JPH0433908B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to liquid formulations capable of depositing materials on textile surfaces that produce visually or olfactory perceptible effects. This formulation can be used in diluted form and examples of textile surfaces are cotton, polyacrylic, polyamide and polyester fibres, wool and flax. The visually or olfactory material to be deposited is selected to give the desired effect to the surface, and this material is selected from whitening agents, pigments, dyes, fragrances, fungicides and antioxidants. It is something. The present invention provides a solubility in the aqueous phase of from about 25 to about 99%.
a non-cationic organic matrix material of not more than 200 ppm; b selected from about 0.5 to about 25% of cationic surfactants and cationic fabric softeners with a solubility in water of not more than 5 g/25°C; a cationic material; and c about 0.5 to about 50% of a whitening agent, pigment, dye,
from about 0.5 to about 50% by weight of a first dispersed phase consisting of particles that are a mixture of visually or olfactory materials selected from fragrances, disinfectants, and antioxidants; from about 50 to about 99.5%; A liquid textile treatment formulation is provided in the form of a particle dispersion dispersed in an aqueous phase. Optionally, the formulation contains about 0.5% to about 30% of a second dispersed phase comprising a textile tempering material. The term visually or olfactory material refers to a material that, when deposited on a textile surface, is directly or indirectly detectable by the human sense of sight or smell. For example, perfumes of materials suitable for deposition are fragrant compositions that are detected by the olfactory organ, and fluorescent agents are visually perceptible. Items with materials that can be recognized visually or olfactory;
For example, fragrances act directly on the human senses, while some materials can be perceived indirectly by acting on other substances. An example of this is a disinfectant, which can be detected by a reduction in fabric odor due to its bactericidal action against microorganisms that grow on the fabric. Another olfactory perceptible material that provides odor reduction is an antioxidant. In some formulations, effects at the surface may be obtained by deposition of organic matrix materials. That is, this organic substrate can impart the desired effect in addition to that obtained from visually or olfactorily perceptible materials. For example, with respect to textiles, the deposition of long chain fatty alcohols that can be used as organic matrix materials provides a detectable effect on textile handling. It is necessary that a minimum proportion of soluble cationic material in ionic form be present in the aqueous phase. The reason is that this cationic material in the liquid phase selectively
Or at least it competes with and adsorbs the particles of the first dispersed phase. This selective or competitive adsorption prevents effective deposition of the dispersed phase on the surface. One factor that prevents effective deposition is the charge reversal of a naturally negatively charged surface, which means that enough positively charged ions are absorbed onto it such that it becomes numerically greater than the inherent negative charge of the surface. This occurs when
This inversion occurs on synthetic polymer surfaces, such as polyacrylic, polyester, and polyamide fabrics. Negative charges on these materials are not as abundant as on hydrophilic materials, such as cotton. When the positively charged ions are derived from the cationic materials described herein, the alkyl chains on these molecules are absorbed onto the synthetic polymer surface and bonded by hydrophobic interactions. Therefore, the binding of these cationic materials does not simply depend on the charge interaction between the positive center of the cationic material and the negative location on the substrate. This charge reversal effect was demonstrated by measuring zeta potential by streaming potential technique on acrylic fiber and cotton fabric samples. These samples were prepared using a solution of sodium chloride (5 x 10 ^-4
mol). Addition of cetyltrimethylammonium bromide (CTAB) to a concentration of 10 ^-4 molar reversed the zeta potential for the acrylic sample in sign, whereas that of the cotton sample did not. The particle size of the first dispersed phase is typically from about 0.1 to about 20 microns, more usually from about 1.0 to about
In the 20 micron range. The cationic material in the first dispersed phase is preferably present in an amount of about 2 to about 10% of the phase. This first dispersed phase is present in an amount up to about 10%. This range is preferred as the substrate material also provides a visually or olfactory perceptible effect. If the formulation includes a second dispersed phase, the first dispersed phase is preferably present in an amount up to about 2%. The ingredients and parameters for the deposition formulation are discussed below. Organic Substrate Material The substrate material should have a solubility in the liquid phase at 25° C. of less than 200 ppm, preferably less than 50 ppm. Examples of substrate materials are primary or secondary aliphatic alcohols of the formula ROH, such as stearyl alcohol, oleyl alcohol, cetyl alcohol and tallo-alcohol, hydrocarbons of the formula RCH ₃ , such as octadecane, eicosane,
docosane and tetracosene, aldehydes and ketones of the formula RCOR ² , such as methyl stearyl ketone and stearyl aldehyde, of the formula
Fatty acids of the formula RCOOH, such as tallow fatty acids, coconut fatty acids, oleic acid, stearic acid and behenic acid, and esters of these acids of the formula RCOOR ¹ or RCOOR ² , such as ethyl palmitate and stearyl stearate. In these formulas, R and R ¹ are saturated or unsaturated alkyl or alkylaryl groups, and may be either straight chain or branched. The number of carbon atoms is from 8 to 22, preferably from 14 to 22. R ² is hydrogen or an alkyl group having 1 to 4 carbon atoms. Other examples of substrate materials that may be used include the formula
RCONR ³ R ⁴ (wherein R ³ and R ⁴ are each hydrogen, an alkyl group having 1 to 4 carbon atoms, -
_CH2CH2OH , -( _CH2 ) _{3OH or} -CH( _CH3 )
fatty acid amides of the formula RNR ³ R ⁴ or RR ¹ NR ³ , such as stearyldiethanolamine and ditallow-methylamine, such as stearyldiethanolamine _and ditallow-methylamine, such as tallow diethanolamide and coconut monoethanolamide (CH ² OH); or an ether with ROR ² , such as stearyl ethyl ether and the formula For example, stearyl epoxide can be mentioned. Alkylene oxide adducts of fatty alcohols, fatty acids and fatty amides can also be used as substrate materials. These adducts each have the formula R(CHR ⁵ CH ₂ O) _o OH, R
(CHR ⁵ CH ₂ O) _o COOH and R (CHR ⁵ CH ₂ O) _o
Expressed as CONR ³ R ⁴ . R ⁵ is hydrogen or a methyl group and n is chosen so as not to exceed the solubility limits mentioned above, for example tallow alcohol condensed with an average of 3 mol of ethylene oxide, an average of 5
mol of ethylene oxide and oleic acid condensed with an average of 3 moles of ethylene oxide. Dibasic carboxylic acids are also examples of substrate materials that can be used. Although carboxylic acids are included in this example, these materials have low solubility in the liquid phase and even lower dissociation constants. In the dispersed phase of the formulation these can act as matrix materials. This organic tempered material is non-cationic and preferably non-ionic. The term nonionic refers to materials that do not produce ionic species or produce ionic species only to a negligible extent when contacted with an aqueous phase. Cationic Materials Suitable materials are both soluble and insoluble cationic materials. Any cationic material used must not have a solubility in water of more than 5 grams per hour at 25°C. Thus, both cationic surfactants and cationic materials useful as fabric softeners can be used, with the latter being preferred. Amphoteric compounds in which the ionic species depends on the pH of the liquid phase can also be used, giving cationic materials depending on the selection of the pH of the system. In amphoteric compounds, when the pH is shifted to acidic, they become cationic at a certain PH and are useful in the formulations of the present invention. It is generally difficult to draw a clear boundary between soluble and insoluble materials; even materials that are generally considered soluble may become insoluble if the length of one or more alkyl chains exceeds a certain limit. It may be considered that Cationic materials with lower solubility are preferred. The reason is that these are not as easily leached from the dispersed particles during storage. Those having a solubility of about 50 ppm or less are preferred. Common examples of soluble cationic materials are listed below: Alkyl quaternary ammonium salts: RN ⁺ (R ¹ R ² R ³ )X ⁻ , such as cetyltrimethylammonium bromide and tallo-trimethylammonium bromide. Alkylpyridinium salt:

[Formula] For example, laurylpyridinium chloride and cetylpyridinium chloride. Alkylaryl quaternary ammonium salt: R ⁺ N (R ¹ R ² ) ₂ C ₆ H ₅ X ^- , for example stearyldimethylbenzylammonium chloride. Amine salt: R
-N ⁺ R ¹ R ² HX ^- , e.g. C ₁₂ H ₂₅ N ⁺ (CH ₃ )H.
_CH3CO2- ^, (wherein R is _an alkyl group of 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, ^R1 ,
R ² , R ³ , R ⁴ are methyl, ethyl or propyl groups and X is an anion, such as halogen (eg chloride or bromide), sulfate, acetate, methosulfate and ethosulfate). Examples of insoluble cations that can be used as fabric softeners ^are : Dialkyl quaternary ammonium salts: R ¹ R ² N ⁺ R ³ R ⁴ , and di(2-stearoyloxyethyl)dimethylammonium chloride. Amine salt derivatives: R ¹ R ² N ⁺ R ³ HX ^- , e.g.
C ₁₇ H ₃₅ CONHCH ₂ N ⁺ H (CH ₃ ) (C ₁₇ H ₃₅ )
CH ₃ COO ^- and (C ₁₇ H ₃₅ CONHCH ₂ CH ₂ ) ₂ N ⁺ H ₂ HCOO ^- . Compounds with one long alkyl chain: R ¹ N ⁺ R ³ R ⁴ R ⁵ X ^- , e.g.
C ₁₇ H ₃₅ COOCH ₂ CH ₂ N ⁺ H(CH ₃ ) ₂ CH ₃ COO ⁻ , where R ¹ and R ² are an alkyl chain of 12 to 25 carbon atoms optionally containing an amide or ester bond;
R ³ and R ⁴ are methyl, ethyl or propyl groups,
R ⁵ is H, methyl, ethyl or propyl;
X ^- is an anion, such as Cl ^- , Br ^- , I ^- ,
_CH3SO4- ^, _C2H5SO4- ^, _{CH3COO- , SO42- )} ^{. _} _{_} Examples of amphoteric compounds that can be used are listed below: Alkylsulfobetaines: R-N ⁺ (R ¹ ) ₂ R ² SO ₃ ^- , e.g. hexadecyldimethylammonium propanesulfonate R-CH (N ⁺ R ¹ ₃ ) R ² SO _3- ^_ for example Amine oxide: RN→O, e.g. hardened tallow-dimethylamine oxide. Carboxybetaine _: R _{- N} ⁺ ₍ ^R1 ) ^{2R2COO- ,} e.g. _C18H37N ⁺ ( _CH3 ) _2CH2CH2COO- ^. Hydroxyamine betaine RN ⁺ (R ¹ ) ₂ CH ₂ CONHOHCl ⁻ , for example C ₁₈ H ₃₇ N ⁺ (CH ₃ ) ₂ CH ₂ CONHOHCl ⁻ (wherein R is alkyl of 8 to 22, preferably 12 to 18 carbon atoms) chain, R ₁ is methyl or ethyl and R ² is a short alkyl chain of 1 to 4 carbon atoms). Another class of cationic fabric softeners that can be used in the first dispersed phase are those based on imidazolines,
It is expressed by the following general formula: (wherein R and R ¹ are each a substantially linear aliphatic hydrocarbon group having 15 to 24 carbon atoms,
R ² is an alkyl group having 1 to 4 carbon atoms, R ³ is a divalent alkylene group having 1 to 4 carbon atoms, X is an anion, and n is an integer equal to the charge of X. Liquid phase The liquid phase is aqueous, but usually contains other materials such as short-chain alcohols, buffers to maintain the necessary PH since any amphoteric surfactants or modifiers are present in cationic form. , and electrolytes may also be present. Emulsifiers, coloring materials, fragrances, disinfectants and surfactants are also optional components of the aqueous liquid phase. An optional ingredient in the liquid phase is a dispersed fabric conditioner in an amount of about 0.5 to about 30%, preferably it can be present in an amount of about 2 to about 15%. This agent may be a fabric softener, and examples of these materials are described in the preceding paragraph illustrating cationic materials present in the first dispersed phase. Methods of Manufacture Several methods of manufacture have been found to provide the desired deposition properties, and some of these methods are suitable. A preferred method includes, as a first step, dispersing and melting together the organic matrix material, the cationic material, and the visually or olfactory material. The melt is then dispersed in hot water and subsequently cooled, or the melt is solidified and then dispersed in cold water. Other optional components of the aqueous phase and the second dispersed phase can then be added. Examples of equipment that can be used to disperse organic matrix materials in the liquid phase are high speed stirrers, ultrasonic dispersers,
It is a vibrating reed and continuous mixer. These devices provide a variety of particle sizes and are each used specifically for various formulations. Examples of formulations according to the invention are shown below. EXAMPLE 98 g of tallow alcohol (TA3EO) ethoxylated with an average of 3 moles of ethylene oxide (as organic substrate material) and 2 g of Sudan Black B (Solvent Black 3 - Color Index 26150)
were melted together. Cetyltrimethylammonium bromide (CTAB) was dissolved in this mixture at the following concentrations: 0, 0.5,
1.0, 2.0, 5.0 and 10.0g. These mixtures were emulsified with water while in the molten state at 80°C using a Minisonic (Ultrasonics, Shipley, Yorks) 4 homogenizer to a concentration of 1%. Telugu for 5 minutes under stirring at a rate of 50 times per minute.
A dilute solution of these emulsions (30 g of emulsion per 1 water) was applied to cotton terry towels and bulky acrylic in an O-Tometer (US Testing Co.) at 25°C at a liquid-to-fabric ratio of 75:1. Rinse the knit fabric pieces. The fabric was removed and excess liquid was removed with a spin dryer before the fabric pieces were completely dried in a heated drying cabinet. The reflectance of the fabric was measured with a spectrophotometer before and after treatment. The reflectance was measured using a Zeisler reflectance spectrophotometer at a light wavelength of 620 nm and the K/S value (K = absorbance coefficient, S = scattering coefficient). The K/S value is proportional to the weight of colored material present. The difference ΔK/S between the K/S of the dyed fabric and the original fabric was calculated. This value represents the amount of dye deposited on the fabric during rinsing. The results were as follows:

[Table] In this system, the reloading amount of CTAB for textiles is greater than 1% and for acrylics 0.5-2% by weight of the non-ionic material. These optimum ranges overlap at 1-2% CTAB, in which improved deposition is achieved for both fabrics. Example Tallow alcohol 3EO and Sudan black B were melted together in the same amounts as in the example, and
It was emulsified in water as described therein without adding CTAB. A CTAB solution was prepared and added to the tallow-alcohol 3EO/Sudan Black B mixture.
CTAB was added separately to the dispersion so that the proportion was the same as in the example. This mixture was used to treat fabrics as in the example and the following results were obtained:

Table: Optimal levels of CTAB for cotton were approximately 1% and for acrylic between 0.5 and 2% by weight of the substrate material. EXAMPLES Example mixtures were prepared but were allowed to cool and solidify before being dispersed in cold water. Other test parameters were the same as in the examples. The results were as follows:

[Table] In this case, the optimal amount of CTAB for cotton is 0.5~
5% and for acrylic 0.5% of the substrate material.
It was 5% by weight. It is noted that these results are better than those shown in the examples in which the dispersed phase was dispersed in the molten state. From the results obtained in the examples and, it can be seen that the effects decrease in the order of and. This decrease follows the amount of free cations in the liquid phase. The manufacturing method used in the examples minimizes the amount of cationic material in the liquid phase. Example Tallow alcohol 3EO 98g and Sudan black
2 g of B was melted with 0, 0.5, 1.0, 2.0, 5.0 or 10.0 g of distearyldimethylammonium chloride. A dispersion was prepared using the method of the example. The results were as follows:

[Table] The optimal amount of cationic material for cotton is 2% or more, and for acrylic, the optimal amount of nonionic material is 2% or more.
It is 0.5 to 5% by weight. Therefore, the optimum concentration for both fabrics is 2-5% cationic material. EXAMPLE The example was repeated using dodecyltrimethylammonium bromide (DTAB) in place of CTAB. The results were as follows:

Table The optimum amount of cationic material for cotton was 2% or more and for acrylic 0.5-10%. That is, by using 2 to 10% of the cationic material to the weight% of the nonionic material,
Enhanced deposition was achieved in both fabrics. EXAMPLE 9 g of tallow-alcohol 3EO and 1 g of di-tert-butylhydroxytoluene (antioxidant) were melted together with 2 g of distearyldimethylammonium chloride, thoroughly mixed and solidified. This waxy solid was made into a paste and then ground into a cream using a pestle and mortar while adding water little by little. Finally, the cream was dispersed in water by stirring for 1 minute with a high speed stirrer to make product A with a total volume of 500 ml. Control product B was prepared as 2 by dissolving 4 g of antioxidant in acetone (10 ml) and adding water. Place the naturally soiled pillow case in a paddle washing machine at 40°C.
and washed for 5 minutes. The only difference was that there was no gradient, and 0.2% of a regular detergent product was used. After rinsing, the pillow case was cut in half and one of the halves was further rinsed with 2 ml of water containing 10 ml of the dispersion described above.
℃ for 5 minutes). The other half was treated similarly with Control Product B. Next, 20 assessors compared each half of the pillow case for odor, but no significant differences were found. However, after one week of storage in a separate container,
The Product A treated halves were preferred over the control halves in 35 out of 40 comparisons. This result shows that the antioxidant in the formulation according to the invention
antioxidants have been shown to be more uniformly deposited on textiles than other antioxidants, and thus to suppress malodors more effectively. Example Emulsions C and D having the following compositions were prepared by dispersing tallow alcohol 3EO (TA3EO), a fragrance mixture, and distearyldimethylammonium chloride (DDAC) in water:

[Table] For manufacturing, TA3EO, fragrance and DDAC
were melted and mixed together, the mixture was allowed to solidify, and then cold water was gradually added to obtain a crude dispersion. This was then treated with ultrasound to prepare a smooth emulsion. Use a ratio of 17 parts liquid to 700 g of fabric,
and added 10ml of one of the emulsions and washed in a paddle-operated washing machine (Hot Point Supermachine).
Dilute solutions of these emulsions were used to rinse resin-finished polyester/cotton fabrics. The fabric was stirred in the liquid for 15 minutes at room temperature, then removed and dried. When 20 appraisers asked whether the cloth smelled,
All were able to detect differences in fragrance levels between fabrics treated with the two emulsions. Those treated with D had a stronger odor than those treated with C. This is as expected from the difference in flavor content of the two emulsions.
Both treated fabrics were significantly more scented than those rinsed with a perfume-only suspension of the same perfume concentration as Emulsion D. Examples Stearyl stearate (6 g), fragrance mixture (4 g), distearyldimethylammonium chloride (1 g) were prepared by the method described in the examples.
A dispersion containing 100 g of water was prepared. 25 ml of this dispersion was then mixed with 475 ml of a 4.5% dispersion of distearyldimethylammonium chloride in water.
added to. To another sample of this 4.5% dispersion, the same perfume mixture alone was added to a concentration of 0.2%. These two dispersions were then used for the final rinsing of the laundry (load). The leveled laundry containing cotton terry hand towels was laundered in an AEG Mule Pine Tresina drum type washer using a 60°C wash program. Each load of laundry was treated in the final rinse with one of the two dispersions described above. After treating four laundry loads with each dispersion, the hand towels were evaluated for softness by an expert and no significant differences were found between the two dispersions. However, all agreed that towels treated with the carrier-containing dispersion smelled more highly than those treated with the perfume mixture alone. Examples N,N-ditallo-ethalamine (5 g), distearyldimethylammonium chloride (0.5 g), optical brightener, 1-p-carboxymethylphenyl-3-p were prepared by the method described in the examples.
A dispersion containing -chlorophenyl-Δ ² -pyrazoline (0.05 g) and water (100 ml) was prepared. A diluted solution of this dispersion containing 50 ml in 4.5 kg of non-fluorescent cotton terry towel for 10 minutes at room temperature
I rinsed it. A similar load of towels with a 0.5% dispersion of distearyldimethylammonium chloride 50
Rinse with a solution containing ml. As another control, attempts to obtain a 5% dispersion of N,N-ditallo-ethanolamine were unsuccessful. This formulation is an example of an organic matrix material providing the desired benefit, ie, fabric softening action. This fluorescent agent is a nylon direct type, but according to the present invention it has been changed to a cotton direct type.

Claims (1)

[Scope of Claims] 1. Each particle has a solubility in the aqueous phase of about 25 to about 99%, 200 ppm.
a non-cationic organic matrix material having a solubility in water at 25°C of less than or equal to 5 g/m selected from about 0.5 to about 25% of cationic surfactants and cationic fabric softeners; ionic materials; and c about 0.5 to about 50% of whitening agents, pigments, dyes,
Approximately 0.5 particles consisting of a mixture of visually or olfactory materials selected from fragrances, disinfectants and antioxidants
A liquid textile treatment formulation in the form of a particle dispersion comprising ~50% by weight of a first dispersed phase dispersed in a from about 50% to about 99.5% aqueous phase. 2. The liquid formulation of claim 1 comprising from about 0.5% to about 30% of a second dispersed phase comprising a textile tempering material. 3. The liquid preparation according to claim 2, wherein the textile conditioning material is a textile softening agent. 4 The cationic material in the first dispersed phase
Claim 1 of the foregoing present in an amount of about 10%
Liquid formulation according to any one of items 1 to 3. 5. A liquid formulation according to any one of claims 1 to 4, wherein the first dispersed phase is present in an amount up to about 10% by weight of the formulation. 6. The liquid formulation of claim 5, wherein the first dispersed phase is present in an amount up to about 2%. 7. A liquid formulation according to any one of claims 2 to 6, wherein the textile tempering material is present in an amount of about 2 to about 15%. 8. A liquid formulation according to any one of claims 1 to 7 above, wherein the organic matrix material is a nonionic organic material having a solubility in the aqueous phase of 200 ppm or less. 9. A liquid formulation according to claim 8, wherein the solubility of the organic matrix material is not greater than 50 ppm. 10 Aliphatic alcohols in which the organic matrix material contains 8 to 22 carbon atoms, aliphatic alcohols ethoxylated with up to about 5 moles of ethylene oxide, formula
RCOOR ¹ (wherein R and R ¹ are each an alkyl or alkenyl group containing about 8 to about 22 carbon atoms)
Claims 1 to 2 selected from esters of
Liquid formulation according to any one of clause 9.