JPH024709B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention provides a softener composition that can impart excellent flexibility and antistatic properties to fibers, clothing, hair, etc.
In particular, the present invention relates to an aqueous liquid softener composition that can impart excellent flexibility and antistatic properties to chemical fiber products such as acrylic nylon and polyester, and has excellent dispersion stability. [Prior Art] Quaternary ammonium having two long-chain alkyl or alkenyl groups in its molecule has been used to prevent deterioration of texture and antistatic properties due to repeated washing of textile products at home. Softeners containing salt as an ingredient are used. Typical examples of the quaternary ammonium salt include di-hardened beef tallow alkyl dimethyl ammonium chloride and methyl-1-beef tallow alkyl dimethyl ammonium chloride and methyl-1-beef tallow alkylimidazolinium methyl sulfate. Although it can impart excellent flexibility to synthetic fiber products, it cannot be said to have sufficient effects in terms of flexibility and antistatic properties for synthetic fiber products. Therefore, modification of the quaternary ammonium salt itself (JP-A-55-51876, etc.), combination of the quaternary ammonium salt with other specific di-long chain alkyl quaternary salts (JP-A-55-51874, etc.) 55−62268, 55−
103364, 55-103365, etc.), the combination of the quaternary ammonium salt and tri-long chain alkyl quaternary salt (JP-A-55
-112375, 55-1112377, 56-79768, etc.), the fourth
A combination of a quaternary ammonium salt and a specific mono-long chain alkyl quaternary salt (JP-A-57-205581, etc.), a combination of the quaternary ammonium salt and an anionic surfactant (JP-A-53-19497, 53- 38794, 53−52799, 58−
13775, etc.), but although these methods have shown some improvement, the effects are still insufficient, and in some cases, the flexibility of cotton may be impaired. Therefore, up to now, there is no household fabric softener that can impart sufficient flexibility to both cotton and synthetic fiber products and has an excellent antistatic effect on synthetic fibers. On the other hand, in order to solve the above problem, the applicant has
We have discovered that excellent effects can be obtained by combining a carboxylic acid type anionic polymer with a grade ammonium salt, and have already applied for a patent (Patent application 1982-
127722), but it was found that these two components alone tend to cause phase separation or rapid increase in viscosity over time of storage, and cannot provide sufficient dispersion stability, which is essential for commercial value. Apart from these, granular detergent additives have been proposed that use a combination of a di-long-chain alkyl quaternary ammonium salt and a specific anionic polymer (Japanese Patent Laid-Open Nos. 59-6298 and 61-7398). but,
Since these are granular and have insufficient dispersibility and solubility in water when used alone, the purpose of the present invention cannot be achieved even if these granular additives are used in a normal washing and rinsing process. [Problems to be Solved by the Invention] Therefore, the present invention is capable of imparting flexibility equivalent to conventional products to cotton in the softening treatment carried out in the washing and rinsing process at home, while imparting flexibility to synthetic fibers. It is an object of the present invention to provide an aqueous liquid softener composition which can impart significantly superior flexibility and antistatic properties as compared to conventional products, and which also has superior dispersion stability. [Means for Solving the Problems] The object of the present invention is to provide a nonionic interface between a carboxylic acid type anionic polymer and a polyoxyethylene addition type to a predetermined sparingly water-soluble quaternary ammonium salt type cationic surfactant. It has been found that this can be achieved by using an active agent in combination. That is, the present invention provides (A) a poorly water-soluble quaternary compound having 2 to 3 alkyl groups or alkenyl groups having 14 to 24 carbon atoms in the molecule;
(B) a carboxylic acid type anionic polymer, (C) a polyoxyethylene addition type nonionic surfactant, and (D) an aqueous vehicle; The weight ratio of C) is 100/1 to 3/1
A liquid fabric softener composition is provided. Examples of the poorly water-soluble quaternary ammonium salt of component (A) used in the present invention include those represented by the following general formula () or (). These can be used alone or as a mixture of two or more, and each of these can optionally be -OH, -O-,

【formula】

2 to 3 linear or branched alkyl or alkenyl groups having 14 to 24 carbon atoms substituted or interrupted by a functional group such as [Formula] in the molecule.
It is a unique cationic surfactant. [In the formula, at least two groups among R ₁ to _{R 4} are unsubstituted or optionally -OH-, -O-,

【formula】 〔Effect of the invention〕

According to the softener composition of the present invention, it is possible to impart excellent flexibility not only to cotton fibers but also to synthetic fibers, and also to impart excellent antistatic properties to synthetic fibers. It is a composition. Furthermore, it does not thicken significantly even when stored at high temperatures for a long period of time, has excellent restorability even when frozen, and is excellent in practical use because it does not cause abnormal phase separation. Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto. [Example] The preparation, performance evaluation, and dispersion stability evaluation of the softener composition in the example were carried out by the following methods. Preparation method of Γ aqueous dispersion Dissolve the other components except component (A) in water, and
The mixture was heated to 45°C, and the melted component (A) was added dropwise thereto while stirring to uniformly disperse it, and then cooled to 25°C. Γ Finish Treatment Method Commercially available cotton towels and acrylic cloths were washed twice at 50°C using a commercially available laundry detergent in an electric washing machine, and then thoroughly rinsed with tap water at room temperature to prepare test cloths. Next, the softener composition was added to 30 g of tap water at 25° C. so that the amount of component (A) added was 1 g to form a homogeneous solution. Each test cloth was immersed in this solution at a bath ratio of 30 times, treated for 3 minutes, and then dehydrated for 2 minutes. After air-drying the fabric treated in this way, the cotton towel for evaluating the softening effect was left at 25℃ and 65%RH for 24 hours, and the acrylic cloth for evaluating the antistatic effect was left at 20℃ and 50%RH for 24 hours. Leave it under conditions for 72 hours,
It was used for each evaluation test. Γ Performance evaluation method (a) Flexibility: The feel of the cotton towel before and after treatment was compared and evaluated based on the following criteria. +5...Very soft +4...Quite soft +3...Soft +2...Slightly soft +1...Slightly soft 0...Same as before treatment (B) Antistatic property: Static Honest Meter (manufactured by Shishido Shokai) The polyester cloth was charged with an applied voltage of 7 KV and a target distance of 20 mm.
The half-life (seconds) of the charged voltage after the voltage was removed was measured. Γ Dispersion stability evaluation method (a) Viscosity change: For each prepared softener composition, immediately after preparation, stored at -15℃ for 40 hours and frozen, then thawed at 25℃, and 1 month at 45℃ The stored product was measured using a B-type viscometer (manufactured by Tokyo Keiki) (measurements were carried out at 25°C). (b) Judgment of liquid separation: Pour each prepared softener composition into a transparent cylindrical bottle with an inner diameter of 45 mm from the bottom.
After filling up to 70 mm and storing it for one month at 5°C, the separation length was measured. Judgment ○: No separation △: Separation length less than 3 mm ×: Separation length 3 mm or more Example 1 Various liquid softener compositions having the compositions shown below were prepared, and the performance and dispersion stability were evaluated. Display the results -
Shown in 1. (A) Component: Dihardened beef tallow alkyldimethylammonium chloride: 5 (%) (B) Component: (polymer shown in Table 1): [equivalent to component (A) in charge molar ratio] (C) component: POE (=40) nonyl phenyl ether: 0.25% [(A)/(C) weight ratio = 20/1] (D) component: 3% ethylene glycol aqueous solution: remainder In addition, the above (A) component is a combination of isopropanol and Since it is provided as a mixture, approximately 1.7 (%) of isopropanol is incorporated into the composition.

【table】

[Table] From Table 1, it can be seen that the product of the present invention is a softener composition with excellent performance and dispersion stability. That is, even when di-cured beef tallow alkyldimethylammonium chloride alone shows quite excellent flexibility,
The addition of component (B) clearly improves the flexibility and antistatic properties of the acrylic cloth, especially Nos. 1 and 5.
It can be seen that it exhibits very excellent antistatic properties.
In addition, according to the experience of the present inventors, an increase in viscosity under the above storage conditions is acceptable up to about 1500 centipoise in terms of commercial value; It can be seen that this condition is satisfied without causing liquid separation due to the effect of adding . Example 2 Charge molar ratio (a)/(b) of component (A) and component (B) is 1/0.8
Various softener compositions were prepared in the following manner, and their performance and dispersion stability were evaluated. The results are shown in Table-2.

【table】

Table 2 shows that all of the compositions of the present invention have good performance and excellent dispersion stability. On the other hand, as shown in the comparative example, when the ratio of component (C) to component (A) is too small outside the range specified by the present invention (No. 17), the viscosity increases significantly over time of storage; If the amount is too large (No. 18), it is not preferable because liquid separation tends to occur and the performance that should be improved by the addition of component (B) tends to be adversely affected. Example 3 Using dioleyldimethylammonium chloride as component (A) and varying the amount of polyacrylic acid as component (B), softener compositions having the following compositions were prepared and their performance was evaluated. The results are shown in Table-3. (A) component; dioleyldimethylammonium chloride (iodine value = 73): 9 (%) (B) component; polyacrylic acid (average molecular weight = 1000):
0 to about 2.3 (%) (C) component; POE (=50) oleylamine: 2 (%)
[(A)/(C) weight ratio = 4.5/1] Component (D): Salt: 0.2 (%) Glycerin: 10 (%) Ion-exchanged water: remainder The above component (A) is used as a mixture with isopropanol. As provided, isopropanol is incorporated into the composition at about 3%.

[Table] From Table 3, it can be seen that the addition of component (B) improves the flexibility and/or antistatic properties of acrylic cloth, but it may also improve the flexibility of cotton towels. It is also clear that In other words, these effects occur when the charge molar ratio (a)/(b) is 1/0.2
It is more noticeable in the range of 1/2.0 to 1/2.0, more preferably 1/0.5 to 1/1.0. Furthermore, the dispersion stability of the compositions of the present invention is good, and this is presumed to be mainly attributable to the effect of adding glycerin in components (C) and (D). Example 4 Charge molar ratio (a) of sodium polyacrylate as component (B) to various poorly water-soluble di/tri long chain alkyl/alkenyl quaternary ammonium salts listed in Table 4 as component (A) A softener composition having the following composition was prepared so that /(b) was equivalent, and its performance was evaluated and compared with a case in which sodium polyacrylate was not added. The results are shown in Table 4. (A) Component; (Quaternary ammonium salt listed in Table 4): 5.0 (%) (B) Component; Sodium polyacrylate (average molecular weight
7000): 0 (%) or the amount at which the charge molar ratio (a)/(b) becomes 1/1 (C) component; POE (=20) branched alkyl ether (C ₁₃ . ₁₅ , branching rate 50%): 0.4 (%) [(A)/(C) weight ratio = 12.5/1] (D) component; Propylene glycol: 6.0 (%) Ion exchange water: remainder

【table】

Table 4 shows that the carboxylic acid type anionic polymer used in the present invention has a performance improving effect on any poorly water-soluble quaternary ammonium salts having different structures. That is, in Table 4, it can be seen that by adding an equivalent amount of sodium polyacrylate to component (A), the performance, especially the flexibility and antistatic properties of the acrylic cloth, was significantly improved in all cases. Further, the dispersion stability of the above-mentioned compositions of the present invention is good.

Claims (1)

[Scope of Claims] 1 (A) a poorly water-soluble quaternary ammonium salt type cationic surfactant having 2 to 3 alkyl or alkenyl groups having 14 to 24 carbon atoms in the molecule; (B) a carboxylic acid type cationic surfactant; It contains an anionic polymer, (C) a polyoxyethylene-added nonionic surfactant, and (D) an aqueous vehicle, and the weight ratio of (A)/(C) is 100/1 to 3/1.
A liquid softener composition characterized in that it is in the range of.