JPH05195436A - Soft-finishing agent - Google Patents

Abstract

PURPOSE:To provide the subject finishing agent containing two specific t-amine components, a long-chain fatty acid, a specific imidazoline, an ethylene oxide adduct of a higher alcohol, etc., and a specific amide, etc., at specific ratious and capable of imparting excellent softness, etc., to various fibers. CONSTITUTION:The objective soft-finishing agent can be produced by compounding (A) 4-30wt.% of an esteramide type t-amine, etc., of formula I (R<1> is 1-4C alkyl, etc.; R<2> and R<3> are 11-21 alkyl, etc.; (m) is 1-10; (n) is 2-3), (B) 0.1-5wt.% of an alkanolamide type t-amine of formula II (R<1b> is 1-4C alkyl, etc.; R<2b> is 11-21C alkyl, etc.; (p) is 1-10; (q) is 2-3), (C) 0.1-3wt.% of a long-chain fatty acid, etc., of formula III (R<2c> is 11-21C alkyl, etc.), (D) an imidazoline compound of formula IV of formula V (R<4> is 11-21C alkyl; R<5> is group of formula VI or formula VII; R<6> is 11-21C alkyl; R<7> is methyl, etc.; R<8> is 12-22C alkyl; R<9> is methyl, etc.; R<10> is methyl ethyl or (C2H4O)rH; (r) is 1-3; X is halogen CH3SO4, C2H5SO4), (E) 0-5wt.% of an ethylene oxide adduct of a 8-22C higher alcohol, etc., and (F) 0-5wt.% of an amide compound, etc., of formula VIII (R<11> is 7-21C alkyl; X is H, CH3, C2H4OH; Y is H, CH3, C2H4OH, CSH2SCCrOM or CSH2SSO3M; (S) is 1-3; M is H, etc.).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a softening finish, and more specifically, it can impart excellent flexibility and elasticity (puffiness) to various fibers and can be stored under severe conditions. It relates to a stable liquid softening finish.

[0002]

2. Prior Art and Problems to be Solved by the Invention
Most of the products marketed as household softening agents are mainly quaternary ammonium salts having two long-chain alkyl groups in one molecule, as represented by di (hardened tallow alkyl) dimethylammonium chloride. And the composition. The reason for this is that a small amount of quaternary ammonium salt has a good softening effect on various fibers. However, although the above quaternary ammonium salt has a remarkable softening effect on cotton,
It is difficult to say that the effect is sufficient for synthetic fibers such as polyester and polyamide, and if the treatment is performed at a higher concentration, the elasticity of the clothing may be reduced and the texture may be impaired. Furthermore, since the above quaternary ammonium salt has a strong hydrophobicity, when it is poured into the rinse water when the stirring force is weak, the dispersibility in water is poor, and therefore there is a possibility that the garment may be uneven. In addition, especially when storing for a long time at low temperature,
The substance may thicken, gel, or separate. In addition to the above quaternary ammonium salts, commercially available softeners are compounded with additives such as polyoxyethylene-based nonionic surfactants, electrolytes and solvents to improve dispersibility in water and long-term storage stability. However, the effect is still insufficient.

Further, liquid softening finishes having various amines as softening bases have been conventionally known. For example, Japanese Patent Laid-Open No. 52-
59796 discloses a composition for imparting flexibility to a fiber containing a long-chain alkylamine such as methyldi (cured tallow alkyl) amine, and JP-A-58-6070 discloses an acylated alkanolamine, a water-soluble composition. A fiber material finishing agent that imparts smoothness and comfortable feel to a fiber containing a quaternary ammonium salt and a fatty acid ester is disclosed in JP-A-61-167083. Quaternary ammonium compound, higher fatty acid and hydroxy lower alkyl polyamine. A softening agent containing a condensation reaction product with an alkylamine polyglycol ether and having good dispersibility is disclosed in Japanese Patent Laid-Open No. 275474/1986 for treating textiles containing a di (higher alkyl) cyclic amine and a Bronsted acid. A stable aqueous dispersion of the above is disclosed in Japanese Unexamined Patent Publication (Kokai) No. 64-85368, wherein a dilong-chain alkylamine-anionic surfactant ion-pair complex, a non-silicone wax and a non-silicone wax are used. A softening composition containing a liquid carrier is disclosed in JP-A-2-6662, which is a fabric conditioning composition containing an amine such as a condensate of hydroxy lower alkylalkylene diamine and a higher fatty acid and an amphoteric fabric conditioning agent. No. 14076 discloses a fabric conditioning composition containing a dilong-chain alkylamine-polyfunctional carboxylic acid complex, which imparts flexibility and antistatic properties. Furthermore, JP-A-52-5394
The publication describes a fabric conditioning composition containing a mono- or di-long chain alkyl alkylene diamine static inhibitor and a quaternary ammonium softener. However, although the softener containing these amines has relatively good dispersibility and storage stability as compared with the softener containing a quaternary ammonium salt, the softening performance is still insufficient.

[0004]

Means for Solving the Problems As a result of earnest studies on a softener containing an amine, the present inventors have found that a special (dilong chain type) tertiary monoamine compound or a neutralized product thereof or a fourth
A graded product, a (mono long-chain type) tertiary monoamine compound or a neutralized product thereof or a quaternized product, and a long chain fatty acid or a salt thereof,
Specific imidazoline compound or its neutralized salt or its quaternary salt or specific quaternary ammonium salt, higher alcohol or higher amine or ethylene oxide adduct of higher diamine, and specific amide compound or specific ester compound, respectively By adjusting the pH to 1 to 5 by using the amount, it is possible to obtain a soft finish that is excellent in flexibility, can impart elasticity (puffiness) to clothes, and is stable even under storage under severe conditions. As a result, they have completed the present invention.

That is, the present invention includes the following components (a) to (f): (a) component / [(b) component + (c) component] = 50/50
The present invention provides a softening agent having a weight ratio of 95/5 and a pH in the range of 1 to 5. (a); 4 to 30% by weight of a tertiary amine represented by the following structural formula (A) or a neutralized salt or quaternary salt thereof.

[0006]

[Chemical 6]

(Wherein R ^{1 is} an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group R ² , R ^{3 is} an alkyl group having 11 to 21 carbon atoms or an alkenyl group m: 1 to 10 n: 2 to 3 (B); 0.1 to 5% by weight of a tertiary amine represented by the following structural formula (B) or a neutralized salt or quaternary salt thereof.

[0008]

[Chemical 7]

(In the formula, R ^{1b is} an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group R ^{2b is} an alkyl group having 11 to 21 carbon atoms or an alkenyl group p: 1 to 10 q: 2 to 3; ) (C); Fatty acid represented by the following structural formula (C) or a neutralized salt thereof
0.1 to 3% by weight R ^2c COOH (C) (wherein R ^2c means an alkyl group or an alkenyl group having 11 to 21 carbon atoms) (d); an imidazoline represented by the following structural formula (D-1) 0.1 to 10% by weight of one or more compounds selected from a compound, a neutralized salt thereof, a quaternary salt thereof, or a quaternary salt represented by the following structural formula (D-2)

[0010]

[Chemical 8]

(Wherein R ⁴ is alkyl or alkenyl having 11 to 21 carbon atoms)

[0012]

[Chemical 9]

R ⁶ : alkyl or alkenyl having 11 to 21 carbons R ⁷ : CH ₃ or R ⁸ R ⁸ : alkyl or alkenyl group having 12 to 22 carbons R ⁹ : CH ₃ , R ⁸ or (C ₂ H ₄ O) _r HR ¹⁰ : CH ₃ , C ₂ H ₅ or (C ₂ H ₄ O) _r H r: 1 to 3 X: halogen or CH ₃ SO ₄ , C ₂ H ₅ SO ₄ . ) (E): C8-22 higher alcohol or higher monoamine or higher diamine, ethylene oxide 3-50 mol adduct 0-5% by weight (f); compound or 3 represented by the following structural formula (F) To one or two or more compounds selected from esterification products of polyhydric alcohols having 6 to 12 carbon atoms with fatty acids having 8 to 22 carbon atoms 0 to 5% by weight

[0014]

[Chemical 10]

(Wherein R ^{11 is} an alkyl group or alkenyl group having 7 to 21 carbon atoms X: H, CH ₃ or C ₂ H ₄ OH Y: H, CH ₃ , C ₂ H ₄ OH, C _S H _2S COOM or C _S H _2S SO ₃ M s: 1-3 M: H or a monovalent divalent metal.) 3 represented by the formula (A) of the component (a) of the present invention
A representative example of the primary amine compound can be obtained as follows. The following formula obtained by cyanoethylation of the corresponding N-lower alkylalkanolamine or dialkanolamine such as diethanolamine, hydrogenation reaction, etc.

[0016]

[Chemical 11]

It can be obtained by reacting the compound represented by: with a fatty acid having 12 to 22 carbon atoms. In addition, as various compounds and impurities produced as by-products in the course of these reactions

[0018]

[Chemical formula 12]

Although a small amount of etc. is produced, there is no problem even if they are contained. As the acid for obtaining the neutralized product from the tertiary amine (A), inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid, and those having carbon atoms of 6 or less such as acetic acid, lactic acid, glycolic acid, citric acid and maleic acid Organic acids are mentioned, but hydrochloric acid is the cheapest and has the highest performance. In addition, the neutralization process uses a tertiary amine (A)
What was neutralized in advance may be dispersed in water, or the tertiary amine (A) may be added to the aqueous acid solution in liquid or solid form. Of course, the tertiary amine (A) and the acid component may be added at the same time. The quaternary compound of the tertiary amine (A) can be obtained by a known method using methyl chloride, dialkyl sulfuric acid or the like.

The amine compound represented by the formula (B) which is the component (b) of the present invention can be produced simultaneously with the production of the amine compound represented by the formula (A) of the component (a). Of course, it is also possible to synthesize the component (b) separately from the component (a) and mix it in an appropriate amount for adjustment. Also, neutralized salts and quaternary compounds
It can be obtained in the same manner as the component (a), or may be neutralized or quaternized simultaneously with the component (a).

The component (c) of the present invention includes the component (a) and
The component (b) can be contained in the composition by appropriately adjusting the conditions for production, and the component (c) may be blended separately. When using a neutralized salt of a fatty acid, a K or Na salt is generally used. Of course, in the system, the amine compound as the component (a) or the component (b) and the fatty acid or the salt thereof as the component (c) may partially form a complex.

The component (d) of the present invention is an imidazoline compound represented by the structural formula (D-1), a neutralized salt thereof or a quaternary salt thereof, or a quaternary salt represented by the structural formula (D-2). One or two or more compounds selected from the following are used, and more specifically, the following are exemplified. As shown in the structural formula of (D-1),

[0023]

[Chemical 13]

(D-11) can be obtained by an active condensation reaction of an equimolar reaction between N-hydroxyethylethylenediamine and a fatty acid having 12-22 carbon atoms. The compound of (D-12) is D-
Eleven compounds can be further obtained by reaction with a fatty acid or a fatty acid ester such as fatty acid methyl. The compound (D-13) can be obtained by a cyclocondensation reaction of diethylenetriamine and a corresponding fatty acid. When a neutralized salt or a quaternary salt is obtained from the compound (D-1), the neutralization reaction or the quaternization reaction may be carried out simultaneously with the components (a) and (b), or they may be reacted separately. You can also get it. Further, when producing (D-1), the ring-opening product by-produced is present in an amount of (D-1) of the present invention.
Within 20% by weight in the ingredients is acceptable. Also, (D-
Typical examples of the structural formula of 2) are mono-long-chain alkyltrimethylammonium chloride and di-long-chain alkyldimethylammonium chloride.
In addition, di long-chain alkyl short-chain alkyl hydroxyethyl ammonium salts and the like are also used. The preferable blending amount of the component (d) is 0.1 to 10% by weight, and particularly, the blending amount of 1 to 50% by weight based on the total amount of the components (a) to (c) improves flexibility and elasticity. The reason for this is not clear, but it is considered that the component (d) interacts with other components and increases the amount of adsorption to clothing.

More specifically, examples of the component (e) include the following. Alcohols derived from natural fats and oils having 8 to 22 carbon atoms, for example, coconut oil alkyl composition alcohol, beef tallow alkyl composition alcohol, lauryl alcohol, stearyl alcohol, oleyl alcohol, hardened tallow composition alcohol and various synthetic alcohols with 3 to 50 ethylene oxide. 3 to 50 mol, preferably 5 to 40 mol of ethylene oxide in a non-ionic activator added with 5 to 40 mol, preferably a monoamine such as laurylamine or an amine compound of hardened tallow alkyl composition, or a diamine such as oleylpropylenediamine. A nonionic activator with a molar addition is used. In the present invention, the component (e) is 0 to 5% by weight,
It is preferably incorporated in an amount of 0.2 to 3.5% by weight.

Specific examples of the compound represented by the formula (F) of the component (f) of the present invention include the following.

[0027]

[Chemical 14]

Examples of the ester compound as the component (f) include the following. Glycerin, trimethylolpropane, pentaerythritol, sorbitol, triethanolamine and other polyhydric alcohols such as lauric acid, oleic acid, stearic acid, and long-chain fatty acids with 8 to 22 carbon atoms such as hardened tallow fatty acid It is an ester compound. As the ester compound, a compound obtained by esterifying only a part of the OH groups is better than a compound obtained by esterifying all the OH groups. The ester compound can also be obtained by a transesterification reaction between triglyceride and glycerin in addition to the above method. In the present invention, the component (f) is 0 to
5% by weight, preferably 0.2 to 3.5% by weight. It is preferable that the total amount of the component (e) and the component (f) is 0.2 to 5% by weight in the composition.

In the present invention, the component (a) and the component (b) +
The weight ratio of (component (c)) is (a) component / [(b) component + (c) component] = 50/50 to 95/5, preferably 60/40 to 90/10.

The softening agent of the present invention has a pH of 1 to 5,
By adjusting it to preferably 1.5 to 3.0, a liquid softening finish which is stable even under storage under severe conditions can be obtained.

Considering the viscosity and handling property of the product when the soft finishing agent containing the compound of the present invention is essential, the total amount of the compound of the present invention is 5 to 45% by weight, preferably 6 to 30% by weight. %, Particularly preferably 10 to 30% by weight.

When the softening agent of the present invention is prepared, the handling property of the softening agent is improved by adding 0.01 to 1% by weight of an alkali metal salt or an alkaline earth metal salt. These metal salts include NaCl, Na ₂ SO ₄ , and CaC.
l ₂ , KCl, K ₂ SO ₄ , MgCl _{2 and the} like can be mentioned.

In the liquid softening agent of the present invention, the viscosity and the particle size of dispersed particles are determined from the viewpoints of handleability and appearance. The average particle size is a value measured by a light scattering method,
The thickness is 0.03 to 1.0 μm, preferably 0.05 to 0.5 μm. The softening agent of the present invention has a viscosity of 25 by a B-type viscometer.
The measured value at 0 ° C. is 10 to 200 cps, preferably 20 to 100 cps.

Silicone compounds such as dimethylpolysiloxane, dimethylpolysiloxane partially modified with amino groups or polyoxyalkylene groups, and particularly preferably partially modified with polyoxyalkylene groups are added to the softening agent of the present invention. By blending the dimethylpolysiloxane described above, it is possible to improve the feel of the softly treated clothing without impairing the water absorption performance. These silicone compounds are
It is preferably blended in an amount of 0.02 to 1.0% by weight.

Further, in order to improve the appearance and scent of the product, it is general to add a dye or a fragrance. As the dye, an organic dye having both SO ₃ group, amino group or ammonium group in the molecule is preferable from the viewpoint of storage stability, and the addition amount thereof is 1 to 100 ppm, more preferably 5 to 50 ppm. Examples of dyes used in the softening agent of the present invention include the following. [Blue dye] C.I.Direct Blue1 C.I.Direct Blue2 C.I.Direct Blue6 C.I.Direct Blue15 C.I.Direct Blue41 C.I.Acid Blue 1 C.I.Acid Blue 7 C. I.Acid Blue 9 C.I.Acid Blue 15 C.I.Acid Blue 22 C.I.Acid Blue 29 C.I.Acid Blue 90 C.I.Acid Blue 104 C.I.Acid Blue 117 C.I .Acid Blue 138 C.I.Food Blue 1 [green dye] C.I.Direct green 1 C.I.Direct green 6 C.I.Direct green 28 C.I.Acid green 3 C.I.Acid green 9 C.I.Acid green 16 C.I.Acid green 20 C.I.Food green 3 As a fragrance, a hydrocarbon-based fragrance or a functional group is used.

[0036]

[Chemical 15]

It is preferable that the main component is a perfume component consisting of a compound having Particularly stable fragrances include cinnamic alcohol, phenylethyl alcohol (β-phenylethyl alcohol), terpineol (1-methyl-4-isopropyl-1-cyclohexen-8-ol), vanillin (4-hydroxy-3-methoxy). Benzaldehyde), acetylisoeugenol (2-methoxy-4-propenylphenylacetate), p-ter
t-Butylcyclohexyl acetate, edion (methyldihydrojasmonate), geranyl acetate (2,6-dimethyl-2,6-octadiene-8-yl acetate), aldehyde C-14 peach (γ-undecalactone), yonone [4- (2,6,6-Trimethyl-2-cyclohexen-1-yl) -3-buten-2-one], tentalom (6-acetyl-1,1,3,4,4,6-hexamethyl Tetrahydronaphthalene), coumarin (1,2-benzopyrone), ceryl methyl ether, pearlide (1,2
3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-benzopyran) and the like.
Further, the perfume rate is preferably 0.05 to 2.0%.

In order to improve the handling property and moisturizing property of the product, 10% by weight of 1 to 3 valent alcohol having 1 to 3 carbon atoms is used.
The following amounts can also be blended. Examples of such alcohol include methanol, ethanol, isopropyl alcohol, ethylene glycol, glycerin and the like.

Further, a fluorescent brightening agent, a defoaming agent and an antibacterial agent are often blended in the product of the softening agent, which is also applicable to the present invention. The balance other than the components (a) to (f) and the optional component is water.

[0040]

EFFECT OF THE INVENTION The softening agent of the present invention imparts sufficient flexibility and antistatic properties to various fibers, imparts excellent elasticity, and is stable even under storage under severe conditions. Further, the soft component of the present invention is benign and degradable, so that it is less likely to pollute the environment.

[0041]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

The compounds used in Examples and Comparative Examples are shown in Tables 1 to 5 below.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

[Table 4]

[0047]

[Table 5]

Note) * The degree of esterification indicates the average number of ester bonds in the molecule.

Examples 1 to 16 and Comparative Examples 1 to 5 Tables 7 to 9 using the components (a) to (g) (the component (g) is an optional component) shown in Tables 1 to 5 above. A composition having the composition shown in was prepared. In addition, (a), (b),
The total amount of components (c), (d) and (f) was adjusted to 16% by weight, and CI Food Blue 1 was added at 10 ppm in all the formulations, as shown in Table 6.
0.2% by weight of the prepared perfume having the composition shown in Table 1 was added.

[0050]

[Table 6]

<Evaluation of flexibility and elasticity> (1) Treatment method 2 kg of a commercially available cotton towel and 1 kg of an acrylic jersey at 3.5 °
Repeatedly wash 5 times (30 liter washing machine) with commercially available detergent attack (Kao Corporation, registered trademark) with DH hard water,
After removing the fiber treating agent attached to each fiber,
1.5g as the active ingredient of the compounded composition of
It was treated under stirring for 1 minute. (2) Evaluation method The cloth treated by the above method was air-dried indoors, and then left in a constant temperature and humidity room at 25 ° C and 65% RH for 24 hours. The fabrics were evaluated for softness, elasticity and stability. <Evaluation of Flexibility and Elasticity> For the evaluation of flexibility and elasticity, a pair of comparisons were carried out with a cloth treated with 10 cc of a softening agent containing 15% by weight of dihydrogenated tallow alkyldimethylammonium chloride as a control. The evaluation is expressed as follows. +2; softer or more elastic than the control +1; slightly softer or more elastic than the control 0; same as the control -1; slightly softer than the control or slightly less elastic than the control -2: softer or the control Lower elasticity <Evaluation of stability> The compositions having the formulations shown in Tables 7 to 9 were stored and evaluated under the following conditions. (1) Storage condition (a) 50 ℃ (b) Repeating 50 ℃ and 30 ℃ (1 cycle / 1 day) (c) Repeating -20 ℃ and 10 ℃ (1 cycle / 1 day) (d) -10 ℃ (2) Evaluation ○: No change in appearance for 2 months △: No change in appearance for 1 month, separation or thickening after 2 months ×: Separation or thickening after 1 month

[0052]

[Table 7]

[0053]

[Table 8]

[0054]

[Table 9]

Note) 1) pH; pH of undiluted solution. 2) Particle size; average particle size of dispersed particles, measured by light scattering method,
μm. 3) Viscosity; viscosity at 25 ° C measured by B-type viscometer, c
ps.

As shown in Tables 7-9, the formulations of the present invention provide flexibility and resilience and satisfy sufficient stability.

Claims (1)

[Claims] 1. The following (a) to (f) components are included, and (a) component /
[Component (b) + component (c)] = 50/50 to 95/5 (weight ratio), and a softening agent having a pH in the range of 1 to 5. (a); tertiary amine represented by the following structural formula (A) or a neutralized salt or quaternary salt thereof in an amount of 4 to 30% by weight. (In the formula, R ^{1 is} an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group R ² , R ^{3 is} an alkyl group having 11 to 21 carbon atoms or an alkenyl group m: 1 to 10 n: 2 to 3. ) (B); 0.1 to 5% by weight of a tertiary amine represented by the following structural formula (B) or a neutralized salt or quaternary salt thereof: (In the formula, R ^{1b is} an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group R ^{2b is} an alkyl group having 11 to 21 carbon atoms or an alkenyl group p: 1 to 10 q: 2 to 3) (c ); A fatty acid represented by the following structural formula (C) or a neutralized salt thereof
0.1 to 3% by weight R ^2c COOH (C) (wherein R ^2c means an alkyl group or an alkenyl group having 11 to 21 carbon atoms) (d); an imidazoline represented by the following structural formula (D-1) 0.1 to 10% by weight of one or more compounds selected from a compound, a neutralized salt thereof, a quaternary salt thereof, or a quaternary salt represented by the following structural formula (D-2): (In the formula, R ^{4 is} an alkyl group or an alkenyl group having 11 to 21 carbon atoms. R ^6: an alkyl group or alkenyl group R ⁷ of 11 to 21 carbon atoms: CH ₃ or R ⁸ R ^8: alkyl or alkenyl group having 12 to 22 carbon atoms R ^9: CH _3, R ⁸ or (C ₂ H ₄ O) _r HR ¹⁰ : CH ₃ , C ₂ H ₅ or (C ₂ H ₄ O) _r H r: 1 to 3 X: halogen or CH ₃ SO ₄ , C ₂ H ₅ SO ₄ . ) (E): C8-22 higher alcohol or higher monoamine or higher diamine, ethylene oxide 3-50 mol adduct 0-5% by weight (f); compound or 3 represented by the following structural formula (F) To one or two or more compounds selected from esterification products of polyhydric alcohols having 6 to 12 carbon atoms with fatty acids having 8 to 22 carbon atoms 0 to 5% by weight (Wherein, R ^11: alkyl group or alkenyl group of 7 to 21 carbon atoms X: H, CH ₃ or _{C 2 H 4 OH Y: H} , CH 3, C 2 H 4 OH, C S H 2S COOM or C _S H _2S SO ₃ Ms: 1 to 3 M: H or a monovalent divalent metal.)