JPH02139479A - Liquid composition for fabric treatment - Google Patents

Abstract

PURPOSE: To obtain the subject liquid formulation comprising a mixture of a nonionic organic substrate material having a specific solubility or below with a cationic active material having a specific solubility or below and a material which is perceivable on textile surface by visual sense, sense of smell, etc., e.g. a whitening agent, pigment or dye and capable of giving effect which is perceivable on the surface of woven fabric. CONSTITUTION: This liquid formulation for fiber treatment is obtained by mixing (A) about 25-99 wt.% non-cationic organic substrate material having <=200 ppm solubility in an aqueous phase, (B) about 0.5-25 wt.% cationic material having <=5 g/L solubility at 25 deg.C and selected from cationic surfactants and cationic woven fabric softening agents and (C) a material capable of perceiving by visual sense or sense of smell and selected from whitening agents, pigments or dyes, perfumes, bactericides, antioxidants, etc., and making the mixture particulate and dispersing 0.5-50 wt.% disperse phase into about 50-99.5 wt.% aqueous phase. Fiber surface is treated with the dispersion having preferable disperse concentration by using the dispersed and prepared formulation to give effect which is perceivable by visual sense or sense of smell.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a liquid formulation capable of depositing a material on a textile surface to provide a visually or olfactory effect. This formulation can be used in diluted form and examples of textile surfaces are cotton, polyacrylic, polyamide and polyester braids, wool and flax.

The visually or olfactory material to be deposited is selected to give the desired effect on the surface, and this material Fl
is selected from among whitening agents, pigments, dyes, fragrances, disinfectants and antioxidants.

The present invention provides: i) a) a solubility in the aqueous phase of from about 25 to about 99%;
ppm or less of a non-cationic organic matrix material; b) about 0.5 to about 25% of a cationic surfactant and a cationic fabric softener in water at 25°C; C) a cationic material with a solubility of 5 g/l or less; and C) from about 0.5 to about 50% of a visual or olfactory agent selected from whitening agents, pigments, dyes, fragrances, disinfectants and antioxidants. a particle dispersion comprising: i) a first dispersed phase of about 0.5% to about 50% of particles that is a mixture of discernible materials dispersed in an aqueous phase of about 50% to about 99.5%; A liquid formulation for treating textiles is provided.

Optionally, the formulation contains from about 0.5% to about 30% of a second dispersed phase comprising a textile 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, while fluorescing materials are visually perceptible. Some materials that can be perceived visually or olfactory, such as fragrances, have an irradiant effect 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 the 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 Antioxidant C.

In some formulations, the effect at the surface may be achieved by deposition of an organic matrix material. That is, the organic substrate can impart the desired effect in addition to that obtained from the visually or olfactorily perceptible material. For example, with respect to textiles, the deposition of long chain fatty alcohols that can be used as substrate 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 adsorbs selectively or at least competitively with 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 the naturally Ω-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 positively charged ions are deposited on the cationic materials described herein, the alkyl chains on these molecules are absorbed onto the synthetic polymer surface and bonded to hydrophobic interactions. be done. 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 the zeta electric potential on acrylic fiber and cotton fabric samples by the flow 1FJl potential technique. These samples are p11
6 in a solution of sodium chloride (5X 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 typically ranges from 0.1 to about 20 microns, more usually from about 1.0 to about 20 microns.

The cationic material in the first dispersed phase is preferably about 2
It exists in about 10% of Sui. This first dispersed phase is about 1
Present in amounts up to 0%. 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.

The organic 1□L material substrate material needs to have a solubility in the liquid phase at 25° C. of 200 ppm or less, preferably 50 ppm or less.

Examples of substrate materials are secondary or secondary aliphatic alcohols of the formula ROH, such as stearyl aldehyde, oleyl alcohol, hythyl alcohol and tallow alcohol, hydrocarbons of the formula RCH3, such as octadecane, eicosane, tocosane and tetracosene. , formula RC
Aldehydes and ketones of oR2, such as methyl stearyl ketone and stearyl aldehyde, formula RC
Fatty acids of OOH, such as tallo fatty acid, coconut fatty acid, oleic acid, suaric acid and behenic acid, and esters of these acids of the formula RCOOR' or RCOOR2, such as ethyl palmitate and stearyl stearate. In these formulas R and R
1 is a saturated or unsaturated alkyl or alkylaryl group, and may be either straight chain or branched chain.

The number of carbon atoms is from 8 to 22, preferably from 14 to 2
It is 2. R2 is hydrogen or an alkyl group having from co to 4 carbon atoms.

Other examples of substrate materials that may be used include formulas RCO, NR
R (wherein R3 and R4 are each hydrogen, a furkyl group having 1 to 4 carbon atoms, -C112CH20H, -(CH
2) fatty acid amides of the formula R
Amines of the formula NRR or RR1NR3, such as stearylgetanolamine and sitallomethylamine, ethers with the formula ROR or ROR2, such as stearyl ethyl ether, and epoxides with the formula %(2), such as stearyl 1po4-cyto Al4-ren 1-site adducts of fatty alcohols, fatty acids and aliphatic amides can also be used as substrate materials. .OH11 (CHRC
H20). CO(11-1 and R(CHRCH20).

It is expressed as C0NRR. R5 is hydrogen or a methyl group and n is selected so as not to exceed the solubility limits mentioned above, such as tallow alcohol combined with an average of 3 moles of ethylene oxide, tallow amide combined with an average of 5 moles of ethylene oxide, and an average of It is oleic acid condensed with 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, giving rise to even lower dissociation constants. In the dispersed phase of the formulation these can act as matrix materials.

This organic material is non-cationic and preferably non-ionic. Non-ionic in an article refers to a material that does not generate ionic species or generates ionic species only to a negligible extent when in contact with an aqueous phase.

1L Soil λflJ-1 Suitable materials are both soluble and insoluble cationic materials. Any cationic material used has a β
It must not have a solubility in water of more than 5 g per liter. Therefore, both cationic surfactants and cationic materials useful as fabric softeners can be used, with the latter being preferred. Amphoteric compounds whose 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, the shift of the pll to acidity makes the particular pll cationic and useful in the formulations of the present invention.

It is generally difficult to draw a clear boundary between soluble bamboo materials and insoluble materials, and even for materials that are generally considered soluble, the length of one or more alkyl chains exceeds a certain limit. Sometimes it is considered insoluble. Cationic materials with lower solubility are preferred. This is because the pll pile does not leach out as easily from these stored particles. 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 (R1R2R")X-, e.g., t[t?tilt'J
Methylammonium bromide and tallow trimethylammonium bromide. Alkylpyridinium salts: chloride and cetylpyridinium chloride.

Al↓ruaryl quaternary ammonium salt: FIN (R1R
2) CHx, such as stearyldimethylbenzylammonium chloride.

Amine salt: RN'R' R2HX, e.g. C
FIN(Cto+)H-CHCo,
(In the formula, R is an alkyl group of 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, R, R, R, R
' is a methyl, ethyl or propyl group and X is an anion, e.g. halogen (e.g. chloride or promide)
, sulfate i., acetate, methosulfate and ethosulfate).

Examples of insoluble cations that can be used as fabric softeners are the following: Nidialkyl quaternary ammonium salts: R1R2NR3R4x, such as disderyldimethylammonium chloride, dicocodimethylammonium chloride, and di(?-stearoyl quaternary-thieb= dimethylammonium chloride.

Amine salt derivative: R1R2NR31'X, for example C1
71+35CONHCH2NH(CH3)(C1□H3
5) CH3COO and (C17H35CONHCH
2C1+2) 28H,, lIc0O-Compound with a straight alkyl chain: RlN"R3R'R5X",
For example C17H3C17H35C00CH2C12+3
)2C113Coo , (wherein R, R are an alkyl chain of 12 to 25 carbon atoms optionally containing an amide or ester linkage, R3R4 is a methyl, ethyl or propyl group, and R5 is H, methyl, ethyl or propyl and X- is an anion, for example Cj!-1Br-lC
H3SO4, C2H5SO4, CH3Co0so4'-
).

Examples of amphoteric compounds that can be used are listed below: Alkylsulfobetaines: i) RN (R), RSO3, eg hexadecyldimethylammonium propanesulfonate, eg amine oxides: RN→0, eg hardened talodimethylamine oxide.

Carboxybetaine: Cl8H37N(CH3)2CH2CH2CoO Hydroxyamine betaine: RN(R)2CH2CONHOHC1-1 e.g. 018
H3□N (CH3)2 CH,2C0NI-108c
2 in which R is an alkyl chain of 8 to 22, preferably 12 to 18 carbon atoms, R is methyl or ethyl, and R2 is a short alkyl chain of 7 to 4 carbon atoms.

Another type of cationic fabric softener that can be used in the first dispersed phase is based on imidacillin and has the general formula: each is a substantially linear aliphatic hydrocarbon group having 15 to 24 carbon atoms, R2 is an alkyl group having 1 to 4 carbon atoms, and R3 is 1 to 4 carbon atoms;
is a divalent alkylene group containing from to 4 carbon atoms,
(X is an anion and n is an integer equal to the charge of Electrolytes may also be present, including buffers to maintain the necessary pl+ to exist in ionic form. Emulsifiers, color saving materials, fragrances, disinfectants and surfactants are also optional components of the aqueous liquid phase.

An optional component 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, examples of these materials are listed in the paragraph above 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 11. The melt is then dispersed in hot water followed by cooling fJ1, or the melt is solidified and then covered with cold water.

The optional components of the aqueous phase and the second dispersed phase can then be added.

Examples of equipment that can be used to disperse the organic matrix material in the liquid phase are high speed stirrers, ultrasonic dispersers, stirrers, and continuous mixers. 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 a working average of 3 moles of ethylene oxide (as organic substrate material) and 27 g of Sudan Black B (Solvent Black 3 - Color Index 26150) were melted together.

Cetyltrimethylammonium bromide (
CTAB) was melted into this mixture: 0.0. 0.5.1.0, 2.0, 5.0 and 10
0g.

These mixtures were emulsified with water while in the molten state using a Hinison+c (Ultrasonics, Shipley, Yorks) 4 homogenizer at 80°C to a concentration of 1%.

Telugu O. for 5 minutes under stirring at a rate of 50 times per minute.
in a tometer (Ninis Teszing) at 25°C.
Dilute solutions of these emulsions (30 grams of emulsion per 11 parts of water) in a 75:1 ratio were used to rinse fabric pieces of cotton terry towels and bulky acrylic knit fabrics.

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 spectrophotometric needle before and after treatment. 6
Zeiss Erreho reflectance at a light wavelength of 20nl.
Measure the reflectance using a helophotometer,
And the appropriate coloring will be proportional to the weight of the material. Represents the amount of dye deposited on the fabric during dyed fabric and pre-rinsing.

The results were as follows: Compounded CTAB Cotton Terry Towel Acrylic Fabric 0.
015 0.053 0.514 0.849 0.911 In this system, the reloading amount of CTAB for cotton fabric is 1% or more, and for acrylic it is 0.5% of the nonionic material.
~Double fi1%. The optimum range for these is 1-2%C
There is an overlap in the TAB, and in this range an increase in deposition is achieved for both fabrics.

Tallow Alcohol 3EO and Sudan Black B were melted together in the same solution as in Example 1 and then emulsified in water as described therein without adding CTAB.The CTAB solution was The mixture was prepared and added separately to the dispersion so that the ratio of CTAB to Tallow Alcohol 3EO/Sudan Black B mixture was the same concentration as in Example T.

This mixture was used to treat the fabric in the same manner as in the example process,
I got the following results: 0 0.010 0
．． 1200.5
0.4571 0.015 5 0.456 0
．． 11910 0.777 The optimum level of CTAB for cotton was about 1% and for acrylic it was between 0.5 and 2% C of the substrate material.

Example ■ The mixtures of Example ■ were prepared, but they were allowed to cool and solidify before being dispersed in cold water. Other test parameters were the same as in the example construction.

The results were as follows: Compounded CTAB Cotton Terry Towel % ΔK Acrylic Fabric ΔK 0 0.106 0.3
890, 5 0.722 0
．． 9641 0.484
1.2242 0,930
0.5225 0,699
0.48210 0,710
0.211 In this case, the optimal amount of CTAB for cotton was 0.5-5% and for acrylic it was 0.5-5% by weight of the substrate material. It is noted that these results are better than those shown in Example 1, in which the dispersed phase was dispersed in a molten state.

From the results obtained in Examples ■, ■, and ■, the effects are ■, ■
It can be seen that it decreases in the order of and ■. This decrease follows the suspension of is cations in the liquid phase. The manufacturing method used in Example 1 minimizes the amount of cationic material in the liquid phase.

Examples ■ Tallow Alcohol 3EO98y and Sudan Black 82
g of distearyldimethylammonium chloride 0.0
．． 5.1.0.2.0. It melted with 5.0 or 10.0 g. A dispersion was prepared using the method of Example ①.

The results were as follows: The optimal amount of cationic material for cotton is 2% or more;
0.5-5% of non-ionic material for acrylic
It is. Therefore, the optimum concentration for both fabrics is 2-5
% cationic material.

Example V The example procedure was repeated using dodecyltrimethylammonium bromide (DTAB>) in place of CTAB. The results were as follows: Blended DTAB Cotton Terita A Acrylic Fabric 0 0.194 0.5 0.012 1 0.012 2 0.010 5 1.117 10 1.2140.157 0.647 0.751 0.418 0.186 0.214 0.010 0.007 0.060 0.229 0. 329 0.125 0.142 0.404 0.982 0.803 0.464 The optimum content of cationic material to cotton is 2% or more;
And it was 0.5-10% with respect to acrylic. That is, improved deposition was achieved in both fabrics by using 2-10% cationic material to % nonionic material.

Example vI 9 g of tallow alcohol 3EO and 19 g of di-tert-butylhydroxytoluene (antioxidant) were melted together with 2 g of distearyldimethylammonium chloride, thoroughly mixed and then solidified. This waxy solid is made into a paste,
Next, the mixture was ground into a cream using a pestle and mortar while adding water little by little. Finally, the cream was dispersed in water by stirring with a high speed stirrer for 1 minute to form a full ffi 500d product. acet), ′(
Dissolve 4g of antioxidant in 10d) (7, add water and dissolve for 2r
Control product B was manufactured as follows.

Naturally soiled pillowcases were washed in a paddle washing machine at 40°C for 5 minutes. Haku used 0.2% of regular detergent products, just because there was no smell. After rinsing, cut this pillow case in half 1) and add one of the halves to the above-mentioned dispersion.
! (5 minutes at 20°C). The other half was treated similarly with Control Product B.

Next, each half of the pillow case was compared for smell by 20 assessors, but no significant difference was found. However, after one week of storage in a separate container, the product-treated halves were preferable to the control halves in 35 out of 40 comparisons. This result shows that the antioxidant in the formulation according to the invention is deposited more uniformly on the fabric than the antioxidant in product B, which in turn results in more effective odor control. showing ().

Example Vl Tal0-7/Lr1-3EO (TA3EO), fragrance mixture, distearyldimethylammonium chloride (TA3EO) in water
DDAC) was dispersed to produce emulsions C and D having the following compositions: TA3130 Fragrance DDAC water C)
99 1g 2g
100-D) 6! l? 4
To prepare g 1 g 100d, TA3EO, perfume and DDAC were melted together and mixed, the mixture was allowed to solidify, and then cold water was gradually added to obtain a crude dispersion. This was then sonicated to prepare a smooth emulsion I:.

Used in a ratio of 171 parts liquid to 700 parts J of fabric,
and add one of the emulsions 10- and paddle-operated wash 17
i1t! The resin-finished polyester/cotton fabrics were rinsed with dilute solutions of these emulsions in a (Hot Point Supermadec). The fabric was stirred in the liquid for 15 minutes at room temperature, then removed and dried.

When 20 assessors were asked whether the fabrics were perfumed, all of them were able to detect a difference in fragrance levels between the fabrics treated with the two emulsions. Those treated with D had a stronger odor than those treated with C. This is expected from the difference in flavor content between the two emulsions and is in line with Ic.

Both treated fabrics smelled much more strongly than those rinsed with a perfume-only suspension of the same perfume concentration as the emulsion.

Tue/IVI A dispersion was prepared by combining stearyl stearate (6 g), perfume mixture (4 g), distearyldimethylammonium chloride (1 g) and 100 g of water by the method described in Example Vl.

25d of this dispersion was then added to a 4.5% dispersion of distearyldimethylammonium chloride in water. To another sample of this 45% dispersion, the same perfume mixture alone was added to a concentration of 0.2%. Next wash)
These two dispersions were used for the final rinsing of the load.

The leveled laundry containing cotton terry hand towels was washed in an AEG Lavamat Regina tram type laundry 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 washes with each dispersion, a trained expert evaluated the hand towels for softness and found no significant difference between the two dispersions. However, it was unanimous that the towels treated with the dispersion containing the carrier smelled much more highly than those treated with the dispersion containing only the fragrance FA mixture.

Example ■ By the method described in Example ■, N,N-ditaloethalamine (5y), distearyldimethylammonium chloride (0.5g), optical brightener, +-p-carpoxymebulphenyl-3 -p-chlorophenyl-△
-Pyrazoline (0,053) and water (100td)
A dispersion containing the following was produced.

A dilution of this dispersion containing 50 d in 45 fl was used to rinse 3 Kg of non-tipped terry towels for 10 minutes at room temperature. A similar load of towels was rinsed with a solution containing 50 d of a 0.5% dispersion of dis7allyldimethylammonium chloride. Another control attempt to obtain a 5% dispersion of N,N-citallow ethanolamine was unsuccessful.

This formulation is an example of an organic matrix material providing the desired benefit, namely fabric softening action. This fluorescent lamp is a nylon direct type, but the present invention has changed it to a cotton direct type.

Example X Cotton terry towel (20ctm x 20ctn) 1
6 pieces in a 0.4% solution of regular laundry detergent 31
2 for 15 minutes at 60°C. The pieces were rinsed twice with cold water and divided into four sets of four pieces for a third rinse. Each set of four strips was then rinsed for 5 minutes in 800 g of cold water containing:

A- None, this is a control set.

B - 2 ml of a dispersion containing 5% paraffin wax and 0.05% distearyl dimedylammonium chloride, prepared analogously to Example ①.

0.0 of C-distearyl dimedylammonium chloride.
05% dispersion 2ate.

D - 10d of 1% dispersion of paraffin wax in water (5%
(The dispersion is not sufficiently stable to be usable).

After drying, the -set was subjected to each of the above treatments.

Redistributed into four sets of fabrics, each containing one fabric. These sets were assessed for flexibility by five experienced assessors. The format of this assessment is to award 1 point to the softest fabric and 4 points to the roughest fabric for each set of fabrics. Therefore, if one treatment consistently produces the softest fabric in each set, the total score for this treatment is 201. : It will become. Similarly, if one treatment coincides with producing the roughest cloth, its total score would be 80.

The actual 1q points for the above treatments were as follows: Thus, control rinse A was not significantly different from treatments C and D. Treatment B resulted in a significantly softer fabric. The results showed that no single softener was sufficient to make a significant difference, but it was found that the softener and paraffin wax did provide a significant difference when deposited together.

Claims (11)

[Claims] (1) i) a) Solubility in the aqueous phase of about 25 to about 99%2
00 ppm or less of a non-cationic organic matrix material; b) solubility in water at 25° C. of about 0.5 to about 25% selected from cationic surfactants and cationic fabric softeners, 5 g; /l or less of a cationic material; and c) from about 0.5 to about 50% of a visually or olfactory substance selected from whitening agents, pigments, dyes, fragrances, fungicides and antioxidants. a textile in the form of a particle dispersion comprising: ii) about 0.5% to about 50% by weight of a first dispersed phase consisting of particles of a mixture of materials dispersed in an aqueous phase of about 50% to about 99.5%; Liquid preparation for processing. 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 tempering material is a textile softener. (4) the cationic material in the first dispersed phase is about 2 to about 1 part of the phase;
Liquid formulation according to any one of the preceding claims, present between 0%. (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, wherein the organic matrix material provides a second sensory perceptible effect. (9) A liquid formulation according to any one of claims 1 to 8, wherein the matrix material is a nonionic material. (10) A liquid formulation according to claim 9, in which the solubility of the organic matrix material is not greater than 50 ppm. (11) 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 from about 8 to about 22 carbon atoms. liquid preparation.