JPH0718573A - Liquid softener composition - Google Patents

Abstract

(57) [Summary] [Structure] (a) A di-long-chain quaternary ammonium salt having a long-chain alkyl group or alkenyl group divided by an ester group or an amide group represented by the general formula (I) in Chemical formula 1 Or a neutralized product of di-long-chain amine, (b) Color Index Acid Red # 33, # 138, Color Index Reactive Red # 3: 1, # 120, Color Index Food Red # 1
And a liquid softener composition having a pH of 2 to 5, containing one or more coloring agents selected from the group consisting of a mixture thereof. [Effect] Not only can excellent flexibility be imparted to fibers and clothing, but also excellent dye stability can be obtained especially during long-term storage. [Chemical 1] (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 shed alkyl or alkenyl group with an amide group or an alkyl or alkenyl group R ₃ having a carbon number 14~24,, R _4: an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group X ^-: an anion)

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 clothes, and more particularly to a liquid softener composition having excellent dye stability during long-term storage.

[0002]

2. Description of the Related Art Conventionally, a quaternary ammonium salt having a mono- or di-long-chain alkyl group has been used as a softening base for imparting flexibility to fibers and clothing.
This product does not have good biodegradability, and a softening base having good biodegradability is desired. To obtain good biodegradability,
Many of them have an ester bond in the carbon chain, but it is necessary to maintain the pH of the composition on the acidic side because hydrolysis proceeds. On the other hand, in order to enhance the commercial value as a softening agent, it is generally required to mix and color a pigment. However, since the pH of the composition is acidic, a new problem occurs such that the dye is dyed on the fiber during the treatment, and the color is discolored during storage. Therefore, there is a demand for a liquid softener having good biodegradability, which can contain a dye that is stable even under acidic pH.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a liquid softener composition having excellent dye stability during long-term storage.

[0004]

The liquid softener composition of the present invention comprises (a) 1 selected from the following (a 1) and (a 2):
One or two or more kinds of fiber softening bases: 3 to 30% by weight and the following component (b): 0.1 to 100 ppm, and the pH of the composition is in the range of 2 to 5.

(A-1) A di-long-chain quaternary ammonium salt represented by the general formula (I) of Chemical formula 3.

[Chemical 3] (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 shed alkyl or alkenyl group with an amide group or an alkyl or alkenyl group R ₃ having a carbon number 14~24,, R _4: an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group X ^-: an anion)

(A-2) Neutralized product of dilong chain amine represented by the general formula (II)

[Chemical 4] (R_Five: Estheses with 16 to 25 carbon atoms, including splitting groups
Alkyl group or alkyl group separated by
Kenyl group R₆: An ester having 16 to 25 carbon atoms including a splitting group
Alkyl or alkene separated by a group or amide
A nyl group, or an alkyl group having 14 to 24 carbon atoms, or
Alkenyl group R₇: An alkyl group having 1 to 4 carbon atoms or hydroxy group
Rukiru group)

(B) Color index acidic red # 3
3, # 138, Color Index Reactive Red # 3:
1 or 2 or more colorants selected from the group consisting of 1, # 120, color index food red # 1 and mixtures thereof.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As the fiber softening base of the component (a), (a 1) a specific di-long-chain quaternary ammonium salt or (a 2) a neutralized product of a di-long-chain amine is used. To be

The (a-1) dilong-chain quaternary ammonium salt is represented by the following general formula (I).

[Chemical 5] (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 shed alkyl or alkenyl group with an amide group or an alkyl or alkenyl group R ₃ having a carbon number 14~24,, R _4: an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group X ^-: an anion)

This di-long-chain 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, and one long-chain hydrocarbon group. The hydrogen group R ₂ is a hydrocarbyl group, an alkyl group or an alkenyl group. The hydrocarbyl group has the following formula
Is an alkyl group or an alkenyl group divided by an ester group or an amide group.

[0011]

[Chemical 6] (R ₈ : alkyl group or alkenyl group R ₉ : alkylene group or alkenylene group, provided that R ₈
The total number of carbon atoms of the R ₉ is 15 to 24, the carbon number of R ₉ is 1-4 are preferable. )

Specific examples of the di-long-chain quaternary ammonium salt as the component (a) include the following chemical formulas, chemical formulas 8, 9 and 10.
(General formulas I-1 to I-14) are exemplified.

[0013]

[Chemical 7]

[0014]

[Chemical 8]

[0015]

[Chemical 9]

[0016]

[Chemical 10] (R _3, R _4: an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms R _11: an alkyl group or alkenyl group, R ₁₁ and R
_{12 has} a total carbon number of 15 to 24 R ₁₂ : an alkylene group having 1 to 4 carbon atoms R ₁₃ : an alkyl group or an alkenyl group, and R ₁₃ and R
The total number of carbon atoms of ₁₄ is 15 to 24 R ₁₄ : an alkylene group having 1 to 4 carbon atoms R ₁₅ : an alkyl group or an alkenyl group, and R ₁₅ and R
The total carbon number of ₁₂ is 15 to 24. R ₁₆ is an alkyl group or an alkenyl group, and R ₁₆ and R
_{14 has} a total carbon number of 15 to 24 R ₁₇ : an alkyl group or an alkenyl group having a carbon number of _{14 to} 24 X ⁻ : anion)

R ₁₁ CO- and R ₁₃ 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 fats and oils are derived and derived from fatty acids, among which oleic acid and stearin are particularly preferred. 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 ₁₁ and R ₁₃ may be the same or different. R ₁₂ and R ₁₄ are alkylene groups having 1 to 4 carbon atoms, specifically, a methylene group, an ethylene group, a propylene group, and a butylene group, which may be linear or branched.
Specific examples of R ₁₅ , R ₁₆ and R ₁₇ 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 a halogen atom anion such as chlorine, bromine and iodine, and a sulfate anion represented by R ₃₁ SO ₄ . Here, R ₃₁ is an alkyl group having 1 to 3 carbon atoms, and a methyl group is particularly preferable. Similarly, the (a) component (a-2) dilong-chain amine is represented by the general formula (II) of the following chemical formula 11, and more specifically, the following chemical formulas 12, 13 Conversion 14,
The compounds represented by Chemical formula 15 (general formulas II-1 to II-14) are used.

[0019]

[Chemical 11] (R_Five: Estheses with 16 to 25 carbon atoms, including splitting groups
Alkyl group or alkyl group separated by
Kenyl group R₆: An ester having 16 to 25 carbon atoms including a splitting group
Alkyl or alkene separated by a group or amide
A nyl group, or an alkyl group having 14 to 24 carbon atoms, or
Alkenyl group R₇: An alkyl group having 1 to 4 carbon atoms or hydroxy group
Rukiru group)

[0020]

[Chemical 12]

[0021]

[Chemical 13]

[0022]

[Chemical 14]

[0023]

[Chemical 15] (R ₇ : an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group R ₂₁ : an alkyl group or an 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
The total number of carbon atoms of ₂₄ is 15 to 24. R _27: an alkyl group or alkenyl group having 14 to 24 carbon atoms. )

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 a lauryl group, myristyl group, palmityl group, stearyl group, oleyl group, linole group and linolene group. R
₇ is an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, and specific examples thereof 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. However, a methyl group, an ethyl group and a hydroxyethyl group are particularly preferable.

The above di-long chain amine is neutralized with a commonly used acid. Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and organic acids such as benzoic acid, citric acid and polymeric acrylic acid. The fiber softening base of the component (a) may be a combination of (a 1) a dilong-chain quaternary ammonium salt and (a 2) a neutralized product of a dilong-chain amine, either alone or in combination. The total amount is preferably 3 to 30% by weight, preferably 5 to 15% by weight in the softener composition. If the content is less than 3% by weight, the flexibility tends to decrease, while if it exceeds 30% by weight, formulation becomes difficult. In the softener composition of the present invention, a neutralized product of tri-long-chain amine represented by the following chemical formula 16 (general formula III) may be blended.

[0026]

[Chemical 16] (R_Five, R₆, R₄₁: Hydrocarbi having 16 to 25 carbon atoms
Ru group)

Specific examples of the tri-long-chain amine include tri (stearoyloxyethyl) amine, tri (oleoyloxyethyl) amine and tri (palmitoyloxyisopropyl) amine. Specific examples of the acid used for neutralization are the same as those in the case of (a-2) the di-long-chain amine neutralized product. These tri-long-chain amine neutralized products are preferably blended in an amount of 10% by weight or less based on the fiber softening base of the component (a). If it is blended in excess of this amount, the softening effect on cotton will be reduced.

As the colorant of the component (b), color index acidic red # 33, # 138, color index reactive red # 3: 1, # 120, color index edible red # 1 and a mixture thereof are used. One or two or more selected from the group consisting of the following are used, and stable coloring performance is exhibited even in the coexistence of the component (a) and in the acidic pH range. The colorant as the component (b) is added to the softener composition in an amount of 0.1 to 100 ppm, preferably 1 to 50 ppm. If the blending amount is less than 0.1 ppm, a pinkish tint may not be imparted, which is not preferable. On the other hand, if it exceeds 100 ppm, it may cause dyeing of fibers and clothing, which is not preferable.

In the liquid softener of the present invention, in addition to the above-mentioned components, known components which are usually added to softener compositions can be added as long as they do not impair the effects of the present invention. The final product is balanced with water. 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, silicones, hydrocarbons, cellulose derivatives, ultraviolet absorbers, optical brighteners, and fragrances. It is important that the liquid softener composition of the present invention has a pH in the range of 2 to 5, preferably 2 to 4. If the pH range deviates from the above range, hydrolysis of the softening base will occur, which is not preferable.

[0030]

INDUSTRIAL APPLICABILITY According to the present invention, (a) a fiber softening base selected from a specific di-long chain quaternary ammonium salt having a hydrocarbyl group and a di-long chain amine neutralized product and a specific colorant are used. By using together and adjusting the pH to 2 to 6 to form a liquid softener composition, not only excellent flexibility can be imparted to fibers and clothing, but also excellent dye stability especially in long-term storage can be obtained.

[0031]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but prior to this, the evaluation methods adopted in the Examples will be shown.

(1) Dyeing property test A multi-woven mixed woven fabric consisting of 9 kinds of fibers of polyester, cotton, acrylic, rayon, wool, acetate, vinylon, nylon and silk is used. 10% of a softening agent composition (aqueous dispersion liquid), which will be described later, using a multi-woven mixed woven fabric with a draw ratio of 200%.
Is dropped on all the fibers of the cloth, left for 3 hours, rinsed with tap water for 3 minutes, and naturally dried. Then, the dyeing on the dried cloth is visually observed, and the degree of dyeing on the clothing is evaluated according to the following criteria. ◯: Almost no dyeing is found Δ: Some dyeing is found ×: Dyeing is found

(2) Stability (discoloration / fading) test The softener composition described below is put in a glass bottle and sealed to obtain a sample. This sample is placed in a constant temperature bath of 80 ° C., and after 40 hours, the color tone is compared with that of a product stored at 5 ° C., and the stability to heat is evaluated according to the following criteria. ◯: Discoloration / fading is not observed Δ: Discoloration / fading is slightly recognized ×: Discoloration / fading is clearly recognized

Examples 1 to 13 Liquid softening agent compositions shown in Tables 1 to 6 were prepared, and stability (discoloration, decolorization) and dyeing property to various fibers were evaluated. The results are shown in Tables 5 and 6.

[0035]

[Table 1] Table 1: Overall composition of the softening agent composition (wt%) A composition B composition component: (a) component; described in Tables 2 and 3 Tables 5 and 6 described (b) component; table Listed in Tables 4 and 5 Common components: Ethanol 21 Ethylene glycol 6 3 Salt 0.1 0.01 Perfume 0.5 0.2 Polyoxyethylene (60 mol on average) Beef tallow alkylamine 2.0- (Lion Akzo: trade name Esomin T70) Poly Oxyethylene (average 40 mol) nonyl phenyl ether-0.2 water balance 100 wt% total balance The pH of the composition was adjusted to 2.5 with hydrochloric acid.

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4] Table 4: (b) Colorant b component: b-1 Color index acidic red # 18 (comparative product) b-2 Color index acidic red # 92 (comparative product) b-3 Color index acidic red # 94 (Comparative product) b-4 Color index Basic red # 10 (Comparative product) b-5 Color index Acidic red # 33 b-6 Color index Acidic red # 138 b-7 Color index Reactive red # 3: 1 b- 8 Color Index Reactive Red # 120 b-9 Color Index Food Red # 1

[0039]

[Table 5] Table 5: Composition and stability of both components (a) and (b), and dyeability (a) component (b) component symbol amount (wt%) symbol amount (ppm) common component stability Dyeability Comparative Example 1 a-1 15 b-1 10 Ax- a-11 1 Comparative Example 2 a-15 b-2 15 A Δ-a-25 a-3 7 a-11 0.1 a-12 0.5 a-13 0.7 Comparative Example 3 a- 35 b-36 Bx- a-13 1 Comparative Example 4 a-6 5 b-4 1 B o x a-16 0.5 Comparative Example 5 a-2 10 b- 3 10 A × -Comparative Example 6 a-11 5 b-2 20 B Δ -Example 1 a-1 15 b-5 10 A ○ ○ a-11 1 Example 2 a- 11 b-5 10 A ○ ○ a-25 a-37 a-11 0.1 a-12 0.5 a-13 0.7

[0040]

[Table 6] Table 6: Composition and stability of both components (a) and (b) and dyeability (a) component (b) component symbol amount (wt%) symbol amount (ppm) common component stability Dyeability Example 3 a- 35 b-6 3 B ○○ a-13 0.5 Example 4 a-45 b-6 3 B ○○ a-14 0.5 Example 5 a-5 5 b-7 5 B ○ ○ a-15 0.5 Example 6 a-5 11 b-8 15 A ○ ○ a-15 2 Example 7 a-6 5 b-8 8 B ○ ○ a-16 1 Example 8 a-5 3 b-6 5 B ○○ a-17 2 Example 9 a-7 3 b-5 3 B ○○ a-17 2 Example 10 a-7 8 b-6 10 A ○○ a-17 5 Example 11 a-3 10 b-9 8 A ○ ○ a-17 3 Example 12 a-35 b-6 3 B ○ ○ Example 13 a-17 10 b-7 15 A ○ ○

Claims (1)

[Claims] 1. (a) The following (a of 1) and (a of 2)
One or more fiber softening bases selected from: 3 to 30
% By Weight The following component (b): 0.1 to 100 ppm is contained, and the pH of the composition is in the range of 2 to 5.
Liquid softening agent composition. (1 of a) The di-long chain fourth represented by the general formula (I) of Chemical formula 1
Grade ammonium salt(R₁: Estheses with 16 to 25 carbon atoms, including splitting groups
Alkyl group or alkyl group separated by
Kenyl group R₂: An ester having 16 to 25 carbon atoms including a splitting group
Alkyl or alkene separated by a group or amide
A nyl group, or an alkyl group having 14 to 24 carbon atoms, or
Alkenyl group R₃, R_Four: An alkyl group having 1 to 4 carbon atoms or hydroxy
Alkyl group X^-: Anion) (a-2) A di-long-chain amine represented by the general formula (II)
Neutralized product (R_Five: Estheses with 16 to 25 carbon atoms, including splitting groups
Alkyl group or alkyl group separated by
Kenyl group R₆: An ester having 16 to 25 carbon atoms including a splitting group
Alkyl or alkene separated by a group or amide
A nyl group, or an alkyl group having 14 to 24 carbon atoms, or
Alkenyl group R₇: An alkyl group having 1 to 4 carbon atoms or hydroxy group
Rukyi group) (b) Color index acidic red # 33, # 13
8, color index reactive red # 3: 1, # 12
0, color index food red # 1 and their mixture
Coloring of one or more selected from the group consisting of
Agent