JPS63260992A - Softening finish agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a fabric softener, and more particularly, a fabric softener that can impart excellent flexibility, antistatic properties, and water absorption properties to various fibers. Regarding drugs.

[Conventional technology and its problems]

When clothing is repeatedly worn and washed, the fiber treatment agent may be washed off, or the fibers themselves may deteriorate and become stiff, resulting in an undesirable feel. Therefore,
In recent years, fabric softeners that can impart flexibility and antistatic properties to fibers have been widely used in many households.

Currently, the commercially available household fabric softeners are:
Most of them are - cationic active agents having 1-2 long chain alkyl groups in the molecule.

Among them, the main component is zo(hardened beef tallow alkyl) dimethylammonium salt.

This quaternary ammonium salt can impart a good softening effect and antistatic effect 4 to various fibers in small amounts. This softening effect is produced by lowering the coefficient of friction on the fiber surface due to the lubricating effect of the lipophilic moieties in the base molecules adsorbed on the surface of the weft fibers.
It is thought that lipophilic properties are essential to exhibit excellent softening effects.

However, this lipophilic property has the disadvantage that it makes treated clothing water repellent and reduces its water absorption, especially when the concentration of fabric softener is high.

From this point of view, studies have been conducted to improve water absorption, and mono-branched alkyl type quaternary ammonium salts [US Pat. No. 3377:382] have been developed.

a395,100], imidazolinium compounds derived from oleic acid [Scharnal Op American Oil Chemical Society (JAOC8),
61, 367 (1984)) etc. have been reported.

These compounds have a sufficient effect on water absorption performance, but on the other hand, have a low softening effect, which is clearly inferior to that of the above-mentioned zo(hardened tallow alkyl) dimethyl quaternary ammonium salt. Therefore, in order to supplement the softening effect, the imidazolinium compound is usually used in combination with distearyldimethylammonium chloride, an imidazolinium compound derived from hardened tallow fatty acid, etc. cannot be obtained. In addition, we are trying to solve this problem by using α-position branched alkyl type quaternary ammonium salts and β-position branched alkyl type quaternary ammonium salts in combination with straight-chain alkyl type quaternary ammonium salts [Unexamined Patent Publication No. No. 49-69998, No. 50-53694
No. 54-122207, No. 58-444174, U.S. Patent No. 89-669, West German Patent No. 2,625,9
No. 45], but all of them have inferior softening effects, and none have been provided that are satisfactory.

[Means for solving problems]

Under these circumstances, the inventors of the present invention have conducted intensive studies to develop a fabric softener that has sufficient flexibility and does not impair the water absorbency of treated clothing. The present invention was completed based on the discovery that an asymmetric two-chain quaternary ammonium salt having a long chain, at least one of which is an alkenyl group, is a flexible base material that meets the above objectives.

That is, 1 the present invention is based on the general formula (1) [wherein R1 is a linear or branched alkyl group, a β-hydroxyalkyl group, or an alkenyl group s
Rt represents an alkenyl group, provided that R and R2 each have 10 to 24 carbon atoms.

R and R1 have a difference in the number of carbon atoms of 3 or more. R1 and R4 are an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, a pencil group, or -(c, u4o
) na (where n represents 2 to 3), and X represents a monoalkyl sulfate group having a halogen atom or an alkyl group having 1 to 3 carbon atoms] Asymmetric two-chain quaternary ammonium salt represented by The present invention provides a softening agent containing the following.

Asymmetric two-chain quaternary ammonium salt (1
) can be obtained by quaternization reaction of the corresponding secondary or tertiary amine.

The secondary amine used as a raw material can be obtained by, for example, reacting a primary amine derived from tallow fatty acid with a long chain branched alcohol in a hydrogen atmosphere (1 to 10 atm) in the presence of a hydrogenation catalyst. It will be done. Further, the tertiary amine can be obtained by a method of reacting a secondary amine with one equivalent of lower alkyl halide in the presence of an equivalent amount of alkali.

The secondary amine or tertiary amine may be purified by distilling off the low boiling point substances contained therein under reduced pressure as an initial fraction, or the reactant itself may be used.

The quaternization reaction of secondary or tertiary amines obtained by such a method is carried out in the following manner: 1 For example, when using methyl chloride as the quaternizing agent, water and isopropyl alcohol are used as the solvent and water and isopropyl alcohol as the alkali in an autoclave. This is carried out by using soda ash or caustic soda, introducing methyl chloride, and reacting at 100 to 110°C for several hours. After the reaction, if the by-produced NIICt is filtered out, 1
The asymmetric two-chain quaternary ammonium chloride (+) used in the present invention is obtained by dissolving water and inpropyl alcohol.

Asymmetric two-chain quaternary ammonium salt (1
) has a gel-liquid crystal transition temperature of 30'C or less and a special KO~15
Preferably it is .degree. The asymmetric two-chain quaternary ammonium salt (1) may be obtained as a mixture depending on the carbon chain length distribution of its raw materials or the manufacturing method, but even in such cases, the product's liquid crystal transition temperature is within the above range. It can be preferably used within this range.

The fabric softener of the present invention can be in liquid form, powder form, or ssollet (aerosol) depending on the purpose.

Furthermore, it can be made into various forms such as sheets impregnated with cloth, nonwoven fabric, paper, e-towel, etc. The blending amount of the asymmetric two-chain quaternary ammonium salt (1) in such a softening agent varies depending on its form, but the amount of the asymmetric two-chain quaternary ammonium salt (1) dispersed in water is In some cases, 3 to 20% by weight (hereinafter expressed as %) is preferable. In this case, the particle size distribution of the dispersed particles is determined by Coulter Counter (TA type I, Anno Q-chartup 50 am %).
It is preferable that 90% or more of the particles have a diameter of 5 μm or less when measured using a C0ULTEREL BCTRONIC 8 company.

Outside this particle size distribution, the flexibility is reduced.

In the softening agent of the present invention, a known cationic softening base may be used in combination with the asymmetric two-chain quaternary ammonium salt represented by the general formula (2), as necessary, to the extent that the effects of the present invention are not impaired. Examples of such cationic flexible bases include the following.

(a) Symmetrical two-chain quaternary ammonium salts such as zocured tallow alkyl quaternary ammonium salts (b) Below (1)
~(4) Expression. Amido ammonium salt having 1 or 2 alkyl groups, alkenyl groups or β-hydroxyalkyl groups having 10 to 24 carbon atoms in the molecule [% R? and R8 are each an alkyl group, alkenyl group, or β-hydroxyalkyl group having 10 to 24 carbon atoms, and R10 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a pencil. group or -(C,H,O), H(p
represents a number from 1 to 3), and q is 2 or 3.

X represents a halogen or a monoalkyl sulfate group having an alkyl group having 1 to 3 carbon atoms. ] (c) Imidazolinium salt represented by the following formula (5) [wherein R11 and l't
t is an alkyl group having 10 to 24 carbon atoms, an alkenyl group or a β-hydroxyalkyl group %nts is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, a pencil group or -(CsH+0)icHb -(CsHsO)z
H (k s t each represents a number from 1 to 3), and X represents a halogen or a monoalkyl sulfate group having an alkyl group having 1 to 3 carbon atoms. ] However, if the amount of these cationic softening bases is too large, the excellent flexibility and water absorbency, which are the objectives of the present invention, may be impaired. Therefore, when these known cationic flexible bases are used together, it is necessary to use known cationic flexible bases so that the gel-liquid crystal transition temperature of the mixed system with the asymmetric two-chain quaternary ammonium salt (r) does not exceed 30°C. It is necessary to adjust the blending amount of the base. In addition to the above-mentioned cationic softening base, the softening agent of the present invention may contain, for example, the following compounds depending on the intended form and function. can.

(,) Amine u, 4-o R1? N-R,.

RIs-o-Rts RIs Co■ stone, [In the formula, s R14 is a saturated or unsaturated linear or branched alkyl group having 8 to 24 carbon atoms, or a C8 to 2
4 is a secondary alkanol group, R36 is an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, or -(CH,
CHtO)tH (t represents a number from 1 to 10), R, aT
h R11 is an alkylene group having 1 to 3 carbon atoms or -
(CH, CH, 0) uI'1 (U represents a number from 1 to 1o), r and - represent a number from 1 to 10, and R1 represents the same group as "14 or RI6." (b ) Nonionic activator R,,-(0CI(,CM, )xiOHCH,0CO
R,4 HOH CM, OH CMtOCOR,.

CHOCOR,I CH,OH R,,Coo(CH,CH,O)xo-Co-R,.

R,4Coo(CH,CH,O),,5-H [wherein, K
O is a number from 1 to 100,! 1%7+,! 1 is x+ + y
A number that satisfies t+zI=100, xl.

y*, zt each represent a number from 0 to 100"l RI
4 and RIs have the same meanings as above. 〕(,)
Fatty acid R,4COOH (in the formula, % R14 has the same meaning as above) (d'
) Anionic surfactant fatty acid salt Sodium alkylbenzenesulfonate, alkyl sulfate ester salt, alkylnaphthalene sulfonate, alkyl phosphate, etc. (,) Ampholytic surfactant Alkyldimethylaminoacetic acid betaine, alkylcarboxymethylhydroxyethylimidazolinium betaine (f) Water-soluble salts, ammonium chloride, calcium chloride, etc. (g) Solvents isozorobyl alcohol, zolopyrene glycol, ethylene glycol sodium, etc. In addition to these, urea, disinfectants, antioxidants, etc. Pigments or dyes'f:% for appearance may also include fluorescent brighteners for whiteness of the finish and perfumes for use and after finish.

〔Effect of the invention〕

The fabric softener of the present invention can impart flexibility and antistatic properties to various fibers without impairing their water absorption performance.

〔Example〕

Examples will be described below, but the present invention is not limited thereto.

(Gel-liquid crystal transition temperature measurement method) The measurement sample was prepared by dispersing 5% by weight of a flexible base in ion-exchanged water, and was measured using a thermal analyzer SSC/580 series DSCIO manufactured by Seiko Electronics Co., Ltd., and the peak The rise was defined as the gamma liquid crystal transition temperature. The detailed conditions are as follows.

Measurement sample 1101R was placed in a 15μt aluminum sealed sample container, and an empty sealed container was used as a control.
0.5-1.0℃/min after cooling to 30℃
Heating is performed at a heating rate of 0 to 60°C. The rise of the peak at this time is defined as the gel-liquid crystal transition temperature.

In addition, when two or more peaks exist in the range of 0-60 degreeC, the rising temperature of the peak on the highest temperature side is adopted.

(Evaluation) (1) Softening treatment method A commercially available cotton towel was washed 5 times with commercially available detergent Zab (manufactured by Kao Corporation, registered trademark), and after removing the detergent from the fabric, 0.1% of the fabric softener was removed. Aqueous solution (a5DH
The mixture was treated with hard water) at 25° C. and a bath ratio of 1/30 for 5 minutes with stirring.

(2) Evaluation method After drying the cloth treated with the above method indoors, 25℃, 65%
It was left in a constant temperature and humidity room at RH for 24 hours. These fabrics were evaluated for flexibility and water absorption.

(2) Flexibility A pairwise comparison was made using a fabric treated with dioctadecyldimethylammonium chloride (sample positive 3, comparative product) as a control, and evaluation was made according to the following evaluation criteria.

+2 Control is softer +1 Control is slightly softer O Same as control 11 Control is slightly softer -2 Control is softer ■ Cotton towel treated with water-absorbing fabric softener 3 CyLX20c
Cut the IL into a strip, and soak one end (2 ctt) in water. The height of water rise after 15 minutes was measured. The flexibility and water absorbency of the treated cotton towels were investigated according to the evaluation method described above. The results are shown in Table 1.

Below is the margin Example 2 Composition Ethylene glycol 4% water by weight

Paragraph 73 The above composition When preparing the softening agent, several aqueous dispersions having different average particle sizes were prepared by changing the blending temperature and the rotational speed of the stirring propeller. Do this for 48 hours, 2
After storage at 5° C., the cotton towels were treated and their flexibility and water absorption were examined according to the methods described above. Second result
It is summarized in the table. In addition, the particle size distribution of the softening agent is determined by Coulter Counter (TA-1 type, A-f Y-f:
L-bu50 pm C0ULTERELECTRON
(manufactured by IC8) on various fabric softeners left at 25℃ for 48 hours.

Claims (1)

[Claims] 1. The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ (I) [In the formula, R_1 is a linear or branched alkyl group, β-hydroxyalkyl group, or alkenyl group, R
_2 represents an alkenyl group, provided that R_1 and R_2 each have 10 to 24 carbon atoms, and R_1 and R_2 have a difference in the number of carbon atoms of 3 or more. R_3 and R_4 represent an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, a benzyl group, or -(C_2H_4O)_nH (where n represents 2 to 3), and X is a halogen atom or a hydroxyalkyl group having 1 to 3 carbon atoms. a monoalkyl sulfate group having an alkyl group] A softening agent characterized by containing an asymmetric two-chain quaternary ammonium salt represented by 2. The softening agent according to claim 1, wherein the asymmetric two-chain quaternary ammonium salt has a gel-liquid crystal transition temperature of 30° C. or lower. The fabric softener according to claim 1, which is dispersed in water such that 90% or more of the particles have a particle size distribution of 5 μm or less.