JP3309102B2 - Liquid softener composition - Google Patents

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 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 to impart flexibility to fibers and clothing.
This product does not have good biodegradability, and a softening base having better biodegradability is desired. To obtain good biodegradability,
Although many have an ester bond in the carbon chain, it is necessary to maintain the pH of the composition on the acidic side because hydrolysis proceeds. On the other hand, in order to increase the commercial value as a softener, it is generally required to blend a pigment and to color the pigment. However, since the pH of the composition is acidic, problems such as dyeing of fibers during treatment and discoloration during storage occur. For this reason, a liquid softener having good biodegradability and capable of incorporating a stable dye even under acidic pH is desired.

[0003]

SUMMARY 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) a liquid softener composition selected from the following (a-1) and (a-2):
One or more fiber softening bases: 3 to 30% by weight and the following component (b): 1 to 100 ppm The following component (c): 0.1 to 1000 ppm, and the pH of the composition is 2 to 5 In the range.

(A-1) A dilong chain quaternary ammonium salt represented by the general formula (I):

Embedded image (R ₁ : an alkyl group or alkenyl group having 16 to 25 carbon atoms including a splitting group; an ester group or an alkenyl group split by an ester group or an amide group R ₂ : an ester group or a C 16 to 25 carbon atom including a splitting group An alkyl group or an alkenyl group separated by an amide group, or an alkyl group or an alkenyl group having 14 to 24 carbon atoms R ₃ and R ₄ : an alkyl group or a hydroxyalkyl group having 1 to ₄ carbon atoms X ⁻ : anion)

(A-2) A neutralized dilong chain amine represented by the general formula (II):

Embedded image (R_Five: Esters having 16 to 25 carbon atoms including a splitting group
An alkyl group or an alkyl group
Kenyl group R₆: An ester having 16 to 25 carbon atoms including a splitting group
Alkyl group or alkyl group
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 hydroxya
Ruquil group)

(B) Color index acid yellow # 3
And / or a colorant consisting of acidic yellow # 141. (C) 2,6-di-tert-butyl-4-methylphenol.

[0008]

DETAILED DESCRIPTION OF THE INVENTION As the fiber softening base of the component (a), (a-1) a di-long chain quaternary ammonium salt or (a-2) a di-long chain amine neutralized product is used.

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

Embedded image (R ₁ : an alkyl group or alkenyl group having 16 to 25 carbon atoms including a splitting group; an ester group or an alkenyl group split by an ester group or an amide group R ₂ : an ester group or a C 16 to 25 carbon atom including a splitting group An alkyl group or an alkenyl group separated by an amide group, or an alkyl group or an alkenyl group having 14 to 24 carbon atoms R ₃ and R ₄ : an alkyl group or a hydroxyalkyl group having 1 to ₄ carbon atoms X ⁻ : anion)

This dilong 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, The hydrogen group R ₂ is a hydrocarbyl group, an alkyl group or an alkenyl group. The hydrocarbyl group has the following formula
And an alkyl group or an alkenyl group separated by an amide group.

[0011]

Embedded image (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 of the component (a) include the following chemical formulas (7), (8), (9) and (10).
(General formulas I-1 to I-14) are exemplified.

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[0013]

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[0014]

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[0015]

Embedded image (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 R ₁₂ total carbon number of 15 to 24 of: alkylene group having 1 to 4 carbon atoms R _13: an alkyl group or alkenyl group, R ₁₃ and R
R ₁₄ total carbon number of ₁₄ is 15 to 24: alkylene group having 1 to 4 carbon atoms R _15: an alkyl group or alkenyl group, R ₁₅ and R
The total number of carbon atoms of ₁₂ is 15 to 24 R _16: an alkyl group or alkenyl group, R ₁₆ and R
_{14 has} a total carbon number of 15 to 24 R ₁₇ : an alkyl or alkenyl group having _{14 to} 24 carbons 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 tallow. , Butterfat, palm oil, palm kernel oil, soybean oil, safflower oil, sunflower oil, olive oil, etc., are derived from fatty acids obtained by decomposing and refining, especially oleic acid, stearin Acids, tallow fatty acids, hardened tallow fatty acids, palm oil fatty acids, hardened palm oil fatty acids, palm kernel oil fatty acids, hardened palm kernel oil fatty acids are preferred. As the unsaturated higher fatty acid, the stereoisomer may be a cis- or trans-form, or a mixture of both, and particularly, the ratio of the cis-form / trans-form is 25/75 to 100/0. (Weight ratio).

R ₁₁ and R ₁₃ may be the same or different. R ₁₂ and R ₁₄ are an alkylene group 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 a lauryl group, a myristyl group, a palmityl group, a stearyl group, an oleyl group,
Examples include a linole group and a linolenic group. R ₃ , R
₄ may be the same or different and each has 1 carbon atom
4 to 4 alkyl groups or hydroxyalkyl groups,
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 preferred. 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 di-long chain amine (2) of the component (a) is represented by the following general formula (II).

[0018]

Embedded image (R_Five: Esters having 16 to 25 carbon atoms including a splitting group
An alkyl group or an alkyl group
Kenyl group R₆: An ester having 16 to 25 carbon atoms including a splitting group
Alkyl group or alkyl group
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 hydroxya
Specific examples of the di-long chain amine (a-2) include the following.
The following general formulas II-1 to II,
Examples indicated by II to 14 are given.

[0019]

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[0020]

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[0021]

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[0022]

Embedded image (R _7: alkyl or hydroxyalkyl group having 1 to 4 carbon atoms R _21: an alkyl group or alkenyl group, R ₂₁ and R
The total number of carbon atoms of ₂₂ is 15 to 24 R _22: an alkylene group having 1 to 4 carbon atoms R _23: an alkyl group or alkenyl group, R ₂₃ and R
The total number of carbon atoms of ₂₄ is 15 to 24 R _24: an alkylene group having 1 to 4 carbon atoms R _25: an alkyl group or alkenyl group, R ₂₅ and R
The total carbon number of ₂₂ is 15-24. R _26: an alkyl group or 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 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 tallow. , Butterfat, palm oil, palm kernel oil, soybean oil, safflower oil, sunflower oil, olive oil, etc., are derived from fatty acids obtained by decomposing and refining, especially oleic acid, stearin Acids, tallow fatty acids, hardened tallow fatty acids, palm oil fatty acids, hardened palm oil fatty acids, palm kernel oil fatty acids, hardened palm kernel oil fatty acids are preferred. As the unsaturated higher fatty acid, the stereoisomer may be a cis- or trans-form, or a mixture of both, and particularly, the ratio of the cis-form / trans-form is 25/75 to 100/0. (Weight ratio).

R ₂₁ and R ₂₃ may be the same or different. R ₂₂ and R ₂₄ are an alkylene group 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 ₂₅ , R ₂₆ , and R ₂₇ include a lauryl group, a myristyl group, a palmityl group, a stearyl group, an oleyl group,
Examples include a linole group and a linolenic group. R ₇ is an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, or a hydroxybutyl group. Among them, a methyl group, an ethyl group and a hydroxyethyl group are particularly preferred.

The dilong 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 high molecular acrylic acid. The fiber softening base of the component (a) comprises (a-1) a dilong chain quaternary ammonium salt and (a)
2) The di-long chain amine neutralized product may be used alone or in combination. The softener composition may be used in a total amount of 3 to 30% by weight, preferably 5 to 15% by weight. It is preferable to mix them in. When the amount is less than 3% by weight, the flexibility tends to decrease. On the other hand, when the amount exceeds 30% by weight, preparation becomes difficult.

In the softener composition of the present invention, the following chemical formula 1
6 (general formula III) can also be blended with a neutralized tri-long chain amine.

Embedded image (R_Five, R₆, R₄₁: Hydrocarby having 16 to 25 carbon atoms
Group)

Specific examples of the above tri long chain amine include tri (stearoyloxyethyl) amine, tri (oleoyloxyethyl) amine, tri (palmitoyloxyisopropyl) amine and the like. Specific examples of the acid used for the neutralization are the same as those in the case of (a-2) neutralized dilong chain amine. These neutralized tri long chain amines are preferably blended in an amount of 10% by weight or less based on the fiber softening base of the component (a). If the amount exceeds this amount, the effect of imparting softness to cotton is reduced.

As the colorant of the component (b), color index acid yellow # 3 and / or acid yellow # 141
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 blended in the softener composition in an amount of 1 to 100 ppm, preferably 1 to 50 ppm. If the amount is outside the above range, a yellowish hue may not be imparted. As the colorant of the component (b), the dye of color index yellow # 3 and the dye of color index # 141 may be used alone or in combination. Component (c) 2,6-di-tert-butyl-4
-Methylphenol is present in the softener composition at 0.1 to 10
00 ppm, preferably 5 to 500 ppm.
When the amount is less than 0.1 ppm, the color tone is deteriorated,
On the other hand, when it exceeds 1000 ppm, the composition may be thickened by storage.

The liquid softener of the present invention may contain, as other optional components in addition to the above-mentioned components, known components which are usually added to the softener composition as long as the effects of the present invention are not impaired. The final product is balanced with water. Examples of the optional component include quaternary ammonium salts such as di-long-chain alkyl di-short-chain alkyl quaternary ammonium salts, higher fatty acids such as stearic acid and oleic acid, and portions of 2-ethylhexanoic acid with glycerin or pentaerythritol. Nonionic surfactants such as esterified compounds, water-soluble salts such as sodium chloride, 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 Chelating agents such as 1- hydroxyethane -1,1-diphosphonic acid, urea, bactericides, antioxidants, silicones, hydrocarbons, cellulose derivatives, ultraviolet absorbers,
Examples include a fluorescent whitening agent and a fragrance. 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 is not preferred.

[0030]

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 neutralized di-long chain amine, and a specific (b) By using a colorant and (c) 2,6-di-tert-butyl-4-methylphenol in combination to adjust the pH to 2 to 5 to obtain a liquid softener composition, it is excellent in fibers and clothing. In addition to imparting flexibility, excellent dye stability, especially during long-term storage, is obtained.

[0031]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples. Prior to this, an evaluation method adopted in the examples will be described. (1) Dyeability test A multi-woven fabric composed of nine kinds of fibers of polyester, cotton, acrylic, rayon, wool, acetate, vinylon, nylon and silk is used. 10% of a softening agent composition (aqueous dispersion) to be described below so that the squeezing ratio is 200%.
Is dropped onto all the fibers of the cloth, left for 3 hours, rinsed with tap water for 3 minutes, and air-dried. Then, the dyeing on the dried cloth is visually observed, and the degree of dyeing on the clothes is evaluated according to the following criteria. ：: Almost no dyeing is observed △: Slightly dyeing is observed ×: Dyeing is observed (2) Stability (discoloration / fading) test Afterwards, the softener composition is placed in a glass bottle, sealed, and sealed with the sample. I do. This sample is placed in a constant temperature bath at 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 △: Discoloration / fading is slightly observed ×: Discoloration / fading is clearly observed

[0032] The liquid softener compositions shown in Examples 1 to 11 Table 1-6 were prepared and stability to various fibers (discoloration, withdrawal colors) was evaluated dyeability. The results are shown in Tables 5 and 6.

[0033]

[Table 1] Table 1: Total composition blending amount (wt%) of the softener composition: Component (a); described in Tables 2 and 3 Tables 5 and 6 (b) Component; described in Table 4 Component (c) described in 5, 6 ; 2,6-di-tert-butyl-4-methylphenol Common component described in Tables 5 and 6 : Ethanol 2 Ethylene glycol 6 Salt 0.1 Perfume 0.5 Polyoxyethylene ( (Average: 60 mol) Tallow alkylamine 2.0 (manufactured by Lion Akzo Co., Ltd., trade name: Esomine T70) Water balance 100% by weight The pH of the composition was adjusted to 3.0 with hydrochloric acid.

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

Table 4: (b) Colorant b component: b-1 Color index Acid yellow # 3 b-2 Color index Acid yellow # 141 b-3 Color index Acid yellow # 141 / Acid blue # 9 = 10 / 1 (weight ratio) b-4 color index acid yellow # 23 (comparative product)

[0037]

[Table 5] Table 5: Composition of components (a), (b) and (c), dye stability and dyeing properties (a) component (b) component (c) Component evaluation symbol amount (wt%) Symbolic amount (ppm) Amount (ppm) Stable dyeing 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-1 100 × ×

[0038]

[Table 6]

Continuation of the front page (56) References JP-A-6-123081 (JP, A) JP-A-4-28826 (JP, A) JP-A-6-128876 (JP, A) JP-A-5-230763 (JP) , A) JP-A-4-33364 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D06M 13/463

Claims (1)

(57) [Claims] 1. (a) The following (a-1) and (a-2)
One or more fiber softening bases selected from: 3 to 3
0% by weight The following component (b): 1 to 100 ppm The following component (c): 0.1 to 1000 ppm, and the pH of the composition is in the range of 2 to 5.
Liquid softener composition to be characterized. (A-1) Dilong chain fourth group represented by the general formula (I)
Grade ammonium salt(R₁: Esters having 16 to 25 carbon atoms including a splitting group
An alkyl group or an alkyl group
Kenyl group R_Two: An ester having 16 to 25 carbon atoms including a splitting group
Alkyl group or alkyl group
A nyl group, or an alkyl group having 14 to 24 carbon atoms, or
Alkenyl group R_Three, R_Four: An alkyl group having 1 to 4 carbon atoms or hydroxy
Alkyl group X^-: Anion) (a-2) Di long chain amide represented by the general formula (II)
Neutralized substance of (R_Five: Esters having 16 to 25 carbon atoms including a splitting group
An alkyl group or an alkyl group
Kenyl group R₆: An ester having 16 to 25 carbon atoms including a splitting group
Alkyl group or alkyl group
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 hydroxya
(B) a color index acid yellow # 3 and / or
Is a colorant consisting of acidic yellow # 141. (C) 2,6-di-tert-butyl-4-methylphenyl
Enol