JP3283264B2 - Textile softening composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a liquid textile softening composition introduced during the rinse stage of a textile washing cycle. In particular, it relates to a so-called concentrated type textile softening composition.

PRIOR ART Conventional textile softening compositions generally comprise as their active ingredient a relatively water-insoluble cationic compound comprising a quaternary ammonium group having a long-chain alkyl group at the nitrogen atom. Examples of such compounds include dihydrogenated dimethyl tallow ammonium salts and the corresponding unhydrogenated tallow derivatives. These compounds are usually used as an aqueous dispersion.

If the storage space for laundry articles is limited or if it is desirable to reduce the volume of the product to be packaged, concentrated textile softening compositions containing high levels of active ingredients are preferred. It is known to add electrolytes, viscosity controlling polymers and co-activators to increase the amount of cationic compounds contained in the aqueous dispersion. However, it is still difficult to increase the concentration of the cation component to 30% by weight or more. If the concentration of the cationic component is high, the composition tends to be unstable or undesirably high in viscosity, especially during storage.

Another method is to make a solution of the cationic textile softening component by incorporating an organic solvent into the composition. Although large amounts of water-insoluble components can be incorporated in this method, the resulting compositions generally have an undesirably high flammability and also an unpleasant odor.

However, the inventors have found that by appropriately selecting the cationic textile softening compound, compositions containing high concentrations of textile softener can be made using less flammable organic solvents. I found it. In addition, we have:
It has been found that by appropriately selecting a cationic compound and a solvent, a composition having low flammability and low solidification temperature can be obtained. This is contrary to previous experience that it is necessary to use a large amount of an organic solvent having a low flash point in order to obtain a composition having a low freezing temperature. Low coagulation temperature compositions are of interest when laundry products such as Japan are stored on the market outside under cold conditions.

EP-4-0,234,082 is a cationic surfactant and C
A solid textile softening composition comprising _4-7 saturated dicarboxylic acids is disclosed. Surfactants used in the examples,
Alkylammonium chloride.

EP-A-0,038,862 discloses the use of certain amines as textile softeners. Amines are synthesized by reacting diethylenetriamine or higher analogs thereof with 2 moles of fatty acids, followed by mono-ethoxylation and, if desired, total or partial neutralization. Amine
It may be used with water-miscible organic solvents such as isopropanol, hexylene glycol, propylene glycol, ethylene glycol, monomethyl ether and mixtures thereof.

GB-A-2,168,392 discloses the use of hexylene glycol alone or in combination with a lower alkanol or another glycol or glycol ether as a liquid carrier for cationic textile softeners. The softener may be a quaternary ammonium compound,
A typical example is an alkyl ammonium compound.

DISCLOSURE OF THE INVENTION According to the present invention, (1) 10 to 70% by weight of the formula (I): [Wherein each a is independently 1-5, preferably 1-3, b is also 1-5, preferably 1-3, and c is 1-1.
0, preferably 1 to 6, more preferably 1 to 3,
Each R is independently selected from saturated and unsaturated alkyl groups having 14 to 22, preferably 14 to 18 carbon atoms, and Y is an anion selected from, for example, halides, methyl sulfate and ethyl sulfate. . (2) 10 to 60% by weight of an organic solvent or an organic solvent mixture,
And optionally, (3) a textile softening composition comprising water, wherein the cationic textile softening agent is soluble in the organic solvent or organic solvent mixture and optionally present water; The textile softening composition characterized in that the mixture is selected such that the flash point of the composition is at least 25 ° C, preferably at least 30 ° C, particularly preferably at least 40 ° C, ideally at least 50 ° C. Things are provided. Preferably, a substantially isotropic solution results when the cationic fabric softener is dissolved in an organic solvent or solvent mixture and optionally present water. That is, the solution is preferably clear or only slightly hazy.

Flash point refers to the lowest temperature at which the vapor instantaneously ignites in the presence of a flame under standard conditions (eg, equilibration time and pressure) when the product is heated in a closed cup. The flash point specified in this specification is setaflash
(Trademark; manufactured by Stanhope-Seta (Chertsey)). Temperature measured using an equilibration time of 1 minute and atmospheric pressure.

The cationic fabric softener of formula (I) is preferably
It is present in the textile conditioner composition in an amount of from 20 to 60% by weight, particularly preferably from 40 to 50% by weight. The cationic fabric softener may be a single compound, but may also be a mixture of compounds, for example, a mixture of compounds having R groups of different chain lengths and degrees of saturation. One example of a suitable textile softener commercially available is Varisoft 222 (trademark; R)
ewo Sherex). This is given by the formula (I) where a =
1, b = 1 and c = 1.7, and Y ⁻ is a methylsulfate ion).
The long chain distribution of the R group of risoft 222 is (= Means that one double bond exists, 2 = means 2
Means that two double bonds are present. ).

To make a substantially isotropic liquid composition,
It is considered necessary to appropriately select the distribution of the chain length and the degree of saturation. In general, the higher the molecular weight of the cationic compound and the longer the R group, the higher the degree of unsaturation or the more unsaturated R groups, which is more preferable. Generally, the proportion of saturated carbon chains having 18 or more carbon atoms is preferably less than 10%,
In particular, it is less than 5%, particularly preferably 3% or less.

The textile softening composition is preferably 20-50% by weight,
Particularly preferably, it contains 20 to 40% by weight of an organic solvent or an organic solvent mixture.

The solvent mixture may include low boiling solvents derived from the cationic fabric softener or present in the softener as a result of the manufacture or processing of the cationic fabric softener.
Examples of such solvents include isopropyl alcohol and ethanol. For example, listed above
Varisoft 222 ™ is 90% containing 10% ethanol
It is commercially available as an active system. Low molecular weight alcohols (e.g., C ₁ -C ₃ monoalcohols) low boiling point solvent such as can be added to the textile softening compositions. However, it is preferable that the total of solvents having a boiling point of less than 100 ° C contained in the textile softening composition is 10% by weight or less. If there is too much low boiling solvent, the flash point of the composition will be too low.

The present inventors have found that a number of relatively high boiling solvents are effective solvents for the cationic fabric softener of formula (I). The effectiveness of the solvent and solvent mixture can be confirmed by plotting a phase diagram of a ternary system comprising the fabric softener, the test solvent or test solvent mixture and water. Preferred solvents are those that can easily produce isotropic liquids over a wide range of concentrations of the textile softening component.

The effectiveness of the solvent can also be determined by examining the effect of the solvent on the solidification temperature of the ternary system containing the solvent. In general, lowering the coagulation temperature means that the effectiveness of the solvent increases. The surprisingly low coagulation temperatures obtained when the compounds of the formula (I) are formulated into the compositions, which the inventors have found, allow the use of various types of textile softener compounds in model systems, It is convenient to examine the effect of the solvent on the temperature. For example, 40% Prapagen 3
445 (trademark; commercially available ditallow dimethyl ammonium chloride), the test solvent and the balance can measure the solidification temperature of the water composition. Solvents that have a coagulation temperature of 10 ° C. or less when present in this test system at a level of 30% or less are preferred solvents. Particularly preferred solvents are those having an effect at least as good as diethylene glycol butyl ether (also known as butyl carbitol). 40% of diethylene glycol butyl ether
The solidification temperature in a system containing Prapagen 3445, 30% diethylene glycol butyl ether, 30% water is about 9-10
° C.

Preferred solvents are more effective according to the tests outlined above and have a flash point of the textile softening composition of at least 40.
C., preferably at least 60.degree. C., with a sufficiently high boiling point. Preferably, most of the organic solvent or organic solvent mixture has a boiling point of 100 ° C. or higher, preferably 150 ° C.
As described above, the solvent is particularly preferably constituted by a solvent at 180 ° C. or higher. Preferably, the weight ratio of high boiling solvent (100 ° C. or higher) to low boiling solvent (lower than 100 ° C.) in the composition is at least 2: 1, preferably at least 3: 1, particularly preferably at least 5: 1. .

Examples of suitable high boiling solvents include polyols, especially diols such as propylene glycol, butylene glycol, pentylene glycol and hexylene glycol; alkyl ethers of glycols or polyglycols, especially alkyl ethers of diethylene glycol such as butyl carbitol; C ₂ -C ₆ mono -, di -
Or a small amount of an organic acid such as a tri-carboxylic acid (e.g.,
Propionic acid or lactic acid). In many cases,
It is preferred to use a mixture of high-boiling solvents, for example to increase the effectiveness of the solvent mixture or to reduce the undesired effects of the individual components. For example, it is generally not preferred to incorporate large amounts of organic acids into the composition because of the potential for irritation.

A particularly preferred high boiling solvent in terms of price is propylene glycol. However, propylene glycol alone is not particularly effective as a solvent for the compound of formula (I). Therefore, it is preferred to use propylene glycol in combination with another more effective high boiling solvent. Preferably, the weight ratio of propylene glycol to other high boiling solvent in the composition is between 20: 1 and 1:10, preferably
10: 1 to 1: 5, particularly preferably 5: 1 to 1: 1. Preferred solvents for use in combination with propylene glycol include butyl carbitol, hexylene glycol and propionic acid.

A particularly preferred composition of the invention comprises 30 to 60% by weight of a textile conditioner of formula (I), 20 to 40% by weight of propylene glycol, 5 to 15% by weight of another high boiling solvent (butyl carbitol or Xylene glycol), and 0-10% by weight of a low boiling solvent (such as ethanol or isopropyl alcohol).

The composition of the present invention is preferably -5 ° C or lower, especially -10 ° C.
It has a solidification temperature below ℃, ideally below -15 ℃.

In some embodiments, the compositions of the present invention can include small amounts of other known cationic textile conditioners in addition to the textile softener of Formula (I). However, they dissolve in the solvent mixture to give a substantially isotropic or almost transparent liquid. Preferably, the weight ratio of the fabric softener of formula (I) to all other cationic fabric softeners is at least 1: 2, preferably at least 1: 1, particularly preferably at least 2: 1. .

Other cationic textile softeners have a solubility in water of less than 10 g / l in water at pH 2.5 and 20 ° C.
Any abric-substantive cationic compound may be used. Highly preferred materials are -OH, -O-,
-CONH -, - COO- substituted or interrupted by functional groups such as a two C ₁₂ -C ₁₄ quaternary ammonium salts having an alkyl or alkenyl chain.

Known substantially water-insoluble quaternary ammonium compounds have the formula: [Wherein, R ₁ and R ₂ represent a hydrocarbon group having 12 to 24 carbon atoms; R ₃ and R ₄ represent a hydrocarbon group having 1 to ₄ carbon atoms;
Is an anion, preferably selected from halide, methyl sulfate and ethyl sulfate radicals. ].

Representative examples of these quaternary ammonium softeners include:
Ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, dihexadecyl dimethyl ammonium chloride, di (hydrogenated tallow alkyl) dimethyl ammonium chloride, octadecyl dimethyl ammonium chloride, dieicosyl dimethyl ammonium chloride, didocosyl dimethyl ammonium chloride, Examples thereof include di (hydrogenated tallow) dimethylammonium methyl sulfate, dihexadecyldiethylammonium chloride, and di (coconut alkyl) dimethylammonium chloride. Also preferred are dialkylethoxylmethylammonium sulfates based on soft or hard fatty acids. Ditallow dimethyl ammonium chloride, di (hydrogenated tallow alkyl) dimethyl ammonium chloride, di (coconut alkyl) dimethyl ammonium chloride and di (coconut alkyl) dimethyl ammonium methosulfate are preferred.

Another class of preferred cationic compounds that are water insoluble are of the formula: Wherein, R ₆ is from 1 to 4 carbon atoms, preferably 1 or 2 alkyl or hydroxyalkyl group, R ₇ is an alkyl or alkenyl group having 8 to 25 carbon atoms, R ₈ is 8 carbon atoms 25 is an alkenyl group, R ₉ is hydrogen or an alkyl group having 1 to 4 carbon atoms, and A ⁻ is an anion, preferably selected from halides, methosulfate and ethosulfate. ] It is thought that it has an alkyl imidazolinium salt. Preferred imidazolinium salts include 1-methyl-1- (tallowylamido) ethyl-2-tallowyl-4,5-dihydroimidazolinium methosulfate and 1-methyl-1- (palmitoylamide) chloride.
Ethyl-2-octadecyl-4,5-dihydroimidazolinium. Other useful imidazolinium compounds are 2-heptadecyl-1-methyl-1- (2-
Stearylamido) -ethyl-imidazolinium and 2-lauryl-1-hydroxyethyl-1-oleyl-imidazolinium chloride. Also suitable are the imidazolinium textile softening components of USP 4127489. Mixtures of various cationic textile softeners can also be used with the compounds of formula (I).

The composition may also comprise a pH buffer such as a weak acid, for example, phosphoric acid, benzoic acid or citric acid (the pH of the composition is preferably 6.
It is less than 0. ), Re-wetting agents, electrolytes formulated at levels of 20-6000 ppm, viscosity modifiers such as C ₉ -C ₂₄ fatty acids, anti-gelling agents, fragrances, fragrance carriers, fluorescent agents, coloring agents, hydrotropes, defoamers Agents, anti-redeposition agents, enzymes, fluorescent brighteners, opacifiers, stabilizers such as guar gum and polyethylene glycol, anti-shrink agents, anti-wrinkling agents, textile crisping agents, anti-stain agents, stain release Agents, fungicides,
Antioxidants, corrosion inhibitors, preservatives such as commercially available Bronopol ™ which is 2-bromo-2-nitropropane-1,3-diol, dyes, bleaching and bleaching precursors, draping agents, electrostatics It can also include one or more desired ingredients selected from inhibitors and ironing aids such as silicones.

Each of these desired ingredients, when present, is present at a level of up to 5% by weight of the composition. The type and amount of the desired components are preferably selected so that they can be dissolved in the solvent mixture without affecting the substantially isotropic nature of the preferred textile softening composition. Silicones suitable for use in the compositions of the present invention include primarily linear polydialkyl or alkylaryl siloxanes (where the alkyl group has 1 to 5 carbon atoms). The siloxane may be substituted with an amide or amino. When the siloxane is amino-substituted,
The amine group may be a quaternary amine.

The composition can also incorporate, in addition to the cationic textile softener, other non-cationic textile softeners, such as non-ionic textile softeners. Such materials are typically present at a level ranging from 5 to 10% by weight of the composition.

In use, the textile conditioning composition of the present invention is added to a large amount of water to form an aqueous solution which is contacted with the textile to be treated. Generally, the total concentration of the textile softener in the aqueous solution is between 30 and 500 ppm. The weight ratio of textile to aqueous solution is preferably less than 25: 1, most preferably 10: 1 to 4: 1.

The compositions of the present invention can be made by various methods that will be apparent to those skilled in the art. It is convenient to simply mix the components at room temperature, preferably mixing the cationic compound and the organic solvent first, and then mixing the optional water.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1A and 1B show phase diagrams of a ternary system of Varisoft 222 (indicated by “V” in the figure), water (indicated by “W” in the figure) and an organic solvent; The test solvents were (i) ethanol (E); (ii) propylene glycol (PG);
(Iii) butyl carbitol (BC); and (iv) 4: 1
Propylene glycol: butyl carbitol (PG /
BC), "L" in the phase diagram indicates an isotropic liquid, "Lα" indicates a lamellar phase, and "G" indicates a gel.

FIG. 2 shows the change in solidification temperature on the y-axis with the percentage by weight of organic solvent on the x-axis in a system of 40% Prapagen 3445, various test solvents and the balance water, in which "PG"
Indicates propylene glycol, `` BC '' indicates butyl carbitol, `` HG '' indicates hexylene glycol, `` IPA '' indicates isopropyl alcohol, and `` P.
"A." indicates propionic acid.

Embodiments of the invention are described below by way of example with reference to the drawings.

Embodiments of the Invention Example 1 Identification of a Suitable Solvent A. Phase Diagram A ternary system of Varisoft 222 / solvent / water was made by simply mixing the components at room temperature and finally adding water. Va
risoft 222 was lyophilized to remove alcohol before use.

The phase diagram of the ternary system is shown in FIG. The region designated by L in the phase diagram indicates a concentration range in which an isotropic liquid is formed. Phase diagram (i) using only ethanol as the organic solvent shows that ethanol is a very effective solvent for Varisoft 222,
It shows that it is possible to form an isotropic liquid at a wide range of Varisoft 222 concentrations. However, ethanol alone is not a suitable solvent for blending into the composition of the present invention. This is because the flash point becomes very low only with ethanol.

Phase diagram (ii) shows the effect of using propylene glycol, a very flammable solvent, instead of ethanol. The figure shows that isotropic liquid is formed only at low concentrations of Varisoft 222. That is, propylene glycol imparts desirable flammability, but when used alone, is not an ideal solvent for use in the compositions of the present invention.

Phase diagram (iii) shows that the use of butyl carbitol, another less flammable solvent, is
Indicates that it is formed at Varisoft concentration. Figure (iv) shows that for a solvent mixture based on propylene glycol with a small amount of butyl carbitol (4: 1 propylene glycol: butyl carbitol), the phase diagram is similar to that obtained with butyl carbitol alone. To indicate that That is,
By using a solvent mixture, large amounts of the more expensive butyl carbitol can be avoided.

B. Solidification Temperature FIG. 2 shows the effect of organic solvents on solidification temperature in a test system of 40% Prapagen 3445, x% organic solvent and (60-x)% water. The effect of the solvent on the solidification temperature in this system was determined by Varisoft instead of Prapagen 3445.
It can be considered as an indicator of the effectiveness of the solvent in systems containing 222 or other cationic softener of formula (I). In general, the lower the coagulation temperature, the more effective the solvent, the figure shows a ranking, in the order of decreasing effectiveness, propionic acid> isopropyl alcohol> hexylene glycol> butyl carbitol> propylene glycol.

The coagulation temperature was measured by placing the test solution in an ethylene glycol-water bath and lowering the temperature by 1 ° C every 2 hours until solidification of the solution was observed.

As already mentioned, the compositions based on the compounds of the formula (I) preferably comprise at least some organic solvents whose efficacy according to this test is equal to or higher than butyl carbitol.

C. Flash Point A series of solvents with different boiling points were tested in the following compositions to determine the flash points of the compositions.

Varisoft 222 40% Propylene glycol 30% Test solvent 10% Ethanol (Varisoft) 4.44% Water 100% Amount The flash point is determined on a Setaflash ™ device using the appropriate British standard [BS390-A14 (1986), BS6664 part IV (198
6) and BS3679 (1983)].

As an example, the flash points of the products obtained using a series of test solvents with different boiling points are given below (Table I).

These results indicate that if the boiling point of the solvent is significantly lower than 100 ° C., it is difficult to obtain a composition having a flash point of 40 ° C. or higher.

In summary, these results indicate that when a compound of formula (I) such as Varisoft 222 is used as a fabric softener,
It is shown that by the proper choice of solvent, an isotropic liquid with a high flash point and a low flammability can be produced.

Example 2 Examples of compositions of the present invention and their flash points and freezing temperatures are shown in Table II below. All compositions exhibit a flash point of 30 ° C. or higher and a solidification temperature near or below -15 ° C. Vari
soft 222 is commercially available as a 90% active system containing 10% ethanol. The percentages given below for Varisoft indicate the weight percentage of active ingredient. Setafl of the flash point of the composition
Measured using an ash device. The coagulation temperature was measured in an ethylene glycol-water bath as described above.

These results indicate that an isotropic liquid textile conditioner composition having a satisfactory flash point and freezing temperature,
It shows that it can be obtained in a wide range of concentrations.

The following tests were performed to ensure that compositions based on concentrated organic solvents exhibited satisfactory behavior when diluted with water in a washing machine. The softening test was performed after the washing / rinsing step in a Japanese type washing machine. The softening effect is a 40% active product based on organic solvents and the corresponding 5% Varisoft used at the same activity level
A direct comparison was made between the LT90 aqueous dispersion. These tests did not identify the product,
It shows that the softening effect obtained with the composition based on organic solvents is comparable to that of the aqueous composition.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Naley, William Frederik's Sawter UK, El 48.2 GTE, Merseyside, Wirral, Calday, Beatty Close 2 (56) Reference Reference JP-A-62-223374 (JP, A) JP-A-1-501492 (JP, A) US Patent 4,460,47 (US, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D06M 13 / 00-13/535 CA (STN)

Claims (14)

(57) [Claims] (I) 20 to 60% by weight of the formula (I): Wherein, a and b is 1-5 each independently, c is 1 to 10, each R is selected from saturated and unsaturated alkyl group of 14 to 22 carbon atoms independently, Y ^- Is an anion. Cationic fiber product softener, (ii) 10-60% by weight of organic solvent or organic solvent mixture,
And, optionally, (iii) a textile softening composition comprising water, wherein the cationic textile softening agent is soluble in the organic solvent or organic solvent mixture and optionally present water, and The solvent mixture is selected such that the flash point of the composition is at least 25 ° C., the composition comprises no more than 10% by weight of a solvent having a boiling point of less than 100 ° C., and a solvent having a boiling point of 100 ° C. or more. Is 1
A textile softening composition characterized in that the weight ratio with the solvent below 00 ° C is at least 2: 1. 2. The composition according to claim 1, wherein the flash point is at least 30 ° C. 3. The composition according to claim 2, wherein the flash point is at least 40 ° C. 4. The composition according to claim 3, wherein the flash point is at least 50 ° C. 5. The method according to claim 1, wherein all or most of the organic solvent or the organic solvent mixture comprises one or more solvents having a boiling point of 100 ° C. or higher. Composition. 6. An organic solvent mixture comprising at least one solvent having a boiling point of less than 100 ° C. and at least one solvent having a boiling point of at least 100 ° C., wherein the solvent having a boiling point of less than 100 ° C. The weight ratio of the solvent occupying at most 10% by weight and having a boiling point of at least 100 ° C. to the solvent having a boiling point of less than 100 ° C. is at least 2: 1. A composition according to claim 1. 7. The composition according to claim 5, wherein the solvent having a boiling point of at least 100 ° C. is selected from organic acids, polyols, glycols or alkyl ethers of polyglycols and mixtures thereof. 8. The composition according to claim 7, wherein the solvent is selected from propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, butyl carbitol, propionic acid, lactic acid and mixtures thereof. 9. The composition according to claim 8, wherein the solvent is selected from propylene glycol, hexylene glycol, butyl carbitol and mixtures thereof. 10. An organic solvent mixture comprising propylene glycol and at least one other solvent having a boiling point of at least 100 ° C., wherein the weight ratio of propylene glycol to at least one other solvent is from 20: 1 to 1: 1. The composition according to any one of claims 1 to 9, wherein the composition is in the range of: 10. 11. A textile conditioner of formula (I) of 30 to 6% by weight, propylene glycol of 20 to 40% by weight,
Claims: 5 to 15% by weight of at least one other solvent having a boiling point of 100C or more, and 0 to 10% by weight of at least one low-boiling solvent having a boiling point of less than 100C. The composition according to any one of claims 1 to 10. 12. The composition according to claim 1, wherein the composition has a solidification temperature of -5 ° C. or lower. 13. The composition according to claim 12, wherein the coagulation temperature is -15 ° C. or lower. 14. The composition according to claim 1, wherein the composition is a substantially isotropic liquid.