JPH0123585B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a fabric softener composition that can impart excellent flexibility and antistatic properties to various fibers. [Prior Art] Household fabric softeners currently on the market are mainly composed of quaternary ammonium salts having one to two long-chain alkyl groups in one molecule. The reason is that quaternary ammonium salts exhibit softness and antistatic properties for clothing. However, such quaternary ammonium salts
Although it shows an excellent flexibility imparting effect on cotton, it does not show sufficient flexibility and antistatic properties on synthetic fibers. In order to improve these drawbacks of quaternary ammonium salts, softening agents have been proposed that use quaternary ammonium salts in combination with various bases. For example, a softening agent using a combination of a quaternary ammonium salt and an anionic surfactant has been proposed (JP-A-53-19497, JP-A-53-38794, JP-A-53-
52799, JP 54-18993, JP 55-112377, JP 58-13775, JP 58-109682, JP 59-
59794, Japanese Unexamined Patent Publication No. 59-59797, etc.), although these have shown some improvement in characteristics, they are still insufficient. In addition, additives for cleaning agents that use a combination of quaternary ammonium salts and anionic polymers have been proposed (Japanese Patent Laid-Open Nos. 59-6298, 61-7398, etc.), but these additives are not suitable for granular cleaning agents. It is an additive and when used as a regular fabric softener, the standard wash time is 10
The problem is that the quaternary ammonium salt is insufficiently hydrated when used for about 10 minutes, and its ability to form benzyl in the washing bath is therefore low, so that it is adsorbed on the fiber surface as coarse particles. As a result, it does not exhibit excellent flexibility and antistatic properties, and also has disadvantages in that adhering particles tend to stand out and stickiness tends to occur. [Problems to be Solved by the Invention] When softening various fibers together, it is necessary to use a large amount of softener to impart flexibility and antistatic properties to all the fibers;
It has been desired to reduce this usage amount. However, to date, no fabric softener has yet been found that exhibits an excellent softening effect even when used in a small amount and also exhibits an excellent antistatic effect on synthetic fibers. The object of the present invention is to provide a fabric softener composition that exhibits the same flexibility imparting effect on cotton as conventional ones, and that exhibits significantly superior flexibility and antistatic properties imparting effect on synthetic fibers compared to conventional ones. It is about providing. [Means for Solving the Problems] As a result of intensive research to achieve the above object, the present inventors have found that by using a predetermined quaternary ammonium salt and a carboxylic acid type anionic polymer in combination, The inventors have discovered that the above problems can be solved, and have completed the present invention. That is, the present invention provides one or more cationic surfactants (component A) represented by the following general formula [],
Provided is a fabric softener composition, which contains a carboxylic acid type anionic polymer (component B), and is characterized in that the component A forms a completely hydrated aggregate. (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are an alkyl group, an alkenyl group, a hydroxylalkyl group, an oxyalkyl group, a polyoxyalkylene group, or a benzyl group, and at least one of them has 8 carbon atoms. ~22 long chain group, X represents halogen, alkyl sulfate, alkyl phosphate, carboxyalkyl or alkylbenzene sulfonate having an alkyl group having 1 to 3 carbon atoms.) Component A represented by the above general formula [] R ₁ ~
At least one of R ₄ is a long chain group, but R ₁ to R ₄
Preferably, two of the groups are long chain groups. Further, the long chain group is particularly preferably one having 16 to 22 carbon atoms. The long chain group is preferably a straight chain type, but may be a branched type. Preferred specific examples of the quaternary ammonium salt of component A include dilauryldimethylammonium salt, dimyristyldimethylammonium salt, dipalmityldimethylammonium salt, distearyldimethylammonium salt, dieicosyldimethylammonium salt, and dibehenyldimethyl. Ammonium salt, dioleyldimethylammonium salt, monopalmityltrimethylammonium salt, monostearyltrimethylammonium salt, trimyristylmethylammonium salt, tripalmitylmethylammonium salt, dihydrogenated beef tallow alkyldimethylammonium salt, trihydrogenated beef tallow alkylmethyl Ammonium salt, dihydrogenated tallow alkylbenzylmethyl ammonium salt, distearylmethylhydroxyethylammonium salt, dipalmitylmethylhydroxypropylammonium salt, distearyldihydroxyethylammonium salt,
Bis(2-methylstearyl)dimethylammonium salt, bis(β-hydroxystearyl)diethylammonium salt, di(3-octadecanoxy-2-hydroxypropyl)dimethylammonium salt, di(3-octadecanoxy-2-hydroxypropyl)methylhydroxy Examples include ethyl ammonium salt, di-(polyoxyethylene-3 octadecanoxy-2-hydroxypropyl) dimethyl ammonium salt, and the like. It is also possible to use imidazolinium salts and amide ammonium salts. As a specific example of X in the general formula [],
Cl, Br, CH ₃ SO ₄ , C ₂ H ₅ SO ₄ , CH ₃ PO ₄ ,
C ₂ H ₅ PO ₄ , CH ₃ COO,

[Effect]

In the fabric softener composition of the present invention, due to the presence of the carboxylic acid type anionic polymer, the amount of quaternary ammonium salts forming fully hydrated aggregates adsorbed onto the fiber surface is significantly increased. , thereby exhibiting excellent flexibility and antistatic properties. The fact that cationic surfactants form fully hydrated aggregates has been reported, for example, in the literature (thermal measurements, 11 ,
104 (1984) by measuring the transition point temperature using a differential scanning calorimeter. That is, by forming a completely hydrated aggregate of the cationic surfactant, the transition point temperature is shifted to a lower temperature side than that of a solid crystal. [Effects of the Invention] The softener composition of the present invention exhibits the same flexibility imparting effect on cotton as the conventional one, and has a much superior softening effect and antistatic effect on synthetic fibers than the conventional one. Shows preventive effect. [Example] Examples and comparative examples of the present invention will be shown below to more specifically explain the effects of the present invention. 1 Method for preparing fabric softener composition sample A 7% by weight dispersion solution of dihardened beef tallow alkyldimethylammonium chloride (Alucard 2HT) was prepared.
By ultrasonic irradiation at 80° C. for 1 hour, an aggregate dispersion in which the cationic surfactant was completely hydrated was obtained. On the other hand, by preparing aqueous solutions of polyacrylic acid or its salts at various concentrations and mixing them with a cationic surfactant dispersion at a predetermined ratio, the flexibility of the cationic surfactant/polyacrylic acid (salt) ratio can be adjusted. Finish composition sample (cationic surfactant concentration is
(constant 5wt%) was obtained. On the other hand, Alucard when preparing this composition
The hydrated solid state transition point of the 2HT dispersion aggregate is determined by differential scanning calorimetry, indicating complete hydration38
It was confirmed that the temperature was ℃. Furthermore, Alucard
The transition point of 2HT in its barely hydrated crystalline state is 60°C. In addition to the method described above, the fabric softener composition may be prepared by adding a solution of a cationic activator such as ethylene glycol directly to an aqueous solution of polyacrylic acid or a salt thereof while stirring. 2. Softening treatment method Using 20ml of the sample composition added to 30% tap water, acrylic cloth and cotton cloth were subjected to softening treatment for 3 minutes at a water temperature of 25°C and a bath ratio of 30 times. 1
After dehydration for a minute, the cloth was conditioned for 48 hours at 20° C. and 50% RH to obtain a test cloth for confirming the effect of imparting flexibility and the effect of imparting antistatic properties. 3 Evaluation Method 1 Adsorption Increase Rate It is known that quaternary ammonium salts exhibit flexibility imparting effects and antistatic properties imparting effects when adsorbed onto clothing. The present inventors believe that an increase in the adsorption amount of quaternary ammonium salts on the fiber surface due to the addition of a carboxylic acid type anionic polymer is a major factor in improving the flexibility imparting effect and the antistatic property imparting effect. The adsorption increase rate shown in the following equation (1) was evaluated by combining the effect of imparting static properties and the effect of imparting antistatic properties. Adsorption increase rate (%) = X-Y/Y x 100...(1) : Adsorption amount when only quaternary ammonium salt is used. Note that the adsorption amount of quaternary ammonium salt on the fabric surface is based on the amount of adsorption of quaternary ammonium salt present in the bath before and after softening treatment. It was determined from the difference in concentration when measured using the method. 2 Softness imparting effect The feel of softened acrylic cloth and cotton cloth is 10
Let human judges judge, and from the average of 10 judges,
The softening effect of the fabric softener composition was evaluated.
The feel was evaluated based on the following criteria, with the feel of acrylic cloth and cotton cloth treated in the same manner as above, except that no fabric softener was used, as zero. Extremely soft 5 points Quite soft 4 points Soft 3 points Slightly soft 2 points Slightly soft 1 point 3 Antistatic property imparting effect Acrylic cloth was charged with an applied voltage of 7KV for 30 seconds using a static honest meter, and the half-life of the charging voltage was measured. Did. As in the case of the adsorption increase rate, the improvement in the effect of imparting antistatic properties due to the addition of the carboxylic acid type anionic polymer was evaluated as the half-life decrease rate shown in the following formula (2). Half-life reduction rate [%] = L - M / L × 100 ... (2) L: Half-life when using a sample containing only quaternary ammonium salt M: Quaternary ammonium salt and carboxylic acid type anionicity Half-life test example 1 using a sample containing a polymer or other anion component A softener composition having the following composition was prepared, and the adsorption increase rate and half-life decrease rate on acrylic cloth were determined. The results are shown in Table-1. (Composition) Component A: Dihardened beef tallow alkyldimethylammonium salt chloride (Alucard 2HT):
5% by weight Component B: Sodium polyacrylate (average molecular weight 1000): 0 to 5 times equivalent in charge molar ratio to component A Water: Balance

[Table] Number/Number of positively charged moles of dicured beef tallow alkyldimethylammonium chloride As shown in Table 1 above, quaternary ammonium salt and sodium polyacrylate are mixed at 1/0.2~
The fabric softener composition samples containing a molar ratio of 1/2.0 (Examples 1-9) exhibit excellent adsorption increase and half-life decrease rates, whereas the sample without sodium polyacrylate (Comparative Example 1) It can be seen that it does not show excellent effects. Test Example 2 A fabric softener composition having the following composition was prepared, and the adsorption increase rate and half-life decrease rate on acrylic cloth were determined. The results are shown in Table-2. (Composition) Component A: Dihardened beef tallow alkyldimethylammonium chloride (Alucard 2HT): 5
Weight% Component B: Compound shown in Table 2: 0.8 times equivalent in charge molar ratio to component A Water: Balance

【table】

[Table] As is clear from Table 2 above, the samples (Examples 4, 10 to 26) in which carboxylic acid type anionic polymers were added to quaternary ammonium salts had excellent adsorption increase rates and half-lives. It can be seen that the figure shows a decreasing rate. On the other hand, the samples to which anionic monomers were added (Comparative Examples 2 and 4) did not show excellent effects, and the samples to which sodium polystyrene sulfonate was added (Comparative Example 3) showed excellent adsorption increase rates, but It can be seen that the half-life reduction rate is extremely reduced, and the antistatic property imparting effect is not shown. Test Example 3 The following two types of granular softeners (Comparative Examples 5 and 6) were prepared, and the adsorption increase rate and half-life decrease rate on acrylic cloth were determined. The results are shown in Table-3. (Comparative Example 5) A granular fabric softener obtained by granulating component A and component B in the same molar ratio as in Example 4 according to JP-A-59-6298. (Comparative Example 6) A granular fabric softener similar to Comparative Example 5 except that sodium polyacrylate having an average molecular weight of 5,000,000 was used as the B component.

[Table] As is clear from Table 3 above, the granular fabric softener shows an excellent adsorption increase rate, but the half-life decrease rate is small. This is because the granulated particles have a low hydration ability in the bath, so the particles are adsorbed onto the cloth surface. On the other hand, in the liquid fabric softener of the present invention, the cationic surfactant is adsorbed on the cloth surface as a completely hydrated aggregate in the bath, and therefore, both the increase in adsorption rate and the decrease in half-life are excellent. In addition, Alucard in the particles of Comparative Examples 5 and 6
It was confirmed that 2HT has a transition point temperature of 60°C and is in a crystalline state. Test Example 4 The effect of imparting flexibility to acrylic fabric and cotton fabric by treatment with a fabric softener was investigated. The results are shown in Table 4. The composition of each test is as follows. (Comparative Example 7) Only water (Comparative Example 8) 5% by weight aqueous dispersion of only component A in Test Example 1 (Comparative Example 9) Granular fabric softener same as Comparative Example 5 (Example 27) Example 4 and Same fabric softener

[Table] As is clear from Table 4, the fabric softener of the present invention exhibits an excellent softening effect on both acrylic fabric and cotton fabric.

Claims (1)

[Scope of Claims] 1 Contains one or more cationic surfactants (component A) represented by the following general formula () and a carboxylic acid type anionic polymer (component B), wherein said component A is completely A fabric softener composition characterized by forming a hydrated aggregate. (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are an alkyl group, an alkenyl group, a hydroxylalkyl group, an oxyalkyl group, a polyoxyalkylene group, or a benzyl group, and at least one of them has 8 carbon atoms. ~22 long-chain group, and X represents halogen, alkyl sulfate, alkyl phosphate, carboxyalkyl, or alkylbenzene sulfonate having an alkyl group having 1 to 3 carbon atoms. 3 to 30% by weight based on the agent composition, and the blending ratio of component A and component B is the ratio of the number of positively charged moles of component A (a) to the number of negatively charged moles of component B (b) (a). The softener composition according to claim 1, wherein )/(b) is 1/0.2 to 1/2.0.