NO149510B - LIQUID PREPARATION FOR TREATMENT OF TOEY, AND PROCEDURE FOR THE PREPARATION OF SUCH PREPARATION - Google Patents

Description

The invention relates to a liquid preparation which is capable of depositing a material which produces an effect which can be perceived sensorially on cloth surfaces. The preparation can be used in diluted form, and examples of cloth surfaces are cotton, polyacrylic, polyamide and polyester fibres, wool and linen.

The material that is perceived sensorially and is to be deposited will be selected for providing a desired effect on the surface, and examples of this material are fluorescent agents, whitening agents, perfume, pigments, dyes, bactericides, textile conditioners, e.g. plasticizers, antioxidants and antistatic agents.

The liquid preparation for fabric treatment according to the invention thus contains a material that can be perceived sensorially selected from whiteners, pigments, dyes, perfumes, textile conditioners, bactericides, antioxidants and antistatic agents, and the preparation is characterized in that it contains at least:

I) 0.5-50% by weight of a disperse phase consisting of particles

which is a mixture of:

a) 25-99% by weight of non-cationic organic material with a solubility in the water phase of not more than 200 ppm at 25°C; b) 0.5-25% by weight cationic material with a water solubility not greater than 5 g/l at 25°C and which is selected from cationic surfactants and cationic fabric softeners; and c) 0.5-50% by weight of a material that can be perceived sensorially and is selected from whiteners, pigments, dyes,

perfume, fabric conditioners, bactericides,

antioxidants and antistatic agents, and

II) optionally 0.5-30% by weight of another dispersed phase comprising a textile conditioning agent,

III) 50-99.5% by weight of a water phase in which the said particles are dispersed.

The textile conditioning material is preferably a fabric softener.

The term "material which can be perceived sensorially" is used to define a material which, when deposited on a cloth surface, is directly or indirectly detectable by a human sense. Thus, perfume, a preferred material for deposition, is a fragrance preparation detected by the sense of smell, a fabric softener is perceived by the tactile sense (feeling), and fluorescent agents are perceived by the sense of sight. Materials that are able to change the surface of cloth so that the sound changes during movement are also included. Some materials that are perceived sensorially act directly on a human sense, e.g. a perfume, while some materials will be perceived indirectly by their impact on another substance. An example is a bactericide which can be detected by a reduction in the smell of laundry due to bacterial action on microorganisms.

These microorganisms will accumulate on the cloth during use. Another sensory-perceivable material that provides odor reduction is an antioxidant.

In some preparations, an effect on the surface will be achieved by depositing the organic base material. That is to say, the organic base mass can produce a desired effect in addition to that obtained from the material that is perceived sensorially.

In the case of textiles, e.g. deposition of long-chain fatty alcohols, which are applicable as the organic matrix material, a demonstrable effect with regard to textile handling.

It is necessary to ensure a minimum proportion of soluble cationic material in ionic form in the aqueous phase, as such free cationic material in the liquid phase will adsorb preferentially, or at least adsorb in competition with the particles from the first dispersed phase . This preference or competition could lead to an inefficient deposition of the dispersed phase on the surface.

One reason for inefficient deposition is charge reversion of the naturally negatively charged surface, which can occur if sufficient positively charged ions are adsorbed on the surface to be numerically greater than the inherent negative charge on the surface. This reversal occurs with synthetic polymer surfaces, e.g. textiles of polyacrylic, polyester and polyamide. These are hydrophobic. On these materials the negative charges are not as abundant as they are on hydrophilic materials, e.g. cotton. Where the positively charged ions originate from cationic materials as described here, the alkyl chain of these molecules can absorb on synthetic polymer surfaces and bind by hydrophobic interaction. Thus, the binding of these cationic materials is not only dependent on a charge interaction between the positive center of the cationic and a negative site on the substrate. This charge-reversing effect was shown by measuring zeta potentials by a flowing potential technique on

acrylic and cotton textile samples. These samples were immersed in solutions of sodium chloride (5xl0<->^ molar) at a pH value of 6. Upon addition of cetyltrimethylammonium bromide (CTAB) at a strength of 10 molar, the zeta potential of the acrylic sample clearly reversed while the same was not the case for the cotton sample. The particle size of the first dispersed phase will usually be in the range from 0.1 to 20 µm, more commonly 1.0 to 20 µm.

The cationic material in the first dispersed phase is preferably present in an amount of from 2 to 10% of the phase. The first dispersed phase may be present in an amount of up to approx. 10%. This area will preferably be used when the base material also provides an effect that is perceived sensorially. When the preparation contains another dispersed phase, the first dispersed phase will preferably be present in an amount of up to approx. 2%.

The components and parameters for the deposition preparation shall be discussed in the following.

Organic base materials

It is necessary that the base material has a solubility at 25°C in the liquid phase of no more than 200 ppm, preferably no more than 50 ppm. Examples of matrix materials are primary or secondary fatty alcohols of the formula R.OH, e.g. stearyl alcohol, oleyl alcohol, cetyl alcohol and tallow alcohol, hydrocarbons of the formula R.CH,, e.g. octadecane, eicosane2, docosane and tetracosene, aldehydes and ketones with the formula R.CO.R, e.g. methyl stearyl ketone and stearyl aldehyde, fatty acids of the formula R.COOH, e.g. tallow fatty acid, coconut fatty acid, oleic acid, stearic acid

1

and behenic acid, as well as esters of such acids of formula R.CO.OR

or R.CO.OR o, e.g. ethyl palmitate and stearyl stearate. In these formulas, R and R"<*>" are saturated or unsaturated alkyl or alkylaryl groups and may be straight chain or branched. The number of carbon atoms will be from 8 to 22, preferably 14 to 22.

2

R is hydrogen or an alkyl group with 1-4 carbon atoms.

Other examples of classes of base material materials such as 3 4

can be used, are fatty acid amides of the formula R.CON.R R where R 3 and R 4 are each hydrogen, alkyl groups with 1-4 carbon atoms,

-CH2CH2OH, -(CH2)3OH or -CH(CH3)CH2OH, e.g. tallow diethanolamide and coconut monoethanolamide. Amines of formula RN.R^R^

13

or R.R.NR, e.g. stearyldiethanolamine and ditalcmethylamine,

12

ethers of formula RO.R or RO.R , e.g. stearyl ethyl ethers and

epoxides of formula

e.g. stearyl epoxide. The alkylene oxide adducts of fatty alcohols, fatty acids and fatty amides are also usable as matrix materials. These adducts have the respective formulas R(CH.R5.CH_0) OH, R(CH.R<5><CHo0) .COOH and R(CH.R<5.>CH„0) .CON.R<3> R<4>.

^ 2 n 2 n =v 2 n

R is hydrogen or a methyl group and n is chosen so that the solubility limits stated above are not exceeded, e.g. tallow alcohol condensed with an average of 3 moles of ethylene oxide, tallow amide condensed with an average of 5 moles of ethylene oxide and oleic acid condensed with an average of 3 moles of ethylene oxide. Dibasic carboxylic acids are also examples of applicable matrix materials.

It should be noted that the above list of examples includes carboxylic acids. These materials have low solubility in the liquid phase and furthermore have a low dissociation constant. In the dispersed phase in the preparation, they are able to serve as base material.

The organic matrix material will be non-cationic and will preferably be non-ionic. The term non-ionic defines a material which does not produce ionic groups in contact with the water phase, or which produces such groups only to a negligible extent.

Cationic materials

Suitable materials are found in both the soluble and insoluble classes of cationic materials. Any cationic material used must not have a solubility in water greater than 5 g per liter at 25°C. Therefore, both cationic surfactants and cationic materials useful as fabric softeners can be used. The latter is preferred. The class of amphoteric compounds whose ionic groups are dependent on the pH value in the liquid phase, can also be used for providing the cationic material with selection of the system's pH value. For amphoteric compounds, as the pH value moves towards the acidic range, the groups become cationic at a specific pH value and will become effective in the preparation according to the invention.

It should be understood that the boundaries between soluble and insoluble materials cannot be clearly drawn, and therefore a class of materials generally considered soluble can be considered insoluble when the length of the alkyl chain or chains exceeds . a specific limit. The less soluble cationic materials are preferred, as they will not be leached as easily from the dispersed particles during storage. These materials will preferably have a solubility that is not greater than approx. 50 ppm.

Generic examples of soluble cationic materials are listed below: + 12 3 Alkyl quaternary ammonium salts: R.N(R R R ).X , e.g. cetyltrimethylammonium bromide and tallow trimethylammonium bromide.

Alkylpyridinium salts:

e.g. laurylpyridinium-

chloride and cetylpyridinium chloride.

+ 12 Alkylaryl-quaternary-ammonium salts: R.N(R R )2CgH^X , e.g. stearyldimethylbenzylammonium chloride.

Amine salts: R - N.rVh X~, e.g. C12H25.<N>(CH3)2H.CH3CO~, where R is an alkyl chain with 8-22 carbon atoms, preferably 12-18 carbon atoms,

12 3 4

R , R , R , R are methyl, ethyl or propyl radicals,

X is an anion for example halogen (e.g. chloride or

bromide), sulphate, acetate, methosulphate and ethosulphate.

Examples of the insoluble cationic materials which are useful as fabric softeners are: 12+ 3 4 Dialkyl-quaternary-ammonium salts: R R N R R .X , e.g. distearyldimethylammonium chloride, dicoco dimethylammonium chloride and di (2-stearoyloxyethyl) dimethylammonium chloride.-Amine salt derivatives: R<1>R<2>N R<3.>H.X~, e.g. C17H35CONHCH2-NH(CH3)(C17<H>35)CH3COO<_> and (C17H35CONHCH2CH2)2NH2HCOO~.

Compounds with a long alkyl chain: R N R R R .X , e.g.

+ - 12 <C>17H35COOCH2CH2NH(CH3)2CH3COO , where R , R are alkyl chains with 12-25 carbon atoms that optionally contain amide or 3 4 5 ester bonds, R , R is methyl", ethyl or propyl, R- is H, methyl, ethyl or propyl, X is an anion, for example Cl~, Br", I~, CH3S<0>4-, <C>2H5SO~, CJ^COCT, S0~.

Examples of the amphoteric compounds that are applicable are given below: <+> 1 2

Alkyl sulfobetaines: I) R - N (R )'2R SO 3 , e.g. hexadecyl dimethylammoniopropane sulfonate.

+ 12-

II) R - CH(NRj)-R SO,

Amine oxides: RN * 0, e.g. hardened tallow-dimethylamine oxide: 1 2 <+ >Carboxybetaines: R - N(R )2R C00 , e.g. C18H37<N>(CH3)2CH2~ CH<2>COO~.

Hydroxamic acid betaine, R N (R1)2CH2CONHOHCl , e.g. C18H37N(CH3)2 CH2CONHOHCl"

where R is an alkyl chain with 8-22, preferably 12-18 carbon atoms,

R"*" is methyl or ethyl,

R 2 is a short alkyl chain with 1-4 carbon atoms.

Another class of cationic fabric softeners useful in the first dispersed phase is based on imidazoline and has the general formula:

where R and R are each substantially linear aliphatic hydrocarbon groups of 15-24 carbon atoms, R is an alkyl group of 1-4 carbon atoms, R 3 is a divalent alkylene group of 1-4 carbon atoms, and X is an anion and n integer equal to the charge on X.

Liquid phase

The liquid phase will be aqueous, but will normally contain other materials, e.g. short-chain alcohols, buffering agents for providing the required pH value, e.g. to ensure that any amphoteric surfactant or conditioning agent is in the cationic form, and electrolytes may also be present. Emulsifiers, coloring materials, perfume, bactericides and surfactants are also possible components of the aqueous liquid phase.

A possible component in the liquid phase is a dispersed textile conditioner in an amount of from 0.5 to 30%. This may preferably be present in an amount of from 2 to 15%. This agent can be a fabric softener. Examples of these materials are given above, in the section describing the cationic materials present in the first dispersed phase.

Manufacturing methods

Although it has been shown that several methods of production provide the desired deposition properties, certain of these methods are preferred, in the preferred method the organic matrix material, cationic material and material that is perceived sensorially are melted at the same time, as a first step.

The melt can then be dispersed in hot water with subsequent cooling, or the melt can be solidified and dispersed in cold water. Any additional components in the water phase, and in the second dispersed phase, can then be added.

Examples of apparatus which are useful for effecting dispersion of the organic matrix material in the liquid phase are high-speed stirrers, ultrasonic dispersers, vibrating tube blades and continuous mixers. These devices provide different particle sizes that will be of specific use for different preparations.

Examples of preparations according to the invention shall be given below.

Example - 1

98 g of tallow alcohol ethoxylated with an average of 3 moles of ethylene oxide (TA3E0) as the organic matrix material and 2 g of Sudan Black B (Solvent Black 3 - Color Index 26150) were fused together. Cetyltrimethylammonium bromide (CTAB) was melted into this mixture at the following levels: 0, 0.5, 1.0, 2.0, 5.0 and 10.0 g for each 100 g of mixture of tallow alcohol 3E0 and Sudan Black B.

These mixtures were emulsified with water at 80°C while still in the molten state, using a Minisonic 4 homogenizer to form 1% concentrations.

Fabrics of cotton terry toweling fabric and bulky knitted acrylic fabric were rinsed in dilutions of these emulsions (30 g emulsion per liter of water) at a liquid/fabric ratio of 75:1, 25°C, in a Terg-O- Tometer (US Testing co. Inc.) for 5 minutes at 50 cycles per minutes of agitation. The fabric was removed and excess liquid was removed using a centrifuge before the pieces were dried completely in a heated drying cabinet.

Reflectivity of the fabric was measured spectrophotometrically before and after the treatment. The reflectance was measured with a Zeiss Elrepho Reflectance Spectrophotometer at a light wavelength of 620 nm and converted to g values (K = absorptivity coefficient, and S = scattering coefficient) using the relevant Kubelka-Munk relationship. — -the quantity is proportional

with the weight of genetic material present. A—K, the difference between — K for the dyed fabric and the original fabric was run in the computer and represents the amount of dye that had settled on the fabric during the rinse.

The results were as follows:

In this system, the optimum amount of CTAB for the cotton fabric is above 1%, and for the acrylic fabric it is between 0.5 and 2% by weight of the non-ionic material. These optimal ranges overlap between 1% and 2% CTAB, where enhanced deposition is achieved on both substances.

Example II

Tallow alcohol 3E0 and Sudan Black B were fused together in the same amounts as stated in Example I and were emulsified in water as described therein, without CTAB. CTAB solutions were prepared and added separately to the dispersion at such levels that the ratios of CTAB to the tallow alcohol 3E0/Sudan Black B mixture were the same as in Example I.

The mixtures were used for the treatment of cloth as indicated in Example I, with the following results:

The optimum level of CTAB for cotton was approx. 1%, and for acrylic cloth it was between 0.5 and 2% by weight of the base material.

Example III

The mixtures of Example I were prepared, but were allowed to cool and solidify before dispersing in cold water. The other experimental parameters were those of Example I.

The results were:

The optimum amount of CTAB in this case, for cotton, was between 0.5 and 5%, and for acrylic cloth it was also between 0.5 and 5% by weight of the base material. It will be seen that these results are better than those reported in Example I where the dispersed phase was dispersed while molten.

The effect achieved in examples I, II and III will be seen to decrease in the order III, I and II. This reduction follows from the amount of free cationic material in the liquid phase. The method of preparation, as used in example III, gives the smallest amount of cationic material in the liquid phase.

Example IV

98 g of tallow alcohol 3 EO and 2 g of Sudan Black B were fused with 0, 0.5, 1.0, 2.0, 5.0, 10.0 g of distearyldimethylammonium chloride. Dispersions were prepared using the method of Example I.

The results were:

The optimum amount of cationic material for cotton is above 2%, and for acrylic it is between 0.5 and 5% by weight of the non-ionic material. The best level for both clothes is between 2 and 5% cationic.

Example V

Example I was repeated using dodecyl trimethylammonium bromide (DTAB) instead of CTAB. The results were as follows:

The optimum amount of cationic material for cotton was above 2%, and for acrylic between 0.5 and 10%. Increased deposition was achieved on both substances between 2 and 10% cationic, by weight of the non-ionic material.

Example VI

9 g of tallow alcohol 3E0 and 1 g of di-tert-butylhydroxytoluene (antioxidant) were fused with 2 g of distearyldimethylammonium chloride, mixed thoroughly and allowed to solidify. The waxy solid was made into a paste and then a cream by grinding an increasing amount of water in a pestle and mortar.

The cream was finally dispersed in water to a total volume of 500 ml, by stirring for 1 minute with a high-speed stirrer, to form product A. Control product B was prepared by dissolving 4 g of the antioxidant in 10 ml of acetone and filling to 2 liters of water.

Two naturally soiled pillowcases were washed for 5 minutes at 40°C in a paddle-type washing machine. An unscented, but otherwise conventional, detergent product was used at 0.2%. After rinsing, the pillowcases were cut in half, and one half of each was further rinsed (5 minutes at 20°C) in 2 liters of water containing 10 ml of the above dispersion. The other halves were treated similarly with product B.

The pillowcase halves were then compared for smell by a panel of 20 judges, and no significant differences were found. However, after storage for 1 week in separate containers, the half that had been treated with product A was preferred over the control half in 35 out of 40 comparisons. This result shows that the antioxidant deposited in a preparation according to the invention is more evenly deposited over the laundry than the antioxidant in product B and therefore suppresses bad odor more effectively.

Example VII

Emulsions C and D were prepared from tallow alcohol 3E0 (TA3E0), a perfume mixture, distearyldimethylammonium chloride (DDAC) in water to the following compositions:

The method of manufacture was to mix TA3E0, perfume and DDAC by melting them together, after which the mixture was allowed to solidify, after which cold water was gradually mixed in so that a coarse dispersion was obtained. This was then treated ultrasonically to form a smooth emulsion.

Resin-finished polyester/cotton fabric was rinsed in dilutions of these emulsions in a paddle-action washing machine (Hotpoint Supermatic) using a ratio of 17 liters of liquid to 700 g of fabric and adding 10 ml of one of the emulsions. The fabric was agitated in the liquid at room temperature i

15 minutes, removed and dried.

A panel of 20 judges was asked to smell the laundry, and all were able to detect the difference in perfume level between laundry treated with the two emulsions. Those treated with D were stronger than those treated with C. This could be expected from the difference in perfume content in the two emulsions. Both treated fabrics were much more strongly perfumed than one that had been rinsed in a suspension of the perfume alone at the same total concentration of perfume as from emulsion D.

Example VIII

A dispersion was prepared, by a method described in Example VII, comprising 6 g of stearyl stearate, 4 g of a perfume mixture, 1 g of distearyldimethylammonium chloride and 100 g of water. 25 ml of this dispersion was then added to 475 ml of a 4.5% dispersion of distearyldimethylammonium chloride in water.

To a further sample of the 4.5% dispersion, the same perfume mixture was added alone, to a level of 0.2%. These two dispersions were then used for final rinsing treatment of wash loads.

Balanced laundry loads containing cotton terry towels were washed in an AEG Lavamat Regina drum type washing machine with an unscented detergent on the 60°C wash program. Each charge was treated in the final rinse with one of the two dispersions mentioned above. After four loads were treated with each dispersion, the towels were assessed by an expert panel for softness. No significant differences were found between the two dispersions. However, the panel agreed that the towels treated with the dispersion containing the carrier were much more strongly perfumed than those treated with the dispersion containing the perfume mixture alone.

Example IX

A dispersion was prepared by the method described in Example VII, comprising 5 g of N,N-ditalg-ethanolamine, 0.5 g of distearyldimethylammonium chloride optical brightener, 0.05 g of 1-p-carboxymethylphenyl-3-p- chlorophenyl-A 2-pyrazoline and 100 ml of water.

A dilution of this dispersion containing 50 ml i

45 liters were used to rinse 3 kg of non-fluorescent cotton terry towels for 10 minutes at room temperature. A similar load of towels was rinsed in a solution containing 50 ml of a 0.5% dispersion of distearyldimethylammonium chloride. Attempts to obtain a 5% dispersion of N,N-di-tallow ethanolamine as a further control were unsuccessful.

This preparation is an embodiment where the organic base material provides a desirable advantage, i.e. fabric softening.

The fluorescent agent is nylon noun, but has been made cotton noun by application of the invention.

Example X

16 pieces of cotton terry towel fabric (20 cm x 20 cm) were washed together at 60°C for 15 minutes in 3 liters of a 0.4% solution of a conventional laundry detergent. The pieces were rinsed twice in cold water and divided into four sets of four pieces for the third rinse. The sets of four were then rinsed for 5 minutes in 800 ml of cold water containing:

A - nothing - this was the control set.

B - 2 ml of a dispersion, prepared as indicated in Example VII,

comprising 5% paraffin wax and 0.05% distearyldimethylammonium chloride.

C - 2 ml of a 0.05% dispersion of distearyldimethylammonium chloride. D - 10 ml of a 1% dispersion of paraffin wax in water (a 5% dispersion was not sufficiently stable to be used).

After drying, the cloth pieces were rearranged into sets of four cloth samples, where one set comprised one cloth from each treatment. These sets were then assessed for softness by a panel of 5 experienced judges. The form of assessment was to rank the cloth samples in each set with 1 point for the softest cloth and 4 points for the hardest. Therefore, if one treatment simultaneously produced the softest fabric in each set, the total score for that treatment would be 20. Likewise, if one treatment simultaneously produced the hardest fabric, its total score would be 80.

The relevant grades for the above treatments were: A 68

B 26

C 55

D 51

Thus, control rinse A was not significantly different from treatments C and D. Treatment B produced a significantly softer set of laundry. This result was found because there was not enough plasticizer alone to make a significant difference, but the plasticizer and paraffin wax did make a significant difference when deposited together.

Claims (11)

1. Liquid preparation for fabric treatment, with a material that can be perceived sensorially selected from whiteners, pigments, dyes, perfumes, textile conditioners, bactericides, antioxidants and antistatic agents, characterized in that the liquid preparation contains at least: I) 0.5-50 % by weight of a disperse phase consisting of particles which are a mixture of: a) 25-99% by weight of non-cationic organic material with a solubility in the water phase of not more than 200 ppm at 25°C; b) 0.5-25% by weight cationic material with a water solubility not greater than 5 g/l at 25°C and which is selected from cationic surfactants and cationic fabric softeners; and c) 0.5-50% by weight of a material that can be perceived sensorially and is selected from whiteners, pigments, dyes, perfumes, textile conditioners, bactericides, antioxidants and antistatic agents, and II) optionally 0.5-30% by weight of another dispersed phase comprising a textile conditioner, III) 50-99.5% by weight of a water phase in which the said particles are dispersed. 2. Preparation as stated in claim 1, characterized in that the textile conditioner consists of a fabric softener. 3. Preparation as specified in any of the preceding claims, characterized in that the cationic material in the first disperse phase is included in an amount of 2-10% by weight, calculated on the phase. 4. Preparation as stated in any of the preceding claims, characterized in that the first disperse phase is included in an amount of up to 10% by weight, preferably up to 2% by weight, calculated on the preparation. 5. Preparation as specified in any of claims 2 to 4, characterized in that the textile conditioner is included in an amount of 2-15% by weight, calculated on the phase. 6. Preparation as stated in any one of claims 1 to 5, characterized in that the non-cationic organic material is a non-ionic material. 7. Preparation as stated in claim 1, characterized in that the non-cationic organic material has a solubility in the water phase of no more than 50 ppm. 8. Preparation as stated in any of the preceding claims, characterized in that the cationic material in the first disperse phase has a solubility in water that does not exceed 5 g/l at 25°C. 9. Preparation as stated in any of the preceding • claims, characterized in that the cationic material in the first disperse phase is a fabric softener. 10. Preparation as stated in any of the preceding claims, characterized in that the non-cationic organic material consists of aliphatic alcohols containing 8-22 carbon atoms, aliphatic alcohols which are ethoxylated with up to approx. 5 mol of ethylene oxide, as well as esters of formula RCOOR<1> whereby R and R^" are each alkyl or alkenyl groups containing 8-22 carbon atoms. 11. Method for producing a preparation as stated in any of the preceding claims, characterized in that the components of the first dispersed phase are fused together and then dispersed in the aqueous phase or a component thereof while they are in a molten state, or after that they have been allowed to harden.