JP2566177B2 - Textile softening composition and method for producing the same - Google Patents

Description

The present invention relates to woven (fabric, knitted, etc.) softening compositions, in particular woven softening compositions containing one or more amines as active materials intended for use in the rinse cycle of the textile washing process. Regarding

The aim of the present invention is to develop a formulation of fabric softening compositions which comprises one or more amines as active material. Another object of the present invention is to provide a fabric softening composition which is environmentally acceptable and exhibits good softening ability. One of the problems with fabric softener compositions containing amines is that they often cannot be as soft as conventional softeners containing quaternary ammonium softeners.

It has been found that the softening ability of amines, including fabric softener compositions, can be significantly improved by carefully adjusting the pH of the aqueous rinse solution each time the fabric is treated. The concentration of amine material in the rinse water is generally 30 to 1000 ppm, preferably around 200 ppm. It has been found that improved flexibility is obtained when the pH of the aqueous rinse containing the amine softener material at a concentration of 200 ppm is less than or equal to the pKa of the amine.

Accordingly, the present invention is a fabric softening composition comprising one or more amine softeners and one or more pH modifiers, wherein the pH of an aqueous liquid obtained by diluting the fabric softener composition to an amine material concentration of 200 ppm. Is at a pH equal to or less than the pKa of the amine material.

Amine Material The term amine softening material, as used herein, refers to any amine material that can be used to soften a fabric, such as one or more amines of the formula It can be used.

Formula (i) Amines (wherein R ₁₅ , R ₁₆ and R ₁₇ are defined below) (ii) Formula Amines (in the formula, R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ and m and n)
Is defined below) (iii) Expression Imidazolines (wherein R ₁₁ , R ₁₂ and R ₁₄ are defined below) (iv) fatty acids and polyamines (selected from the group consisting of hydroxyalkylalkylenediamines and dialkylenetriamines and mixtures thereof) Condensation product formed from the reaction with

Suitable materials are disclosed in European Patent Application No. 199 382 (Procter and Gamble), which is incorporated herein by reference.

When the amine has the above formula (I), R ₁₅ is a C _{6 to} C ₂₄ hydrocarbyl group, R ₁₆ is a C _{1 to} C ₂₄ hydrocarbyl group, and R ₁₇ is a C _{1 to} C ₁₀ hydrocarbyl group. It is a base.
Suitable amines are those in which both R ₁₅ and R ₁₆ are C _{6 to} C ₂₀ hydrocarbyl groups, most preferably C _{16 to} C ₁₈ hydrocarbyl groups and R ₁₇ is a C _1-3 hydrocarbyl group. , Or R ₁₅ is a hydrocarbyl group of at least 22 carbon atoms and R ₁₆ and R ₁₇ are C _1-3 hydrocarbyl groups.

When the amine is the above formula (II), R ₁₈ is a C _{6 to} C ₂₄ hydrocarbyl group, and R ₁₉ and R ₂₁ are of the formula — (CH ₂ CH ₂ O) _y H (where y is 0 to 6). in alkoxylated groups is in the range) of, R ₂₀ is the formula - a (alkoxylated group _{CH 2 CH 2 O) z H} (z in the formula is in the range of Less than six), m is 0 Is an integer in the range of 6 and preferably 3
Is. When m is 0, R ₁₈ is a C ₁₆ -C ₂₂ alkyl group, and the sum of z and y is preferably in the range of 1 to 6, more preferably 1 to 3. When m is 1, R ₁₈ is preferably a C ₁₆ -C ₂₂ alkyl group and the sum of x, y and z is preferably within the range of 3-10. n is 1 to 6
However, 2 is preferable.

Typical commercially available materials of this type are Et
There are homeen (ex Armor) and Ethoduomeen (ex Armor).

When the amine is of formula (III), R ₁₁ is 8 to 25 carbon atoms.
Is a hydrocarbyl group containing R ₈ is 8 to 2 carbon atoms.
Is a hydrocarbyl group containing 5, R ₁₂ is a hydrogen atom or a hydrocarbyl group containing 1 to 4 carbon atoms, and A ⁻ is an anion, preferably a halide, methosulfate or ethosulfate.

Amines of the type (iv) are, for example, those of the formula (IV) (Wherein R ₁ is a C _{15 to} C ₂₁ acyclic aliphatic hydrocarbon group and R ₂ is a divalent C _{1 to} C ₃ alkylene group).

Preferred amine materials have long hydrocarbyl groups (C _6-
C ₂₄₎ 2 amino and short hydrocarbyl group (C ₁ -C ₃₎ which is a material of the formula (I) containing one to. Product name ARMEEN M2HT (Akz
It is preferred to use the commercially available di-cured tallow methylamine as o). 200p when using the latter material
The pH of the rinse solution at pm is preferably 4.5 or less, more preferably less than 3.5.

The expression hydrocarbyl group herein refers to an alkyl or alkenyl group, optionally substituted or interrupted by a functional group such as -OH, -O-, -CONH, -COO- and the like.

pKa value The pKa value is a widely known parameter for protonation of substances. For some amine materials, pKa can be determined by considering the protonation reaction of the amine material: amine + H ⁺ ... amine H ⁺ .

The pKa of an amine is the pH value when the amount of unprotonated amine is equal to the amount of protonated amine. A possible way to determine the pKa of a substance is to determine the titration curve for a 1% dispersion of the substance with increasing amount of acid. That is, the pKa of a substance is the pH value at the midpoint of the steep slope of the titration curve.

In Table I, pKa for various amine soft materials
Value is given.

It is preferred to use amine materials having a pKa value of less than 6.5, preferably less than 5.5, particularly preferably between 5.2 and 4.0.

When more than one amine material is present in the composition of the invention, the pKa value of the amine material is the weight average pKa of the amine mixture.
Should be calculated as a value.

Liquid Products The compositions of the present invention can take various forms such as liquids, pastes, gels, powders, tablets, flakes and the like. The preferred composition of the present invention is a liquid containing an aqueous phase. The proportion of water in such an aqueous liquid is preferably 97 to 20% by weight of the composition, and more preferably 95 to 70% by weight. The concentration of the amine softener material in the product of the present invention, particularly in the liquid product of the present invention, is preferably 1% by weight or more of the composition, more preferably 2% or more, most preferably 3% or more. The concentration of the amine softener material preferably does not exceed 70% by weight of the composition,
%, More preferably less than 3%, and particularly preferably a composition containing 3 to 20% by weight of an amine softener material.

A problem with the formulation of liquid products according to the invention is that a low pH is required for the rinse liquor in the present invention, so that a high concentration of pH regulator is generally required in the undiluted product. That is. These high concentrations of pH regulators destabilize the undiluted product by flocculation of the dispersed amine phase and cause phase separation. The second object of the present invention, while ensuring a suitable amount of pH adjusting agent,
To prevent instability of the undiluted product.

It has been found that by retaining the pH modifier in the undiluted product such that the non-ionized form predominates, the instability of the liquid fabric softener of the present invention can be prevented. further,
The pH of the undiluted product should not be too low for consumer safety. The pH adjusting material must also have a sufficiently low pKa to provide the required pH at an amine concentration of 200 ppm. According to the present invention, the following 1.5 <pKa (pH adjusting agent) <pKa (amine) is more preferable 2.0 <pKa (pH adjusting agent) <pKa (amine) -0.5 Most preferably 2.5 <pKa (pH adjusting agent) <pKa It was found that the above-mentioned various requirements can be achieved in a well-balanced manner by selecting a pH adjuster satisfying the condition of (amine) -1.0.

When using a pH regulator that exhibits more than two steps of deprotonation, the pKa (pH regulator) used in the above equation is the lowest pKa value of the pH regulator. For example, citric acid has a pKa value
Has 3.1, 4.8 and 6.4, but in the above equation the value 3.1
Used as pKa (citric acid).

If more than one pH modifier is used, the pKa value for the mixture of pH modifiers is the weight average pKa of the mixture of pH modifiers.

Other possible ways to increase the stability of the liquid product according to the invention include, for example, a pH which is relatively insoluble in the undiluted product but sufficiently soluble in the rinse solution.
There is the use of regulators and components that prevent flocculation of the dispersed phase.

Examples of suitable deflocculating materials are disclosed in co-pending UK patent application No. 8919669.5 filed August 31, 1989 by the same applicant as the present invention.

pH regulator The composition according to the invention comprises one or more pH regulators. As mentioned above, the pH modifier must provide the rinse water with a specific pH. Once the required pH of the rinse water has been determined according to the above teachings, it would be appropriate for one of ordinary skill in the art to select the type and amount of pH adjusting material needed to obtain the required pH. Generally, the pH adjusting agent is an acid substance.

When the product of the invention is a water-based liquid product, it is preferred that the pH adjusting material has a pKa of 1.5 or higher, but below the pKa of the amine. Again, it would be appropriate for one of ordinary skill in the art to select a suitable acid and its amount as soon as the pKa required for the pH modifier is determined according to the above teachings.

A typical concentration of pH adjusting material in a liquid undiluted product is 1
0.1 to 2.0 moles per unit, more preferably 0.2 to 1.5 moles per unit, and particularly preferably 0.25 per unit.
~ 1.0mole.

The preferred pH adjusting material has a pKa of 2.5 to 3.5. Examples of these materials are p-aminobenzosulfonic acid, bromoacetic acid, chloroacetic acid, o-chloroacetic acid, α-chlorobutyric acid, citric acid, dihydroxybenzoic acid, dimethylmalic acid, dimethylmalonic acid, dinicotinic acid, fumaric acid. Acids, furancarboxylic acids, iodoacetic acid, lactic acid, malic acid, malonic acid, methylmalonic acid, quinolinic acid, sulfanilic acid and tartaric acid. Tartaric acid, lactic acid, citric acid, malonic acid or mixtures thereof are preferred for environmental reasons.

A pH adjusting material having a pKa of 2.5 to 3.5 was prepared by using two long hydrocarbyl groups (C _{6 to} C ₂₄ ) and a short hydrocarbyl group (C ₁
It is preferably used in combination with amines of the formula (I) containing 1 to C ₃ ). It is particularly preferred to use these pH adjusting materials in combination with the di-cured tallow methylamine marketed under the registered trademark ARMEEN M2HT (Akzo).

ADDITIONAL COMPONENTS In addition to the amines and pH adjusting materials described above, the compositions of the present invention may include one or more softening materials selected from cationic, amphoteric and nonionic softening materials. Suitable materials include, for example, those materials described in EP 239 910 (P & G), US Pat. No. 3 915 865 (STEPAN) and US Pat. No. 4 137 180 (LEVER BROTHERS). The weight ratio of these added flexible materials to the total amine flexible material is preferably less than 3: 1 and more preferably less than 1: 1.
Particularly preferred is less than 0.5: 1.

The composition may include non-aqueous solvents such as C ₁ -C ₄ alkanols and polyhydric alcohols, rewetting agents, electrolytic solutions or viscosity enhancers such as long (eg 25-40 EO) alkoxylated fatty alcohols. (Eg calcium chloride), anti-gelling agent, perfume, perfume carrier, fluorescent agent, pigment, hydrotrope, antifoaming agent, anti-redeposition agent, enzyme, optical brightener,
Opacifiers, stabilizers (eg guar gum and polyethylene glycol), emulsifiers, anti-shrink agents, anti-wrinkle agents, textile crisping agents, stain inhibitors, stain release agents, bactericides, linear or branched silicones, fungicides, antiseptic agents. Oxidizing agents, anticorrosion agents, preservatives (eg Proxel, ascorbic acid, Bronoopal® (commercially available in the form of 2-bromo-2-nitropropane-1,3-diol), dyes, bleaches and It may include one or more additional components selected from bleach precursors, drape imparting agents, antistatic agents and ironing aids.

These additional components are preferably added so that they are present in concentrations of up to 5% by weight of the composition.

The composition according to the invention can be prepared in various ways. A preferred method of preparing a liquid product according to the invention is to form a molten mixture of amine material effectively in combination with another soft material and add this premix to water under stirring to form a dispersion, , Adding pH adjusting materials and other additional ingredients.

 The present invention can be further described by the following examples.

Example I (Reference Example) Di-hardened tallow methylamine (Armeen M2HT) was dispersed in water at ambient temperature to a concentration of 200 ppm amine. Amine pK
a is 4.5. In tests 1 to 6, 200 ppm of amine dispersion 1 was adjusted to the pH described below with HCl. A piece of terry towel (40 g total weight) was rinsed in the amine dispersion for 5 minutes. The pieces were dried on the line. The amount of amine deposited was measured by measuring the change in turbidity of the rinse. A high deposition percentage corresponds to better flexibility.

 The following results were obtained.

Table II Test pH% Deposition amine 1 3.0 (pKa-1.5) 95 2 3.5 (pKa-1.0) 81 3 4.0 (pKa-0.5) 68 4 4.5 (pKa) 50 5 5.0 (pKa + 0.5) 40 6 6.0 (pKa + 1. 5) 30 These results show good deposition (> 50%) when the rinse pH is less than or equal to the pKa of the amine.
Is obtained. Good results are obtained especially when the pH of the rinse solution is at least 0.5 less than the pKa of the amine.

Example II The performance and stability of various amines including liquid fabric softening compositions were tested as follows.

A laundry consisting of a terry towel with a wash weight of 1.25 kg and a 1.25 kg cotton sheet fabric is used at 40 ° C for Persil Automatic
(UK) Washed in 100 g Miele 756 Automatic.

90 ml of rinse conditioner (corresponding to an amine concentration of about 200 ppm) containing 5 wt% Armeen M2HT, 1 wt% Tallow 35 EO and varying amounts of pH adjusting material was added to the final rinse cycle. In Table III, the stability of the undiluted product, the pH of the undiluted product and the pH of the rinse are shown. The lower pH value of the rinse solution corresponds to better softening.

These results indicate that low pka acids such as hydrochloric acid and oxalic acid cannot be used to formulate stable products that provide the required pH in the rinse. This indicates that the lower limit of pka of the pH regulator is 1.5 in the liquid product. When using orthophosphoric acid as a pH regulator,
Stable products will be formulated, but unstable properties will occur at high acid concentrations, and if orthophosphoric acid is used, these high acid concentrations will result in rinse solutions below the pka of the amine. It is necessary to lower the pH. Therefore,
Orthophosphoric acid is not preferred as a pH adjusting material for the Armeen M2HT system.

The use of malonic acid, citric acid or tartaric acid resulted in stable compositions, which gave favorable pH values even at relatively low concentrations of acid material in the rinse. Similar results were obtained using lactic acid. Therefore these materials are preferred for use in the Armeen M2HT system.

The use of succinic acid gives stable products, but these high concentrations of acid material are often costly due to the high concentration of acid material needed to obtain the preferred pH in the rinse. For this reason, it is not preferable.

Claims (7)

(57) [Claims] 1. One or more amine soft materials, one or more pH.
A fabric softening composition comprising a modifier and an aqueous base, comprising:
The pH of the aqueous liquid obtained by diluting the fabric softening composition to a concentration of 200 ppm of the amine soft material is equal to or less than the pKa of the amine soft material, and the one or more amine soft materials are Formula (I) [Wherein (a) R ₁₅ and R ₁₆ are C _{6 to} C ₂₄ hydrocarbyl groups, and R ₁₇ is a C _{1 to} C ₃ hydrocarbyl group;
Or (b) R ₁₅ is a hydrocarbyl group having at least 22 carbon atoms, and R ₁₆ and R ₁₇ are C _{1 to} C ₃ hydrocarbyl groups], wherein the one or more pH values are A fabric softening composition in which the regulator satisfies the following formula 1.5 <pKa (pH regulator) <pKa (amine). 2. The fabric softening composition of claim 1 wherein the pH of the diluted amine liquid is at least 0.5 below the pKa of the amine. 3. The pH adjusting agent has a pKa of 2.5 to 3.5.
Or the fabric softening composition according to item 2. 4. The fabric softening composition according to claim 1, wherein the pH adjusting agent is selected from the group consisting of tartaric acid, lactic acid, citric acid and malonic acid or a mixture thereof. 5. The concentration of the pH adjusting agent is 0.25 to 1.0 mol per unit.
The fabric softening composition according to any one of claims 1 to 4, which is e. 6. A textile soft amine of formula (I) (b),
The fabric softening composition according to any one of claims 1 to 5, comprising 1,2-di-cured tallow oxydimethylpropanamine. 7. A fabric softening composition comprising an amine softening material of 200 ppm.
Of the aqueous liquid obtained by diluting to a concentration
A method of making a fabric softening composition, the pH of which is less than or equal to the pKa of an amine material, comprising the formula (I) [Wherein (a) R ₁₅ and R ₁₆ are C _{6 to} C ₂₄ hydrocarbyl groups, and R ₁₇ is a C _{1 to} C ₃ hydrocarbyl group;
Or (b) R ₁₅ is a hydrocarbyl group having at least 22 carbon atoms, and R ₁₆ and R ₁₇ are C _{1 to} C ₃ hydrocarbyl groups], one or more amine softeners selected from Materials, A method comprising the combination of one or more pH modifiers and an aqueous base satisfying the formula: 1.5 <pKa (pH modifier) <pKa (amine).