JPH06228873A - Liquid softening agent composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent low-temperature stability and imparting clothes with excellent softness by compounding a di(long-chain) quaternary ammonium salt with a neutralized amine containing functional group and a nonionic surfactant. CONSTITUTION:A liquid softening agent composition especially having excellent low-temperature stability is produced by compounding (A) a di(long-chain) quaternary ammonium salt of formula I [R1 is 16-25C (including dividing group) alkyl or alkenyl divided with an ester or amide group (called as hydrocarbyl group); R2 is the above hydrocarbyl group or 14-24C alkyl or alkenyl; R3 and R4 are 1-4C alkyl or hydroalkyl; X is anion] with (B) a neutralized tri(short-chain) t-amine containing functional group and expressed by formula II (R5 is 1-4C alkyl or hydroalkyl; (m) and (n) are 1-4; X and Y are functional groups selected from COOH, OH and NH2) and (C) an alkylene oxide-added nonionic surfactant. The hydrocarbyl group is alkylalkenyl group divided with ester or amide group and expressed by formula III or formula IV (R11 is alkyl, etc.; R12 is alkylene, etc.; total carbon number of R11 and R12 is 15-24; the carbon number of R12 is preferably 1-4).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid softener composition for imparting flexibility to fibers and clothing, and more particularly to a liquid softener composition having excellent stability at low temperatures.

[0002]

2. Description of the Related Art Conventionally, a di-long chain alkyl di-short chain alkyl quaternary ammonium salt has been widely used as a liquid softening agent for clothes because it imparts excellent flexibility. Various additives such as ethoxylates of higher alcohols and amines (Japanese Patent Laid-Open No. 62-223375) have been proposed in order to stabilize a liquid softening agent which is a cationic activator dispersion liquid. There is a drawback that the stability at low temperature is deteriorated due to the difference in the type of agent, which is not satisfactory. Therefore, attempts have been made to stabilize using other additives, but they are still inadequate, and development of compositions that are stable even at low temperatures is desired.

[0003]

SUMMARY OF THE INVENTION The present invention provides a liquid softener composition having excellent stability at low temperatures.

[0004]

The liquid softener composition of the present invention is characterized by containing the following components (a), (b) and (c).

(A) Di-long-chain quaternary ammonium salt represented by Chemical formula 3 (general formula I)

[Chemical 3] (R _1: carbon atoms 16 to 25, including cutting group, preferably 18 to 23, the ester group or amide shed alkyl or alkenyl group with a group (hereinafter also referred to as a hydrocarbyl radical) R ₂ : carbon atoms 16 to 25, preferably hydrocarbyl groups 18-23 or 14-24 carbon atoms, preferably an alkyl group or an alkenyl group R ₃ of 16-18, R _4: an alkyl group having 1 to 4 carbon atoms hydroxyalkyl group X ^-: an anion)

(B) A neutralized product of a functional group-containing amine represented by Chemical formula 4 (general formula II).

[Chemical 4] (R ₅ : an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group m, n: an integer of 1 to 4 X, Y: a functional group selected from —COOH, —OH or —NH ₂ ).

(C) An alkylene oxide addition type nonionic surfactant.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION (a) A dilong quaternary ammonium salt has two long chain hydrocarbon groups R ₁ and R ₂ , at least one of which (R ₁ ) is a hydrocarbyl group, One long-chain hydrocarbon group R ₂ is a hydrocarbyl group, an alkyl group or an alkenyl group. The hydrocarbyl group is
It is an alkyl group or an alkenyl group divided by an ester group or an amide group represented by the following chemical formula 5.

[0009]

[Chemical 5] (R ₁₁ : alkyl group or alkenyl group R ₁₂ : alkylene group or alkenylene group, provided that R ₁₁
And R ₁₂ have a total carbon number of 15 to 24, and the carbon number of R ₁₂ is preferably 1 to 4. )

Specific examples of the di-long-chain quaternary ammonium salt of (a-1) include the following chemical formulas 6, 7, 8 and 9 (general formulas I-1 to I-14). It

[0011]

[Chemical 6]

[0012]

[Chemical 7]

[0013]

[Chemical 8]

[0014]

[Chemical 9] (R _3, R _4: an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms R _21: an alkyl group or alkenyl group, R ₂₁ and R
_{22 has} a total carbon number of 15 to 24 R ₂₂ : an alkylene group having 1 to 4 carbon atoms R ₂₃ : an alkyl group or an alkenyl group, and R ₂₃ and R
_{24 has} a total carbon number of 15 to ₂₄ R ₂₄ : an alkylene group having 1 to 4 carbon atoms R ₂₅ : an alkyl group or an alkenyl group, and R ₂₅ and R
The total carbon number of ₂₂ is 15 to 24 R ₂₆ : an alkyl group or an alkenyl group, R ₂₆ and R
_{24 has} a total carbon number of 15 to 24 R ₂₇ : an alkyl group or an alkenyl group having a carbon number of 14 to 24 X ⁻ : anion)

R ₂₁ CO- and R ₂₃ CO- in the above general formula are usually saturated higher fatty acids such as stearic acid and palmitic acid, unsaturated higher fatty acids such as oleic acid, elaidic acid, linoleic acid and linolenic acid, and beef tallow. , Butterfat, palm oil, palm kernel oil, soybean oil, safflower oil, sunflower oil, olive oil and other natural oils and fats are derived from fatty acids obtained by refining, but among them, oleic acid, stearin Acids, tallow fatty acids, hydrogenated tallow fatty acids, palm oil fatty acids, hydrogenated palm oil fatty acids, palm kernel oil fatty acids, and hydrogenated palm kernel oil fatty acids are preferred. As the unsaturated higher fatty acid, the stereoisomer may be a cis isomer, a trans isomer, or a mixture of the two, and in particular, the cis isomer / trans isomer ratio is 25/75 to 100/0. (Weight ratio) is preferable.

R ₂₁ and R ₂₃ may be the same or different. R ₂₂ and R ₂₄ are alkylene groups having 1 to 4 carbon atoms, specifically, a methylene group, an ethylene group, a propylene group, and a butylene group, and may be linear or branched.
Specific examples of R ₂₅ , R ₂₆ , and R ₂₇ include lauryl group, myristyl group, palmityl group, stearyl group, oleyl group,
Examples thereof include a linole group and a linolene group. R ₃ , R
₄ may be the same or different and each has 1 carbon
~ 4 alkyl group or hydroxyalkyl group,
Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group.
Particularly, a methyl group, an ethyl group and a hydroxyethyl group are preferable. X ⁻ is an anion, and specific examples thereof include halogen atom anions such as chlorine, bromine and iodine, and a sulfate anion represented by R ₄₁ SO ₄ . Here, R ₄₁ is an alkyl group having 1 to 3 carbon atoms, and a methyl group is particularly preferable.

The (a) dilong-chain quaternary ammonium salt is preferably contained in the liquid softener composition of the present invention in an amount of 3 to 30% by weight, preferably 5 to 15% by weight.
As the functional group-containing amine of the component (b), the following chemical formula 1
And compounds represented by formula 11 (general formulas II-1 to II-6).

[0018]

[Chemical 10]

[0019]

[Chemical 11]

In the above formula, m and n are each an integer of 1 to 4, and R ₅ has 1 to 4 carbon atoms like R ₃ and R ₄ of the dilong-chain quaternary ammonium salt of the component (a). Is an alkyl group or a hydroxyalkyl group. The functional group-containing amine is neutralized with a commonly used acid. As an acid,
For example, inorganic acids such as hydrochloric acid and sulfuric acid, acetic acid, benzoic acid, and citric acid. Organic acids such as polyacrylic acid can be mentioned.

The (b) functional group-containing amine neutralized product is preferably blended in the liquid softener composition of the present invention in an amount of 0.01 to 5% by weight, preferably 0.05 to 3% by weight, More preferably, it is added in an amount of 0.1 to 2% by weight. As the alkylene oxide addition type nonionic surfactant as the component (c), an alkylene oxide addition product of alcohol or amine, or a fatty acid polyoxyalkylene ester or a lower alkyl ether thereof is used.

As alcohols or amines, higher fatty alcohols having 8 to 24 carbon atoms, preferably 10 to 20 carbon atoms, synthetic alcohols (those obtained by oxidizing n-paraffin, n-olefin or α-olefin, and artificial alcohols) (Including those in which iso-branching and the like are introduced), and higher fatty amines to which alkylene oxide is added are used. Ethylene oxide, propylene oxide, mixtures thereof and butylene oxide are usually used as alkylene oxides. The number of moles of alkylene oxide added is preferably about 5 to 150 moles on average, and is preferably 15 to 100.

Specifically, POE (p = 50) lauryl ether, POE (p = 50) C ₁₂ -C ₁₄ secondary alkyl ether, POE (p = 50) hardened tallow alkylamine, POE (p = 60) ) Beef tallow alkylamine, POE
(P = 25) 2-hexyldecyl ether, POE (p
= 9) POP (p = 10) C _{12 to} C ₁₄ secondary alkyl ether and the like. Here, POE means polyoxyethylene, POP means polyoxypropylene, and p means the average number of moles of alkylene oxide added.

As the fatty acid polyoxyalkylene ester or its lower alkyl ether which is an ester type nonionic surfactant, those represented by the following chemical formula 11 (general formula III) are used.

[0025]

Embedded image RCO (OA) n OR ′ (III) (R: an alkyl group or an alkenyl group having 8 to 20 carbon atoms, preferably 11 to 17 carbon atoms (OA) n: an alkylene oxide is added in an average of n moles. And n = 5 to 150, preferably 15 to 10
0. As the alkylene oxide, ethylene oxide,
R ': hydrogen or a lower alkyl group having 1 to 4 carbon atoms to which propylene oxide or butylene oxide is added alone or in combination)

The nonionic surfactant as the component (c) is preferably contained in the liquid softener composition of the present invention in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight. It

In addition to the above-mentioned components, the softener composition of the present invention may contain, as other optional components, known components that are usually incorporated in the softener composition, within a range that does not impair the effects of the present invention. . As the optional component, for example, a quaternary ammonium salt such as a di-long-chain alkyldi-short-chain alkyl quaternary ammonium salt, a higher fatty acid such as stearic acid or oleic acid, a portion of 2-ethylhexanoic acid and glycerin or pentaerythritol. Nonionic surfactants such as esterified products, salt, water-soluble salts such as ammonium chloride, calcium chloride, magnesium chloride and potassium chloride, solvents such as ethyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, isoprene glycol and hexylene glycol. , Urea, bactericides, antioxidants, dyes, pigments, silicones, hydrocarbons, cellulose derivatives, ultraviolet absorbers, optical brighteners, and fragrances.

[0028]

INDUSTRIAL APPLICABILITY According to the present invention, a liquid softening agent containing (a) a di-long-chain quaternary ammonium salt, (b) a functional group-containing neutralized amine and (c) a specific nonionic surfactant is blended. By using the composition, the low temperature stability can be improved.

[0029]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but prior to that, the evaluation methods used in the examples will be described.

(1) Evaluation Method of Low Temperature Stability The liquid softener composition was placed in a test tube and stored at -5 ° C for 1 month, and the stability was visually evaluated. Evaluation criteria: ◎ stable for 1 month ○ stable for 15 to 20 days △ stable for 10 to 15 days × destabilized within 10 days

Examples 1 to 8 Liquid softener compositions were prepared by using the components (a), (b) and (c) shown in Tables 1 to 3 and mixing the components in water in the amounts shown in Table 4. The products were prepared and evaluated for low temperature stability and are shown in Table 4.
For the quaternary salt of the component (a), the charge is omitted for convenience. Further, the amine as the component (b) was all neutralized with hydrochloric acid having an equivalent amine value to form a salt.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Table 4] Table 4: Composition of softener and evaluation (a) component (b) component (c) component evaluation type amount amount type amount neutralizing agent type amount stability (wt%) (wt%) (wt%) − 5 ° C ratio a (a) -1 15 − − − (c) -1 3 × Comparative (a) -5 14 − − − (c) -2 2 × Example c (a) -3 5 − − − ( c) -1 0.5 △ 1 (a) -1 15 (b) -1 0.5 Hydrochloric acid (c) -1 3 ◎ 2 (a) -2 15 (b) -2 1 Sulfuric acid (c) -2 2 ◎ 3 ( a) -3 15 (b) -3 0.5 hydrochloric acid (c) -1 3 ◎ 4 (a) -3 14 (b) -3 0.5 sulfuric acid (c) -2 1 ◎ fruit 5 (a) -3 15 (b ) -3 1 Hydrochloric acid (c) -1 2 ◎ 6 (a) -3 14 (b) -3 1 Acetic acid (c) -1 3 ○ 7 (a) -3 15 (b) -3 0.5 Citric acid (c ) -2 2 ○ Application 8 (a) -3 15 (b) -3 1 Benzoic acid (c) -1 3 ○ 9 (a) -3 14 (b) -3 1 PAA (c) -1 3 ○ 10 (a) -4 15 (b) -4 1 Hydrochloric acid (c) -2 1 ◎ Example 11 (a) -5 14 (b) -5 0.5 Sulfuric acid (c) -1 2 ◎ 12 (a) -6 15 ( b) -6 1 hydrochloric acid (c) -1 3 ◎ 13 (a) -3 5 (b) -1 0.2 hydrochloric acid (c) -1 0.5 ◎ 14 (a) -1 15 (b) -1 0.5 hydrochloric acid (c ) -3 3 ○ (Note) PAA: Polyacrylic acid

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location D06M 13/20

Claims (1)

[Claims] 1. A long di-chain quaternary ammonium salt represented by the formula (a) (formula I): (R ₁ : an alkyl group or an alkenyl group having a carbon number of 16 to 25, including a splitting group, which is split by an ester group or an amide group, R ₂ : an ester group having a carbon number of 16 to 25, including a splitting group, or Alkyl group or alkenyl group divided by an amide group, or alkyl group or alkenyl group having 14 to 24 carbon atoms R ₃ , R ₄ : alkyl group having 1 to ₄ carbon atoms or hydroxyalkyl group X ⁻ : anion) (b ) Chemical Formula 2 (general formula II) Neutralized product of functional group-containing amine (R ₅ : an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, m, n: an integer of 1 to 4 X, Y: a functional group selected from —COOH, —OH or —NH ₂ ) (c) alkylene oxide addition A liquid softening agent composition comprising a nonionic surfactant.