JPH06123073A - Soft finishing agent - Google Patents

Abstract

PURPOSE:To obtain a soft finishing agent containing amines having specific different long-chain alkyl groups or their salts or quaternary salts as essential components and capable of imparting various fibers with excellent softening effect and high water-absorption performance. CONSTITUTION:The soft-finishing agent contains either one of amine compounds of formula I to formula III (either one of R<1> and R<2> is 11-21C saturated hydrocarbon group and the other is 11-21C unsaturated hydrocarbon group, 11-21C branched hydrocarbon group or 11-21C hydroxy-substituted hydrocarbon group; (m) and (n) are 2-5; R<3> is 1-4C alkyl), its neutralized salt or its quaternary salt as essential component or, in the case that R<1> or R<2> is 11-21C unsaturated hydrocarbon group, the agent contains an amine compound having steric isomer structure at the unsaturated bond group and consisting of 25-97wt.% of cis- isomer and 3-75wt.% of trans-isomer as preferable essential components. Excellent softening effect can be imparted to various fibers and the water-absorption performance of the fiber can remarkably be improved by applying the soft- finishing agent to the fibers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a soft finish which can impart excellent water absorption to treated garments.

[0002]

2. Description of the Related Art Currently, most of the commercially available softening agents for household use are mainly composed of di (hardened beef tallow alkyl) dimethyl quaternary ammonium salt. Further, recently, amines having various linking groups or salts or quaternary compounds thereof have been disclosed (for example, JP-A-4-108173 and JP-A-4-108174).

These quaternary ammonium salts and the like can impart good softening effect and antistatic effect to various fibers in a small amount. The softening effect due to this is expressed by the reduction of the friction coefficient of the fiber surface due to the lubricating effect of the lipophilic site in the base molecule adsorbed on the fiber surface, so in order to exert an excellent softening effect,
The lipophilic nature is considered essential. However,
This lipophilic property has a drawback that it makes the treated garment water repellent and lowers the water absorption, and particularly when the concentration of the softening agent is high, the water absorption is remarkably reduced.

From this viewpoint, in order to improve water absorption,
Flexible bases are being investigated. Dioleyldimethyl quaternary ammonium salt is known as one of soft base materials having excellent water absorption (see JAOCS, Volume 60, No. 6, pp. 1166 to 1169). However, the softening agent using the base is
Although it is superior in water absorption to di (hardened tallow alkyl) dimethyl quaternary ammonium salt, it is inferior in flexibility. Therefore, if other soft base such as di (hardened beef tallow alkyl) dimethyl quaternary ammonium salt is used in combination to increase the softness, the water absorption is deteriorated.

[0005]

In consideration of such circumstances, the inventors of the present invention have eagerly found out a soft base material having water absorbability and flexibility superior to those of conventional dioleyl type quaternary ammonium salts. As a result of the study, by using an amine having a specific non-identical long-chain alkyl group or a neutralized product or a quaternized product thereof as an essential component of the softening finish composition, sufficient softening performance can be obtained and water absorption performance can be improved. The present invention has been completed by finding that it is remarkably improved.

That is, the present invention provides the following general formulas (1) to (3)
The present invention provides a softening agent containing, as an essential component, one or more amine compounds represented by or a neutralized product or quaternary compound thereof.

[0007]

[Chemical 2]

[Wherein ^one of R ¹ and R ² is a saturated hydrocarbon group having 11 to 21 carbon atoms, and the other is an unsaturated hydrocarbon group having 11 to 21 carbon atoms or carbon number]
It represents a branched hydrocarbon group having 11 to 21 or a hydroxy-substituted hydrocarbon group having 11 to 21 carbon atoms.

M, n; represents 2 to 5.

R ³ represents an alkyl group having 1 to 4 carbon atoms. ].

The compound represented by the general formula (1) according to the present invention comprises the following amine compound (1-A) and an equimolar ester such as R ¹ COOH or R ¹ COOCH ₃ at 150 to 160 ° C. the resulting condensation reacted compound (1-M) Te, then (1-M) and the esters, such as equimolar R ² COOH or R ² COOCH ₃ and 160 to
A condensation reaction (esterification) can be performed at 180 ° C. This reaction is shown below.

[0012]

[Chemical 3]

The compound represented by the general formula (2) according to the present invention is obtained by nitration of R ¹ COOH and hydrogenation to obtain R ¹ CH ₂ NH ₂ , followed by addition of ethylene oxide (2 -M)

[0014]

[Chemical 4]

Can be obtained by esterification in the same manner as above. Further, the compound represented by the general formula (3) according to the present invention is obtained by subjecting the following amine (3-A) to (3-M) as in the case of the compound represented by the formula (1). You can

[0016]

[Chemical 5]

The compounds represented by the general formulas (1) to (3) include hydrocarbons in which R ² in the general formulas (1) to (3) is saturated and R ¹ is an unsaturated or branched or hydroxy-substituted hydrocarbon. Is preferred. The reason is, both compounds are the R ² of is bonded to an ester group, when R ² is a saturated hydrocarbon, in the case of hydrolyzed during long-term storage, part of free fatty acid (R ² This is because COOH) becomes saturated fatty acid, and odor deterioration due to this free fatty acid is less in saturated fatty acid. The compounds represented by the above general formulas (1) to (3) according to the present invention may contain compounds or by-products which are by-produced during the production process.
Therefore, although there are some compounds having different carbon numbers and different types of hydrocarbon groups as impurities, it is sufficient that the main component has 11 to 21 carbon atoms.

R ¹ COOH and R ² CO of the starting materials of the compounds of the present invention
As OH, fatty acids obtained by decomposing and purifying natural fats and oils such as beef tallow, palm oil, sunflower oil, safflower oil, olive oil and rapeseed oil are inexpensive and advantageous. Specific acids include palmitic acid, stearic acid, eicosic acid, isostearic acid, oleic acid, erucic acid, elaidic acid, brassic acid, 12-hydroxystearyl acid and the like.

When R ¹ or R ² is an unsaturated hydrocarbon group, the stereoisomeric structure of the unsaturated bond group is preferably 3% by weight or more in the trans form, and particularly preferably in the cis form.
It is preferable to contain 25 to 97% by weight and 3 to 75% by weight of the trans form. The ratio of cis isomer and trans isomer can be easily obtained by the integral ratio of olefin protons using NMR.

R ¹ is generally derived from natural fats and oils. Usually, R ¹ has only ^one unsaturated bond group,
Those having two or more unsaturated bond groups also coexist. However, the content of those having two or more unsaturated bond groups is preferably 5% or less.

Examples of the acid for obtaining the neutralized product of the amine compound represented by the general formulas (1) to (3) include inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid, and acetic acid, lactic acid and glycolic acid. Examples thereof include organic acids having 6 or less carbon atoms such as citric acid and maleic acid, and hydrochloric acid is the cheapest and has the highest performance. Also, the general formula
The quaternary compound of the amine compounds represented by (1) to (3) can be obtained by a known method using a dialkyl sulfuric acid such as methyl chloride or dimethyl sulfuric acid.

In the softening agent of the present invention, it is preferable that the amine compound or the neutralized product or quaternary compound thereof, which is the feature of the present invention, is added in a total amount of 3 to 30% by weight. The balance of the softening agent of the present invention is an optional component and water.

For the purpose of further improving the flexibility and water absorbency of the softening agent of the present invention, dimethylpolysiloxane or a modified product thereof may be added in a proportion within the range of 0.2 to 5% by weight with respect to the compound of the present invention. it can. Conventionally, silicon is known as a base material which is added to a softening finish to improve its flexibility and ironing characteristics (see, for example, Japanese Patent Application Laid-Open No. 52-53094). Silicon, as seen in these properties,
As such, it has water repellency, and is a base that adversely affects the water absorption performance. However, in the present invention, the fact that when it is used in combination with a specific unsaturated amine compound or a neutralized product or quaternary compound thereof, the water absorption performance can be improved, is contrary to the conventional wisdom and is quite surprising.

Particularly preferred dimethylpolysiloxane or its modified product has a viscosity at 25 ° C. of 20 to 10,000 cps.
The ones are suitable. Modified products include polyoxyethylene modified products and amino modified products, and the modification rate is 10%.
The following are preferred. It is desirable that the dimethylpolysiloxane or a modified product thereof is used by previously emulsifying it with a polyoxyethylene-based nonionic activator or a monoalkylcation-based or dialkylcation-based cationic activator.

In the softening agent of the present invention, the general formula
In addition to the amine compound represented by (1) to (3) or a neutralized product or quaternary compound thereof, polyoxyethylene alkyl or alkenyl ether, polyoxyethylene alkylphenyl ether, within a range that does not impair the effects of the present invention Nonionic surfactants such as polyoxyethylene oxypropylene polyalkylene polyamine, higher fatty acids such as stearic acid and oleic acid, or partial esterification products of 2-ethylhexanoic acid and glycerin or pentaerythritol; sodium chloride, ammonium chloride, calcium chloride Water-soluble salts such as; ethyl alcohol, isopropyl alcohol,
Solvents such as propylene glycol and ethylene glycol;
Urea, a bactericide, an antioxidant, a pigment, a dye, a fragrance and the like can be added.

The pH of the softening agent of the present invention is 1 to 7, preferably 1.5 to 6.0 because of its stability during storage.

[0027]

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

Examples 1 to 11 and Comparative Examples 1 to 4 <Evaluation> (1) Softening Method A commercially available cotton towel or cotton knitted undergarment was repeated 5 times with a commercially available detergent, Zab (registered trademark of Kao Corporation). After washing and removing the detergent attached to the cloth, use a 0.05% aqueous solution of softening agent (3.5 DH hard water) shown in Table 1 at 25 ° C and a bath ratio of 1
/ 30 for 5 minutes under stirring. (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 softness and water absorption of these cloths were evaluated. Softness A pair of comparisons were performed using a cloth treated with a control product (using 10% of dimethyldi-hardened tallow ammonium salt, which is a standard softening substance), and the evaluation was made according to the following evaluation criteria. +2 Softer than control +1 Softer than control 0 Same as control -1 Softer than control -2 Softer than control Cut into strips, one end 2
Soak cm in water. The rising height (cm) of water after 15 minutes was measured.

Table 1 shows the softening bases of the softening finish used in the examples. Further, Table 2 collectively shows the blending ratio of each component in each softening agent and the measurement result of the softening effect. From Table 2, it can be seen that in the case of the softening finish according to the present invention, sufficient flexibility is retained and the water absorption is remarkably improved.

[0030]

[Table 1]

Note) * 1: 1-1, 1-2, and 3-1 are comparative products, and the others are products of the present invention. * 2: The types of R ¹ and R ² have the following meanings. Saturated ... Saturated hydrocarbon group Unsaturated ... Unsaturated hydrocarbon group Branching ... Isostearic acid residue OH ... 12-Hydroxystearic acid residue * 3: Indicates the number of carbon atoms of the main component.

[0032]

[Table 2]

Note) 1): Dimethyl polysiloxane 2): Dimethyl di-hardened tallow alkyl ammonium chloride

Claims (3)

[Claims] 1. A softening finish containing one or more amine compounds represented by the following general formulas (1) to (3) or a neutralized product or quaternized product thereof as an essential component. [Chemical 1] [In the formula, R ¹ and R ² ; either one is a saturated hydrocarbon group having 11 to 21 carbon atoms, and the other is an unsaturated hydrocarbon group having 11 to 21 carbon atoms or carbon number.
It represents a branched hydrocarbon group having 11 to 21 or a hydroxy-substituted hydrocarbon group having 11 to 21 carbon atoms. m, n; represents 2 to 5. R ³ represents an alkyl group having 1 to 4 carbon atoms. ] 2. R ¹ or R ² is an unsaturated hydrocarbon group having 11 to 21 carbon atoms, and the trans isomer ratio thereof is 3 to 75.
The softening agent according to claim 1, characterized in that the softening agent is in weight%. 3. The softening finishing agent according to claim 1, wherein R ² is a saturated hydrocarbon group having 11 to 21 carbon atoms.