JPS6044428B2 - Softening base - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a softening base used as an active ingredient in liquid fabric softeners, clothing softeners, hair rinses, and the like.

More specifically, by using the softening base according to the present invention, excellent flexibility can be exhibited, and the dispersion stability, viscosity change over time, and freeze-recovery properties of the liquid softener can be improved. Softening bases, which are active ingredients in clothing softeners and hair rinses, are formulated with 12 carbon atoms in the molecule, such as distearyldimethylammonium salt, from the viewpoint of reducing the frictional force between fibers and hair and improving texture. Quaternary ammonium salt type cationic surfactants having two alkyl groups or alkenyl groups of ~24 are often used.

These are usually used in a dispersed state in an aqueous medium. However, these dispersions do not have satisfactory liquid properties.

That is, when stored at high temperatures, the quaternary ammonium salt aggregates and the viscosity increases significantly (viscosity stability over time).
Also, even if it is frozen at a low temperature and then thawed, it will return to its original dispersed state (
It has the disadvantage that it has little freeze-restoreability and cannot cope with various environmental and usage conditions. In order to improve these liquid properties, large amounts of nonionic surfactants have been added, but the stability of viscosity over time cannot be improved.

In addition, as a result of the nonionic surfactant acting on the quaternary ammonium salt, the amount of the quaternary ammonium salt attached to the fibers increases. decreases, and flexibility is not fully expressed. On the other hand, there is a method of adding a lower alcohol to a quaternary ammonium salt and dispersing it in water by applying high shearing force using a homogenizer (Japanese Unexamined Patent Publication No. 50-693), and a method of adding a long-chain alkyl alcohol (Unexamined Japanese Patent Application Publication No. 1986-693). No. 105997/1972), it is not possible to obtain excellent viscosity stability over time and freeze recovery properties. Therefore, the object of the present invention is to have great flexibility and
The object of the present invention is to provide a softening base that can improve the change in viscosity over time and the freeze recovery properties of a liquid softener.

The object of the present invention is to form a quaternary ammonium salt having two alkyl groups or alkenyl groups having 12 to 24 carbon atoms in the molecule, which takes a layered lamellar structure in water, and which forms secondary aggregates and tertiary aggregates thereof. is formed, it has a thixotropic viscosity, but this dispersion system has 3 carbon atoms.
Extremely long alkyl group (alkenyl group) from 0 to 50
When a suitable amount of tertiary amine or quaternary ammonium salt having one or two molecules of This is based on the knowledge that resilience is improved. That is, the present invention provides (4) carbon number 12 to
A quaternary ammonium salt having two alkyl groups or alkenyl groups of 24 in the molecule, and (B) general formula (1) (wherein R1 is an alkyl group or alkenyl group having 12 to 50 carbon atoms, R2 is a carbon R3 represents an alkyl group or alkenyl group having 30 to 50 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms.

) or a salt thereof and/or a tertiary amine represented by the general formula (■) (wherein R1, R2, and R3 have the same meanings as above, and R4 is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group) The group X- represents a monovalent anion.

) A softening base containing a quaternary ammonium salt represented by:

The quaternary ammonium salt, which is the component (4) of the present invention, has a carbon number of 12 and is represented by the following general formulas (■) and (■), for example.
It is one type or a mixture of two or more types of ammonium salts, amide ammonium salts, midazolinium salts, etc., each having two to 24 alkyl groups or alkenyl groups in the molecule.

(In the formulas ■ and ■, R5 and R6 each have 12 to 24 carbon atoms.
an alkyl group, a β-hydroxyalkyl group or an alkenyl group, each of R7 and R8 is an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, or a benzyl group,
−＋． A group represented by C2H4O)NH (n = 1 to 5),
Yl and Y2 are each an ethylene group or a propylene group,
m1 and j represent O or the number 1, and Z represents a halogen or a monoalkyl sulfate group having 1 to 3 carbon atoms.

) Specifically, dilauryl dimethyl ammonium chloride, dipalmityl methyl hydroxyethylammonium ethyl sulfate, dihydrogenated beef tallow alkyl dimethyl ammonium chloride, distearyl methyl polyoxyethylene (average degree of polymerization 5 mol) ammonium chloride, di Hydrogenated beef tallow alkylethylbenzylammonium methyl sulfate, ditetracosyldimethylammonium chloride, di[(2-dodecanoylamino)ethyl]dimethylammonium chloride, di[(2
-octadecanoylamino)]propyl]dimethylammonium ethyl sulfate, 2-heptadecyl-1-
One or two of methyl-1-[(2-octadecanoylamino)ethyl]imidazolinium ethyl sulfate, 2-hexadecyl-1-methyl-1-[(2-hexadecanoylamino)ethyl]imidazolinium chloride, etc. It is a mixture of more than one species.

Component (B) of the present invention is one or a mixture of two or more of a tertiary amine represented by the general formula (1) or a salt thereof and a quaternary ammonium salt represented by the general formula (■). .

Specifically, examples include the following. The alkyl group or alkenyl group in the molecule may be linear or branched. In formulas (1) and (■), from the viewpoint of dispersion stability, those having one or two alkyl or alkenyl groups having a branched chain at the β position and having 30 to 50 carbon atoms in the molecule are preferable; In particular, the following general formula (V) and its salts, (
(2) is preferable. (In the formula, R3, R4
, X have the same meanings as above, and R9, RlO. ．． Rl
l each has 12 to 26 carbon atoms and is an alkyl group or alkenyl group, and the total number of carbon atoms of R and Rll is 2
It is within the range of 8 to 48 [preferably 3042].

)in particular, is exemplified.

Furthermore, as R, a hydrogenated beef tallow alkyl group or a coconut alkyl group can also be preferably used. The compounds represented by the general formulas (■) and (■) are produced by a halide reaction of an alcohol having a branched chain at the β position produced by the oxo method or the Garbett method, and then converted to a tertiary amine or a quaternary ammonium by a conventional method. Easily produced as a salt. In addition, as the amine salt, hydrochloride, sulfate, phosphate, formate, acetate, propionate, lactate, oxalate, monomethyl sulfate, etc. can be used.
X- in quaternary ammonium salts is a normal monovalent anion, but halogen ions such as chlorine and bromine,
Monomethyl sulfate ion having 1 to 3 carbon atoms is preferred.

In the softening base of the present invention, the content of component (B) is preferably in the range of 0.005 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of component CA). stomach.

Further, when the softening base of the present invention is used as a liquid softener or a hair rinse agent, the total amount of components (4) and (B) can be set as desired, but from the viewpoint of flexibility, texture, etc.
It is desirable that the amount of rut is 1 to 2%, particularly preferably 1 to 1%. In addition, polyoxyethylene (F=4
-50) Nonionic surfactants such as alkyl (C8-22) ether, polyoxyethylene (F = 5-50) alkyl (C6 - phenyl ether, polyoxyethylene, (F = 3-30) sorbitan fatty acid ester) , higher alcohols such as cetyl alcohol, lower alcohols such as ethanol, urea, inorganic salts, etc. can be added in small amounts.Furthermore, the above F indicates the average degree of polymerization of ethylene oxide, and C indicates the number of carbon atoms (the same applies below). Furthermore, in order to improve the flexibility of synthetic fibers, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, polyoxyethylene alkyl sulfate salts, and fatty acid soaps are added to the softening base/anion interface. It can be added so that the molar ratio of the active agent is within the range of 90/10 to 52/48.When used as a hair rinse agent, higher alcohols, silicones, hydrocarbons, cellulose derivatives, etc. can be blended. can.
In addition, hydrotropes such as ethylene glycol and propylene glycol, bactericides, pigments, dyes, fragrances, fluorescent whitening agents, and the like can be appropriately blended. According to the fabric softener using the softening base of the present invention, in addition to achieving the above objects, it also has excellent flexibility and antistatic properties against synthetic fibers such as polyester, polyamide, and polyacrylic fibers. can also be given.

Next, the present invention will be explained in detail with reference to Examples.

Example 1 The composition and performance of various formulations are shown in Table-1.

The composition was prepared by the following method and its performance was evaluated. Components other than the softening base are dissolved in water of 5 CfC or higher, and the molten mixture of the softening base is added dropwise while stirring, uniformly dispersed, and then cooled to room temperature.

Stability of O viscosity over time After preparation, the viscosity is measured after being left at 25°C for 1 day using a Bruckfield viscometer (viscosity A
lcp).

Next, after leaving it for 30 days on the 4th generation, follow the same procedure for 25 days.
Measure the viscosity at °C (viscosity A2cp). This viscosity difference (A2-a1)CP is used as an index of stability over time.Cp is an abbreviation for centipoise. O Freeze recovery properties After preparation, the samples were left at 25°C for 1 day, stored frozen at -20°C for 1 day and night, and then thawed at 25°C to examine whether the dispersion state before freezing could be obtained.

Those that have returned to the dispersed state before freezing are indicated by O, and the others indicate the state after thawing. A pair of soft cotton towels and nylon cloths treated with a 0.067% aqueous solution of the preparation and treated under the same conditions with a corresponding preparation that does not contain component (B) of the softening base. I made a comparison.

From Table 1, it can be seen that the products of the present invention are clearly superior in viscosity stability over time and freeze recovery properties compared to the comparative examples.

In addition, the flexibility of the product of the present invention was comparable to that of a comparative example that does not contain component (B) when used with cotton towels, and was slightly superior when used with nylon cloth. Example 2 Fabric softener compositions (1 to ■) were prepared in the same manner as in Example 1, and their performance was measured.

(Composition 1) Dihydrogenated beef tallow alkylmethylhydroxyethylammonium methyl sulfate 6% potassium stearate 1.5% polyoxyethylene (P=50) lauryl ether
0.5% colorant fragrance
Jusui Balance (Composition ■) Dihydrogenated beef tallow alkylmethylhydroxyethylammonium methyl sulfate 5% Sodium stearate 1.5% Polyoxyethylene (F=40) Lauryl ether
0.5%-water
Balance (composition ■) Dihydrogenated tallow alkylmethylbenzylammonium chloride
7% Sodium dodecylbenzenesulfonate 3.3%
1 urea 5% ethylene glycol 3% water
Balance (composition ■) Dihydrogenated tallow alkylmethylbenzylammonium chloride
5% dodecylbenzene sodium sulfonate 3.3
% ethylene glycol 3% urea
5% water
Balance (Composition ■) Dipalmityl methyl polyoxyethylene (P=5) Ammonium chloride 1% Coconut fatty acid diethanolamide 0.5
% ethanol 3% polyoxyethylene (F=40) nonylphenyl ether
0.2% water
Balance The performance of these compositions is shown in Table-2.

Compositions 1 to 2 exhibited excellent flexibility on cotton towels and nylon cloth.

When Composition (1) was placed in a container equipped with a spray gun and sprayed onto clothing, an excellent antistatic effect was obtained. Example 3 Dihydrogenated tallow alkyldimethylammonium chloride 2% cetyl alcohol 1.5% hydrogenated lanolin
0.5% stearic acid monoglyceride
A hair rinse consisting of 4% propylene glycol and 3% water was prepared and its performance was evaluated.

Claims (1)

[Scope of Claims] 1(A) A quaternary ammonium salt having two alkyl groups or alkenyl groups having 12 to 24 carbon atoms in the molecule;
B) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼
...(I) (wherein R_1 is an alkyl group or alkenyl group having 12 to 50 carbon atoms, R_2 is an alkyl group or alkenyl group having 30 to 5 carbon atoms
0 alkyl or alkenyl group, R_3 has 1 carbon number
-3 represents an alkyl group or a hydroxyalkyl group. ) tertiary amine or its salt and/or general formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼...
・(II) (In the formula, R_1, R_2, R_3 have the same meanings as above, R_4 is an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, and X^- represents a monovalent anion.) A softening base comprising the following quaternary ammonium salt. 2 Component (A) is general formula (III) or (IV)▲mathematical formula,
There are chemical formulas, tables, etc.▼...(III)▲There are mathematical formulas, chemical formulas, tables, etc.▼...(IV) (In formulas III and IV, R
_5 and R_6 are each an alkyl group having 12 to 24 carbon atoms, a β-hydroxyalkyl group or an alkenyl group, R_
7, R_8 is an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, or a benzyl group, ▲Numerical formula,
There are chemical formulas, tables, etc. ▼ A group represented by (n = 1 to 5), Y_1 and Y_2 are each an ethylene group or a propylene group, m_1 and m_2 are numbers of 0 or 1, and Z is a halogen or a number of carbon atoms of 1 to 3. Indicates monoalkyl sulfate. ) The softening base according to claim 1, which is represented by: 3 Component (B) has a branched chain at the β position and has 30 to 5 carbon atoms
The softening base according to claim 1, which has one or two zero alkyl or alkenyl groups in the molecule. 4. The softening base according to claims 1 to 3, wherein the content of component (B) is within the range of 0.005 to 5 parts by weight based on 100 parts by weight of component (A).