CN1005735B - Textile finishing agent - Google Patents

Abstract

Aqueous dispersions containing amines containing Bronstedt acid and having a pKa value of at least 6 are stable. Added in fabric washing process, used as fabric softener. Application No. 86102993.3 Int. C1. ⁴ D06M13/46 Examination and announcement date 1989.11.08

Description

Textile Finishing Agent

The present invention relates to textile finishing agents. This textile finishing agent is especially suitable for softening fabrics during the rinse cycle of textile laundering, which is beneficial for static control. Its structure is characterized by excellent softness, water dispersibility and storability. It can be stored for a long time under the condition of higher or lower than normal temperature.

Textile finishes that soften fabrics during laundering and facilitate static control are described in this article. And found a wide range of commercial applications. Usually the softener added to the fabric during rinsing contains a reactive group, which is essentially a water-insoluble cationic substance with two long-chain alkyl groups. Commonly used substances are dimethyl ammonium chloride with two tallow groups, or imidazolines with two tallow groups. These prepared materials are generally in the form of aqueous dispersions. In general, the preparation of aqueous dispersions containing more than about 10% cationic softener will seriously affect the viscosity of the product, and also cause problems with shelf-life stability. Although it has been stated in European Patent No.0,000,406 and British Patent No.1601360 that when preparing a high-concentration softener, some non-ionic additives can be combined to add to the softener, but the softening effect of the active agent per unit weight In terms of effect, the efficiency of this structure is relatively low. In addition, the viscosity and stability problems of relatively concentrated aqueous dispersion products have become more prominent and difficult to control. The commercial application range of softeners stipulates that the active agent content is 15% to 20%.

On June 12, 1984, MacGilp et al. disclosed a concentrated liquid fabric softener in U.S. Patent 4,454,049, which contained at least 10% of a water-miscible organic solvent, generally about 30% to 40%.

On August 8, 1961, Luvisi et al. published the acid salts of certain imidazoline derivatives on US Patent No. 2,995,520, which are used for the softness of fiber materials such as cotton and paper. In the treatment tank used for textile finishing, it contains a salt of an imidazoline derivative at a concentration of 0.001% to 1%. For transportation, it is said that the product should be placed in a low molecular weight aliphatic alcohol to prevent it from freezing.

Other patents that are more recent than US Patent 2,995,520 have been published on an imidazoline derivative salt, which is used to soften fabrics. However, as stated herein, quaternary ammonium salts are more effective than acid salts such as acyclic tertiary or cyclic amines from a fabric softening standpoint.

It is therefore an object of the present invention to provide liquid fabric softeners which can be prepared as aqueous dispersions in either diluted or concentrated form without the addition of organic solvents. The products of the present invention have excellent stability even in long-term storage at higher or lower than normal temperature. These compositions can further provide excellent softness, antistatic properties and fabric rewetting properties. Widely used in various fabrics.

The present invention provides a stable aqueous dispersion comprising:

(a) The molecular formula I referred to contains di(higher alkyl) cyclic amines, and the amine content is selected from 1% to 40%. Then mix it up.

(b) A compound selected from conventional quaternary ammonium softeners; it contains two higher alkyl groups, each containing 8 to 30 carbon atoms.

The basis of the invention is the formulation of stable aqueous dispersions with certain cyclic amines, which can be formulated with a conventional medium di(higher alkyl)quaternary ammonium salt even in high concentrations of amines, without the need for large amounts of organic solution.

(a) Amines:

The amines used in the product of the present invention are selected from the group containing the formula I as component (I).

Molecular formula Ⅰ

In the formula, n represents 2, 3 or 4, preferably 2, R ₁ and R ₂ are independent, and are alkyl or alkenyl groups containing 8 to 30 carbon atoms, preferably 11 to 22 carbon atoms The alkyl group is preferably an alkyl group containing 15 to 18 carbon atoms, or a mixture of such alkyl groups. The alkyl radicals of such compounds can be obtained, for example, from coconut oil, "soft" (not hard) tallow and hard tallow.

Q is CH, _CH2 , NL or N. It is best to use N.

X is

In the above formula, T is 0 or NR ₅ , and R ₅ is H or an alkyl group containing 1 to 4 carbon atoms, preferably H. R ₄ is a divalent alkylene group containing 1-3 carbon atoms or (C ₂ H ₄ O)m, where m is 1-8. X may also be R ₄ .

The amine content of the composition of the present invention is 1% to 40%, preferably 2% to 35%, most preferably 2% to 20%.

Detergent residue may be generated during washing. Especially in the case of using the washing machine popular in the United States, there is a tendency to negate the effect of the softener added to the water. It can be seen that the amines of formula I are less active on the detergent residue. For example, compounds such as ditallow dimethyl ammonium chloride.

(b) Quaternary ammonium salts:

Said dispersion contains a conventional di(higher alkyl)quaternary ammonium softener as the second ingredient. The higher alkyl group in the quaternary ammonium salt referred to in this context is an alkyl group with 8 to 30 carbon atoms. Preferably, 11 to 20 carbon atoms are used. For example, conventional quaternary ammonium salts include (I) acyclic quaternary ammonium salts, whose molecular formula is:

Here _R2 is an acyclic aliphatic hydrocarbon group containing 15 to 22 carbon atoms. _R3 is a saturated alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms. _R4 is selected from _R2 or _R3 . A is an anion.

(II) The molecular formula of diamido quaternary ammonium salt is:

Here _R1 is an acyclic aliphatic hydrocarbon group containing 15 to 21 carbon atoms. R ₂ is a divalent alkylene group containing 1 to 3 carbon atoms. R ₅ and R ₈ are saturated alkyl or hydroxyalkyl groups containing 1 to 4 carbon atoms. A ^- is an anion.

(Ⅲ) Molecular formula of diamide alkoxy quaternary ammonium salt:

(Here n takes the value of 1 to about 5. _{R 1} , R ₂ , R ₅ , A ^- as defined above.)

(VI) Quaternary ammonium imidazoline compound:

Component (I) in the examples is well known.

Dialkyl dimethyl ammonium salts such as: ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, di(hydrogenated tallow) dimethyl ammonium chloride, distearoyl dimethyl ammonium chloride, dibehendyl dimethyl ammonium chloride.

Ingredient (II) in the example is methyl bis(ethylamide tallow)(2-hydroxyethyl)ammonium methyl sulfate, methyl bis(hydrogenated ethylamide tallow)(2-hydroxyethyl)amine methyl sulfate. Here _R1 is an acyclic aliphatic hydrocarbon group containing 15 to 17 carbon atoms. _R2 is a vinyl group. _R5 is a methyl group. R ₈ is a hydroxyalkyl group. A is a methylsulfate anion. These compounds are available from Sherex Chemical Company under the tradenames Uarisoft(R)222 and Uarisoft(R)110, respectively.

In the example (Ⅳ) is:

1-Methyl-1-tallowamido-ethyl-2-tallow imidazolinium methyl ethyl sulfate and 1-methyl-1-(hydrogenated tallow amidoethyl)-methylsulfate.

The content of quaternary ammonium salt (b) should be 1% to 20% of the total weight of the product, preferably 2% to 20%.

The weight ratio, amine (a): quaternary ammonium salt (b), ranges from 10:1 to 1:10, preferably 3:1 to 1:3.

This paper preferably selects two (higher alkyl) imidazoline compounds, especially 1-(lower alkyl)-1-(higher alkyl) amidoethyl-2-(higher alkyl) imidazolyl compounds, referred to as "lower "Alkyl" refers to an alkyl group containing 1 to 4 carbon atoms, and "higher group" refers to an alkyl group containing 11 to 22 carbon atoms.

(c) Take the Bronstedt acid.

The dispersion is selected to have a Bronsted acid pKa value of 6 or less.

The acid content requirement is to ensure that the pH value of the dispersant after mixing is not greater than 5, preferably not greater than 4, and the most suitable pH value range is 2.5-4. A typical acid content is 1% to 50% by weight of the amine, preferably 2% to 30%, and most preferably 3% to 15%.

Suitable classes of acids include inorganic mineral acids, carboxylic acids. Especially low molecular weight carboxylic acids containing 1 to 5 carbon atoms, aromatic carboxylic acids such as benzoic acid and alkylsulfonic acids.

Suitable inorganic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and suitable organic acids include benzoic acid, formic acid, acetic acid, methanesulfonic acid and ethylsulfonic acid. Phosphoric acid, formic acid and methanesulfonic acid are preferred.

(d) Organic solvents

The preparation of the product of the present invention does not use any organic solvents. However, organic solvents (such as low molecular weight water-miscible fatty alcohols) will not affect storage stability, viscosity or softness of this product.

Usually, amines are mostly derived from solid chemical substances, which are dissolved in organic solvents to form a solution. Organic solvents such as isopropanol. In any case it is not necessary to remove the organic solvent in the preparation of the product. In fact, it is completely permissible to add some ideal additives.

In addition, organic solutions are more expensive than water, and are flammable, even toxic, and difficult to manage. The ideal formulation of the present invention is to use a small amount of organic solution, i.e. less than 10%, preferably less than 2%.

(e) Selection of organosiloxane ingredients

This product uses aqueous emulsion, mainly linear polydialkylsiloxane or alkylarylsiloxane, where the alkyl group can contain 1 to 5 carbon atoms and can be fully or partially fluorinated. Suitable organosiloxanes are polydimethylsiloxanes, which have viscosities ranging from 100 to 100,000 centistokes at 25°C, with the optimum use range being 300 to 6000 centistokes.

It has been found that the ionic charging characteristics of the organosiloxane used are very important, and it plays a decisive role in the degree of precipitation and the uniformity of distribution of organosilicon, and affects the performance of the finished fabric.

Cationic organosiloxanes accelerate precipitation. Organosiloxanes have been found to be beneficial in improving fabric hand, have a main linear chain, and are preferably polydialkylsiloxanes, the alkyl group being usually methyl. Organosiloxane polymers are generally commercially produced emulsion polymers in nonionic surfactant emulsifiers or nonionic-anionic mixed surfactant emulsifier systems, using strong acids or bases as catalysts.

The organosiloxanes selected for use in the present invention are determined by their cationic properties. Its meaning is as follows.

(a) One main linear chain is two alkyl arylsiloxanes containing 1 to 5 carbon atoms or 1 to 5 carbon atoms, preferably using cationic surfactants as emulsifiers for the emulsion polymer.

(b) α-ω-2 reacted with quaternary ammonium and two alkyl siloxane polymers containing 1 to 5 carbon atoms or alkyl aryl siloxane polymers with 1 to 5 carbon atoms or

(c) Two alkyl or alkylaryl siloxane polymers containing 1 to 5 carbon atoms with an amino functional group. The amino group can be used as a substituent or undergo a quaternary ammonium reaction, and its degree of substitution (d.s) is kept in the range of 0.001-0.1, preferably 0.1-0.075.

Organosiloxanes have a viscosity of 100 to 100,000 centistokes at 25°C.

The content ratio of siloxane to amine in this product can be in the range of 5:1 to 1:100, preferably in the range of 2:1 to 1:10.

The organosiloxane composition which has been fully disclosed in British Patent No. 1549180 is suitable for this product.

(f) Select non-ionic surfactant

The use of nonionic surfactants as softeners has been disclosed. Nonionic surfactants and their amounts are disclosed in US Patent 4,454,049, Mac Gilp et al., June 12, 1984. Reference is made here to its disclosure.

Specific nonionic surfactants suitable for use in this product include glycerides (such as glyceryl monostearate), fatty alcohols (such as stearyl alcohol) and alkoxylated fatty alcohols. The commonly used content of nonionic surfactants is 0.5% to 10% of the total weight of the product.

(g) Other optional ingredients

In order to further improve stability and further adjust their viscosity, the products can contain a small amount of electrolyte. The best electrolyte is calcium chloride (CaCl ₂ ). It has been found that very small amounts of calcium chloride (e.g. 600 ppm) can reduce the Brookfield viscosity (Brookfield) of highly concentrated dispersions to below 100 centistokes.

This product can choose some other textile softening auxiliary agents, including perfume, preservatives, bactericides, colorants, dyes, fungicides, stabilizers, brighteners and opacifiers, and these auxiliary agents are added in conventional amounts.

In addition, in order to increase a certain effect of the finished fabric, for example, the amount of auxiliary agent for perfume products (relative to the product concentration) can be appropriately larger.

Example I-IV

Preparation of several products:

Example 1 Example 2 Example 3 Example 4

DTI1 ⁾ 20% 10% 8% -

DTDMAC2 ⁾ - 10% 12% 15%

PDMS3 ⁾ - - 1% -

Acid 0.2% ⁴⁾ - - 0.4% ⁵⁾

Calcium chloride (PPm) 600 800 900 1200

^GMS6) - 1% - -

Octadecanol - - 1% -

Amines ⁷⁾ 10% 8% 5% 10%

Fragrance 0.9% 0.9% 0.9% 0.7%

Water remaining amount remaining amount remaining amount

1) Ditallow imidazoline

(1-Methyl-1-tallow-amido-ethyl-2-imidazoline chloride)

2) Ditallow dimethyl ammonium chloride

3) Polydimethylsiloxane with a viscosity of 500 centistokes

4) Formic acid

5) Methanesulfonic acid

6) Glycerin monostearate

7) 1-tallow amidoethyl-2-tallow imidazole

The two tallow imidazoline components can be hydrolyzed during processing, but have little effect on the softening effect of the product.

Example V-VIII

In the following several formulation examples, the pH range of each example is 2.5～5.

Components* Example V Example VI Example VII Example VIII

DTDMAC ¹ 2.33 7.0 1.26 3.78

^PDMS2 1.33 5.0 0.333 1.0

Amines ³ 4.33 13 2.34 7.02

Hydrochloric acid 0.268 0.805 0.145 0.435

Calcium chloride 0.005 0.17 - 0.1

Emulsifier ⁴ 0.133 0.5 0.033 0.1

Perfumes/dyes 0.252 0.753 0.251 0.752

Water is dispensed with is dispensed with

100% 100% 100% 100%

^* The content of listed ingredients refers to the percentage of the total weight of the product.

1. The meaning of DTDMAC is the same as in Example Ⅱ, Ⅲ and Ⅳ

2. PDMS refers to polydimethylsiloxane with a viscosity of 5000 centistokes.

3. Amine-1-(2-C ₁₄ -C ₁₈ -amidoethyl)-2-C ₁₃ -C ₁₇ -alkyl-4,5-dihydroimidazoline, CAS No. 72623-82-6.

4. The emulsifier "Sapogenat T-100" (product number) is triisobutylphenol decagly eolether Hoechst.

Claims (18)

1. A stable aqueous dispersion comprising (a) 1% to 40% of an amine mixture selected from di(higher alkyl)cyclic amines of the following general formula; (where n is 2, 3 or 4, R ₁ and R ₂ are C ₈ -C ₃₀ alkyl or alkenyl or a mixture of these groups; Q is CH, CH ₂ , NH or N, X is

, In the formula, T is NR ₅ , R ₅ is H or C _1-4 alkyl, R ₄ is divalent C ₁ -C ₃ alkenyl or (C ₂ H ₄ O) m, m is an integer of 1-8 , X or _R4 ; (b) 1% to 20% of compounds selected from conventional quaternary ammonium softeners having two higher alkyl groups each containing 8-30 carbon atoms; (c) from about 1% to about 50% by weight of the amine of a dispersing aid which is a Bronstedt acid having a pKa value not greater than 6, the acid being present in an amount such that the pH of the composition is 5 or smaller; (d) 0% to less than 10% organic solvents; (e) The remainder of the composition is water. 2. A dispersion according to claim 1, wherein the weight ratio of (a):(b) is in the range of 3:1 to 1:3. 3. A dispersion as claimed in claim 2 which contains from 2% to 35% amine. 4. The dispersion according to claim 3, wherein Q is N, n is 2, and X is

5. The dispersion according to claim 4, wherein the amine is 1-(higher alkyl)amidoethyl-2-(higher alkyl)imidazoline, the higher alkyl represents an alkane of 11 to 22 carbon atoms base. 6. The dispersion according to claim 5, wherein (b) is selected from 1-(lower alkyl)-1-(higher alkyl)amidoethyl-2-(higher alkyl)imidazolinium compounds, The lower alkyl group represents an alkyl group of 1 to 4 carbon atoms, and the higher alkyl group represents an alkyl group of 11 to 22 carbon atoms. 7. A dispersion according to any one of the preceding claims, further comprising a linear di(C ₁ -C ₅ )alkyl or C ₁ -C ₅ alkylaryl siloxane as the main component. Emulsions in which the alkyl groups may be partially or fully fluorinated or substituted by nitrogen-containing cationic groups, siloxanes having a viscosity (25°C) of at least 100 centistokes and up to 100,000 centistokes, silicon in emulsions The weight ratio of oxane content to amine is from 5:1 to 1:100. 8. A dispersion according to claim 7 wherein the silicone is polydimethylsiloxane. 9. The dispersion according to claim 7, which additionally contains 0.5% to 10% of a non-ionogenic compound selected from glycerides, fatty alcohols or alkoxylated fatty alcohols. 10. The dispersion according to claim 7, wherein the pH of the dispersion is 2.5 to 4.