogen, CH_3SO_4, C_2H_5SO_4 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼