JPH0827669A - Liquid softener composition - Google Patents

Abstract

PURPOSE:To provide a liquid softener composition capable of imparting excellent softness to fibers and manifesting excellent coloring matter stability for a long period by using a specific substrate for softening fibers, a colorant and a specific phenol in combination and regulating the pH in an acidic region. CONSTITUTION:This liquid softener composition comprises (A) 3-30wt.% fiber softener selected from among a di-long-chain quaternary ammonium salt represented by formula I [R1 is a 16-25C alkyl or alkenyl group divided by an ester group or an amide group including the dividing group; R2 is R1 or a 14-24C alkyl or alkenyl; R3 and R4 are each a 1-4C alkyl or hydroxyalkyl; X is an anion) and a neutralized substance of a di-long-chain amine represented by formula II (R5 is R1; R6 is R2; R7 is R3 or R4), (C) 1-100ppm colorant comprising C.I. Acid Yellow #3 and/or #141 and (C) 0.1-1000ppm 2,6-di-tert-butyl-4- methylphenol in combination and is regulated to pH2-3.

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):
Or 2 or more kinds of fiber softening bases: 3 to 30 wt% and the following (b) component: 1 to 100 ppm The following (c) component: 0.1 to 1000 ppm are contained, and the pH of the composition is 2 to 5 It is in the range of.

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

Embedded image (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) A neutralized product of a dilong-chain amine represented by the general formula (II) of the chemical formula 4.

[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 yellow # 3
And / or a colorant consisting of Acid Yellow # 141. (C) 2,6-di-tert-butyl-4-methylphenol.

[0008]

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

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

Embedded image (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.

[Chemical 7]

[0013]

Embedded image

[0014]

[Chemical 9]

[0015]

[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)

In the above general formula, R ₁₁ CO- and R ₁₃ CO- 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 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 dilong-chain amine (2) of the component (a) is represented by the general formula (II) shown below.

[0018]

Embedded image (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
Rukyl group) Specific examples of these di-long chain amines (a-2) include:
The following general formulas II-1, 1-2, 13 and 14,
The examples shown in II to 14 are mentioned.

[0019]

[Chemical 12]

[0020]

[Chemical 13]

[0021]

Embedded image

[0022]

[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. )

In the above general formula, R ₂₁ CO- and R ₂₃ CO- 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 ₇ is an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, specifically, 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. Among them, 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) is composed of (a-1) dilong-chain quaternary ammonium salt and (a)
2) The dilong-chain amine neutralized product may be blended alone or in combination, and the total amount is 3 to 30% by weight, preferably 5 to 15% by weight. It is preferable to mix it in. 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, the following chemical formula 1
A neutralized product of tri-long-chain amine represented by 6 (general formula III) can also be blended.

[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 yellow # 3 and / or acidic yellow # 141 is used.
The above dye is used and exhibits stable coloring performance even in the coexistence of the component (a) and in an acidic pH range. The colorant as the component (b) is incorporated in the softener composition in an amount of 1 to 100 ppm, preferably 1 to 50 ppm. If the blending amount deviates from the above range, it may not be possible to impart a yellowish tint. As the colorant as the component (b), the dye having the color index yellow # 3 and the dye having the color index # 141 may be blended alone or in combination. Component (c), 2,6-di-tert-butyl-4
-Methylphenol is present in the softener composition in an amount of 0.1-10
00 ppm, preferably 5-500 ppm.
If the blending amount is less than 0.1 ppm, the color tone deteriorates,
On the other hand, if it exceeds 1000 ppm, the composition may thicken due to storage.

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. Examples include chelating agents such as 1-hydroxy-1,1-diphosphonic acid, 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 and a specific (b) selected from a specific di-long-chain quaternary ammonium salt having a hydrocarbyl group and a di-long-chain amine neutralized product. By using a colorant and (c) 2,6-di-tert-butyl-4-methylphenol in combination, and adjusting the pH to 2 to 5 to obtain a liquid softening agent composition, excellent fibers and clothes were obtained. Not only can flexibility be imparted, but also excellent dye stability can be obtained especially during long-term storage.

[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) Dyeability test A multi-woven mixed woven fabric composed 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 observed Δ: Some dyeing is recognized ×: Dyeing is recognized (2) Stability (discoloration / fading) test The softener composition described below is put in a glass bottle and sealed to obtain a sample. To do. 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 11 Liquid softener 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.

[0033]

[Table 1]Table 1: Overall composition of the softener composition Compounding amount (wt%) Ingredients: (a) component; described in Tables 2 and 3 described in Tables 5 and 6 (b) component; described in Table 4 described in Tables 5 and 6 (C) component; 2,4-di-tert-butyl-4-methylphenol described in Tables 5 and 6 Common ingredients: Ethanol 2 Ethylene glycol 6 Salt 0.1 Perfume 0.5 Polyoxyethylene (60 mol on average) Beef tallow alkylamine 2.0 (Lion Akzo: Trade name Esomin T70) Remaining water Total 100 wt% The pH of the composition was adjusted to 3.0 with hydrochloric acid.

[0034]

[Table 2]  In Table 2, the charge is omitted for convenience.

[0035]

[Table 3]  Dilong chain amines are all neutralized with equimolar hydrochloric acid

[0036]

[Table 4] Table 4: (b) Colorant b component: b-1 color index acidic yellow # 3 b-2 color index acidic yellow # 141 b-3 color index acidic yellow # 141 / acidic blue # 9 = 10 / 1 (weight ratio) Blend b-4 Color Index Acid Yellow # 23 (Comparative)

[0037]

[Table 5] Table 5: Composition and dye stability of (a), (b) and (c) components and dyeability (a) component (b) component (c) component Evaluation symbol amount (wt%) Symbol Amount (ppm) Amount (ppm) Stability Dyeability Comparative Example 1 a-1 13 b-4 30 1 × × a-11 2 Comparative Example 2 a-1 3 b-4 30 30 × × a-11 6 a-3 3 Comparative Example 3 a-4 12 b-4 30 10 × × Comparative Example 4 a-1 15 b-1 10 0 × ○

[0038]

[Table 6] Table 6: Blend composition and dye stability of components (a), (b), and (c) and dyeability (a) component (b) component (c) component Evaluation symbol amount (wt%) Symbol Amount (ppm) Amount (ppm) Stability Dyeability Example 1 a-1 13 b-2 30 300 ○ ○ a-11 2 Example 2 a-1 3 b-2 20 200 ○ ○ a-12 6 a-3 3 Example 3 a-4 12 b-2 20 50 ○ ○ Example 4 a-5 15 b-1 10 100 ○ ○ Example 5 a-6 13 b-1 20 10 ○ ○ b-15 2 Example 6 a-17 15 b-1 20 20 ○ ○ Example 7 a-1 10 b-2 30 250 ○ ○ a-12 3 Example 8 a-6 13 b-1 20 30 ○ ○ a-16 2 Example 9 a-4 10 b-1 20 20 ○ ○ a-14 5 Example 10 a-1 14 b-3 25 300 ○ ○ a-11 1 Example 11 a-2 10 b-1 10 40 ○ ○ a-13 2

Claims (1)

[Claims] 1. (a) The following (a of 1) and (a of 2)
One or more fiber softening bases selected from: 3 to 3
0% by weight The following (b) component: 1 to 100 ppm The following (c) component: 0.1 to 1000 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
Alkyl group) (b) Color index acidic yellow # 3 and / or
Is a colorant consisting of acidic yellow # 141 (c) 2,6-di-tert-butyl-4-methylphenyl
Enor