JPS6051588B2 - Liquid preparation for textile treatment and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to liquid formulations capable of depositing materials that provide a sensory perceptible effect on textile surfaces.

This formulation can be used in diluted form and - Examples of textile surfaces are cotton, polyacrylic, polyamide and polyester fibres, wool and flax. The perceptible material to be deposited is selected to give the desired effect to the surface;
Examples of these materials include fluorescent agents, whitening agents, fragrances, pigments,
dyes, bactericidal agents, textile conditioners, such as textile softeners, antioxidants and antistatic agents. The present invention comprises Ia from about 25% to about 99% substantially water-insoluble organic matrix material; b from about 0.5% to about 25% cationic material; and c from about 0.5% to about 50% dispersed material. a first dispersed phase (dispersoid) consisting of particles, which is a mixture of sensibly perceivable materials, in an aqueous phase of about 50 to about 99.5%; A liquid preparation for textile treatment is provided.

Optionally, the formulation contains from about 0.5 to about 30% of a second dispersed phase consisting of a textile treatment agent. The term sensory perceptible material refers to a material that, when deposited on a textile surface,
"Used to define materials that are directly or indirectly detectable by the human senses."

Thus, perfumes of materials suitable for deposition are fragrant compositions that are detected by the olfactory organ, fabric softeners are tactilely perceptible, and fluorescers are visually perceptible. Also included are materials that can alter the surface of the fabric to alter the sound produced during movement. Some sensually perceivable materials, such as perfumes, act directly on the human senses, while some materials are perceivable indirectly through their effect on other substances. An example is a disinfectant that can be detected by a reduction in fabric odor due to its bactericidal action against microorganisms. These microorganisms concentrate on the fabric during use.

Another sensory perceptible material that provides odor reduction is antioxidants. For some formulations, surface effects may be obtained by deposition of organic matrix materials.

Thus, this organic substrate can provide the desired effect in addition to that obtained from the sensory perceptible material. For example, with respect to textiles, the deposition of long chain aliphatic alcohols that can be used as organic matrix materials provides a detectable effect on textile handling.

It is necessary to ensure that a minimum proportion of soluble cationic material in ionic form is present in the aqueous phase, because this cationic material in the liquid phase is selectively deposited or This is because the particles compete with and are at least adsorbed.

This selection or competition leads to ineffective deposition of the dispersed phase on the surface. A contributing factor to ineffective deposition is the charge reversal of naturally negatively charged surfaces, which causes enough positively charged ions to be absorbed onto it such that it becomes mathematically greater due to the surface's inherent negative charge. Happens in case.

This inversion occurs on synthetic polymer surfaces, such as polyacrylic, polyester, and polyamide fabrics. Negative charges on these materials are not as abundant as they are on hydrophilic materials, such as cotton. When positively charged ions are obtained from the cationic materials described herein, the alkyl chains on these molecules can be absorbed onto the synthetic polymer surface and bonded by hydrophobic interactions. Thus, the binding of these cationic materials does not simply rely on charge interactions between the positive center of the cationic position and the negative position on the substrate. This charge reversal effect was demonstrated by measuring the zeta potential by streaming potential technique on acrylic and cotton fabric samples. These samples are immersed in a solution of sodium chloride (5 x 10-4 mol) at a pH of 6. 10-4
Addition of cetyltrimethylasimonium bromide (CTAB) at molar concentrations 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 about 0.1 to about 20 microns;
More commonly it ranges from about 1.0 to about 20 microns.
The cationic material in the first dispersed phase is preferably about 2
present in an amount of from about 10% to about 10%.

The first dispersed phase is present in an amount up to about 10%; this range is preferably used so that the matrix material also provides a sensory 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 now considered next.

Organic matrix material The matrix material contains no more than 200 ppm, preferably 5
It is necessary to have a solubility in the liquid phase at 25° C. of not greater than 0 ppm.

Examples of this substrate material are primary or secondary fatty alcohols of formula ROH, such as stearyl alcohol, oleic alcohol, cetyl alcohol and tallow alcohol, formula RCH
3 hydrocarbons such as octadecane, eicosane, docosane and tetracosene, aldehydes and ketones of the formula RCOR2, such as methyl stearyl ketone and stearyl aldehyde, fatty acids of the formula RCOOH such as tallow fatty acid, coconut fatty acid, oleic acid, stearic acid and behene and the formula Esters of this acid with RCOORl or RCOOR2, such as ethyl palmidate and stearyl stearate.

In these formulas R and R1 are saturated or unsaturated alkyl or alkylaryl groups and may be straight or branched. The number of carbon atoms is from 8 to 22, preferably from 14 to 22. R2 is hydrogen or an alkyl group having 1 to 4 carbon atoms. Another example of the type of substrate material that can be used is the formula RCONR3R4, where R3 and R4 are each hydrogen, an alkyl group having 1 to 4 carbon atoms, -CH2CH2O
H, -(CH2)30H or -CH(CH3)CH2O
H) such as tallow diethanolamide and coconut monoethanolamide.

Amines with the formula RNR3R4 or RRlNR3, such as stearyldiethanolamine and ditallowmethylamine, ethers with the formula RORl or ROR2, such as stearyl ethyl ether, and epoxides with the formula, such as stearyl epoxide, can be used.

Alkylene oxide adducts of fatty alcohols, fatty acids and fatty amides can also be used as substrate materials.These adducts are R (CHR5CH2O)NOH, . R
(CHR5CH2O)NCOOH and R(CHR5CH
2O) has NCONR3Rl. R5 is hydrogen or a methyl group, and n is 5 selected to ensure that the above-mentioned solubility limits are not exceeded, e.g. tallow alcohol condensed with an average of 3 moles of ethylene oxide, an average of 5
Tallowamide condensed with 1 mole of ethylene oxide and olethetaic acid condensed with an average of 3 moles of ethylene oxide. Dibasic carboxylic acids are also examples of substrate materials that can be used. It will be noted that the above list in this example includes carbozic acids.

These materials have low solubility in the liquid phase and also have dissociation constants. In the dispersed phase of the formulation these can act as matrix materials. This organic matrix material is non-cationic and preferably non-ionic.

The term nonionic refers to materials that do not produce ionic species, or produce such species only to a negligible extent, when contacted with an aqueous phase. Cationic Materials Suitable materials are found in both soluble and insoluble types of cationic materials.

5/' at 25°C for any cationic material used.
It must not have a solubility in water of more than g. Thus, both cationic surfactants and cationic materials useful as fabric softeners can be used; the latter is preferred. Amphoteric compounds of the type where the ionic species is dependent on the pH of the liquid phase can also be used to provide cationic materials with selection of the pH of the system. For amphoteric compounds, when the pH shifts to acidic, this type of compound becomes cationic at a certain pH,
and is effective in the formulations of the invention. It must be recognized that no clear boundaries can be drawn between soluble and insoluble materials, and thus materials that are generally considered soluble must have one or more alkyl chains in length above a certain limit. Sometimes it is considered insoluble.

Less soluble cationic materials are preferred because they are less easily leached from the dispersed particles during storage. Common examples of soluble cations are listed below: Alkyl quaternary ammonium salts: R+N(RlR2
R3): 2X'', such as cetyltrimethylammonium bromide and tallow trimethylammonium bromide.

Alkylpyridinium salt: R--N'daゝj)ゝX
-) For example laurylpyridinium chloride and cetylpyridinium chloride.

Alkylaryl quaternary ammonium salt: R+N (RlR
2) 2C6H5X-, for example stearyldimethylbenzylammonium chloride.

Amine salt: R-NRlR2HX\for example Cl2H25N(CH3)HXCH3CO4-, where R is 8 to 22 carbon atoms, preferably 12 to 18
The alkyl groups of the carbon atoms R1, R2, R3, R4 are methyl, ethyl or propyl groups, and X is a hidden ion, 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 RlR2NR3R4X-, such as distearyldimethylammonium chloride, dicocodimethylammonium chloride, and di(2-stearoyloxyethyl).
Dimethylammonium chloride.

Amine salt derivative ゜R1R2NR3HX-, for example, \w518PVV1 bottleV↓^BiV↓Engineering 2-2J! 1 engineering 2↓
1 to VVO Compounds with one long alkyl chain: R
lNR3R4R5X-, e.g. Cl7H35COOCH2CH2NH(CH3)2CH
3C00\ (wherein R1, R2 are an alkyl chain of 12 to 25 carbon atoms optionally containing an amide or ester linkage, R3, R4 are methyl, ethyl or propyl groups, R5 is H1 methyl, ethyl or propyl and X
- is a hidden ion, such as C1-, Br-, LlCH3SO
4-, C2H5SO4-, SO4- to CH3COO).

Examples of amphoteric compounds that can be used are listed below: alkylsulfobetaine IR-N(R1)2R2S03-, for example hexadecyldimethylammoniopropanesulfonate 11R-CH
(NR3l)-R2SO3-eg amine oxide RH→0, eg hardened tallow dimethylamine oxide.

Carboxybetaine RN(R1)2R2C00-,
For example, Cl5H37NCH3)2CH2CH2C00-
.

Hydroxyamine betaine RN+(R1)2CH2C
0NHCHC1-, e.g. Cl5H37N(CH2-C
ONHOHCl- (wherein R is 8-22, preferably 1
an alkyl chain of 2 to 18 carbon atoms, R1 is methyl or ethyl, R2 is a short alkyl chain of 1 to 4 carbon atoms).

Another type of cationic fabric softener that can be used in the first dispersed phase is based on imidazolines and has the following general formula:
(wherein R and R1 are substantially linear aliphatic hydrocarbon groups each having 15 to 2 atoms, R2 is an alkyl group having 1 to 4 carbon atoms, and R3 is an alkyl group having 1 to 4 carbon atoms. a divalent alkylene group with a ion, X is a hidden ion, and n is an integer equal to the charge of Alcohols, buffers to provide the necessary pH, eg to ensure that any amphoteric surfactants or regulators are 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. The selected components in the liquid phase are approximately 0.
The dispersed fabric conditioner may be present in an amount of 5 to about 30%, and 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 cited above in the paragraph describing 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 co-melting the organic matrix material, the cationic material, and the organoleptic material. The melt is then dispersed in hot water and subsequently cooled, or the melt is solidified and dispersed in cold water. The optional additional ingredients of the aqueous phase and the second dispersed phase can then be added. Examples of devices that can be used to cause dispersion of the organic matrix material into the liquid phase are high speed stirrers, ultrasonic dispersers, vibratory reeds, and continuous mixers.

These devices provide different particle sizes with specific applications for different formulations. Examples of formulations according to the invention are shown below. Example 1 98 g of tallow alcohol ethoxylated with an average of 3 moles of ethylene oxide (TA3EO) (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 levels: 100 g each of a mixture of Tallow Alcohol 3E0 and Sudan Black B.
010.5, 1.0, 2.015.0 and 10 for
．． These mixtures were emulsified with water while still in the molten state at 80° C. using a MinisOnic (Ultrasonics Ltd., Shipley, Yorks) 4 homogenizer to form a 0g01% concentration.

Telugu O for 5 minutes with 50 cycles per minute stirring
25' in a tometer (US Testing Co., Ltd.).
C, dilutions of these emulsions at a liquid-to-cloth ratio of 75:1 (
A lined terry towel and a large piece of acrylic knit fabric were rinsed in 30 grams of emulsion per liter of water.

The fabric is removed and removed by a spin dryer before the fabric piece has completely dried in a heated drying cannulated.

The reflectance of the fabric was measured with a spectrophotometer before and after treatment.

The reflectance was measured using a Zeisserrefreflectance spectrophotometer at a light wavelength of 620rlm, and the reflectance was measured using a Zeisserrefreflectance spectrophotometer at a light wavelength of 620rlm, and the reflectance was measured using a Zeisserrefreflectance spectrophotometer at a light wavelength of 620rlm.
-Munk) relation, the k value (K = absorption coefficient and S
= scattering coefficient) was converted to K1.

The 8 stars are proportional to the weight of coloring material present.

Δ? That is, the difference between k of the dyed fabric and the original fabric is calculated and represents the amount of dye picked up on the fabric during rinsing. The results were as follows: Compounded CTAB/cotton terry towel 1% acrylic fabric
Vk. In this system, the optimum amount of CTAB for cotton fabrics is 1% or more, and for acrylics this is 0.5 to 2% by weight non-ionic.

These optimum ranges overlap between 1 and 2% CTAB, where enhanced deposition is obtained with both fabrics. Example
■ Tallow alcohol 3 in the same amount as in Example 1
Melt E0 and Sudan Black B together and CTA
Emulsified in water without B as described therein.

Prepare CTAB solution and tallow alcohol 3E0/
The CTAB to Sudan Black B mixture was added separately to the dispersion at a level such that the ratio was the same as in Example 1. This mixture was used to treat fabrics as in Example 1 with the following results: CT on cotton.
The optimum weight was about 1%, and for acrylic this was 0.5 to 2% by weight of the substrate material.

Examples ■ The mixtures of Example 1 were prepared, but they were cooled and allowed to solidify before dispersion in cold water.

Other test parameters were as in Example 1. The results were as follows: Compounded CTAB cotton terry towel Acrylic fabric Q amount % cotton, in this case CTAB
The optimum amount of B was 0.5 to 5%, and for acrylic this was also 0.5 to 5% by weight of the substrate material.

It is noted that these results are better than those shown in Example I, where the dispersed phase is dispersed during the melt. Example 1
It can be seen that the results obtained for , ■, and ■ decrease in the order of ■, I, and ■.

This decrease follows the amount of free cations in the liquid phase. The method of manufacture used in Example 2 results in minimal amounts of cationic material in the liquid phase. Example ■ Tallow Alcohol 3E098g and Sudan Black B2
g of distearyldimethylammonium chloride. ．．
0.5, 1.012.015.0, and 10.0g were melted together.

The dispersion was prepared using the method of Example 1. The results were as follows. The optimum amount of cations for cotton is 2% or more, and for acrylics this is less than 0% of the non-ionic
．． 5 to 5% by weight.

The top level for both fabrics is 2 to 5% cations. Example 1 Example 1 was repeated using dodecyltrimethylammonium bromide (DTAB) in place of CTAB.

The results were as follows: for cotton the optimal amount of cations is 2% or more, and for acrylic this is 0.
It was 5 to 10%.

Enhanced deposits of cations of 2 to 10% by weight of non-ions were obtained for both fabrics. EXAMPLE ■ 9 g of Tallow Alcohol 3E and 1 g of di-tert-butylhydroxytoluene (antioxidant) were melted with distearyldimethylammonium chloride, mixed thoroughly and allowed to solidify.

This waxy solid was made into a paste and then into a cream by grinding with increasing amounts of water in a petals and mortar. Finally, product A is made by dispersing this cream in water to a total volume of 500 mt by stirring for 1 minute on a high speed stirrer. Control product B was prepared by dissolving the antioxidant solution in acetone (10ml) and making up to 2e with water. The naturally soiled pillow case was washed in a paddle-type washing machine at 40°C for 5 minutes.

0.2% odorless, but otherwise normal detergent products
It was used in Cut this pillow case in half after rinsing,
This half was further rinsed with 2' of water containing 10 ml of the above dispersion (5 minutes at 20°C). The other half was treated with product B in the same way. A panel of 20 raters then compared these halves of the pillow cases with respect to odor and found no significant differences.

However, after one week of storage in a separate container, the Product A treated halves were better than the control halves by 35 out of 40 comparisons. This result shows that the antioxidant deposited with the formulation according to the invention is deposited more uniformly on the fabric than the antioxidant of product B, and therefore suppresses malodor more effectively. . Example ■ Add tallow alcohol 3E0 (TA3EO) to water in the following composition.
), a perfume mixture, and distearyldimethylammonium chloride (DDAC).

υ υδ 161δ
The method of manufacturing 1υυH is TA3EOl fragrance and DDAC.
to mix them together by melting them together, allowing the mixture to solidify, and then gradually incorporating cold water to give a coarse dispersion.

This was then sonicated to form a smooth emulsion.
Using a ratio of 17e of liquid to 700 g of fabric and adding 10 ml of one of the emulsions, the diluted solutions of these emulsions were used to wash resin-finished polyester in a paddle-action washing machine (Hot Point Supermactic). / Rinse the cotton fabric. The fabric was stirred in solution at room temperature, then removed and dried. When a panel of 20 assessors was asked whether the fabrics smelled, all were able to detect a difference in fragrance levels between the fabrics treated with the two emulsions.

The ones treated with D were stronger than those treated with C;
This is expected from the difference in flavor content of the two emulsions. Both treated fabrics smelled significantly more strongly than those rinsed with the perfume-only suspension at the same total concentration of Emulsion D and perfume. Example i A dispersion containing stearyl stearate (6 g), perfume mixture (4 g), distearyldimethylammonium chloride (1 g) and 100 g of water was prepared by the method described in Example (2).

25 ml of this dispersion was then added to 475 ml of a 4.5% dispersion of distearyldimethylammonium chloride in water.

To another sample of this 4.5% dispersion was added the same perfume mixture only to a level of 0.2%. These two distributions were then used for the final rinse of the wash load. A balanced wash load containing cotton terry hand towels was laundered in a M°C mule pine Tresina drum washer using a 60C wash program.

Each load was treated with one of the two powders mentioned above for a final rinse. The hand towels were evaluated by an expert panel for softness after each distribution of four loads. No significant difference was found between the two variances. However, the panel unanimously agreed that towels treated with the dispersion containing the carrier smelled more highly than those treated with the dispersion containing only the perfume mixture. Example 1 By the method described in Example 2, N,N-ditallow etalamine (5 g), distearyldimethylammonium chloride (a). 5g), optical brightener, 1-p-
Carboxymethyl phenyl-3-P-chlorophenyl-Δ2-pyrazoline (a). 05g) and water (100m
A dispersion containing L) was prepared.

A diluted solution of this dispersion containing 50 ml in 45' was used to rinse 3 kg of 1-dispersion non-fluorescent cotton terry towel at room temperature.

A similar load of towels was rinsed with a solution containing 50 mt of a 0.5% dispersion of distearyldimethylammonium chloride. As another control, attempts to obtain a 5% dispersion of N,N-ditallowethanolamine were unsuccessful. This formulation is an example of an organic matrix material providing the desired benefit, namely fabric softening.

The fluorescent agent is nylon direct, but was made into cotton direct according to the present invention. Example
Both were washed at °C.

The pieces were rinsed twice in cold water - and separated into four sets of four pieces for a third rinse. Each set of four strips was then rinsed for 5 minutes with 800 ml of cold water containing: A-None, this was the control set. B - 2 ml of a dispersion containing 5% paraffin wax and 0.05% distearyldimethylammonium prepared as in Example ① C - 2 ml of a 0.05% dispersion of distearyldimethylammonium chloride D - 1 of paraffin wax in water % dispersion 10mt (5%
distribution is not stable enough to be usable).

After drying, the sets were rearranged into four fabric sets containing one fabric from each of the treatments.

These sets were assessed for flexibility by a panel of five expert assessors. The format of this assessment consists in each set of fabrics being awarded 1 point for the softest fabric and 4 points for the roughest fabric. Therefore, if one treatment consistently produced the softest fabric in each set, the total score for this treatment would be 20. Similarly, if one treatment yields the most textured fabric, its total score will be 80. The actual scores for the above treatments were as follows: Control Rinse A was thus not significantly different from Treatments C and D.

Claims (1)

Claims: 1 i a from about 25 to about 99% of a substantially water-insoluble organic matrix material; b from about 0.5 to about 25% of a cationic material;
and c from about 0.5 to about 50 particles that are a mixture of about 0.5 to about 50% dispersed sensory perceptible material.
A liquid textile treatment formulation comprising ii wt. % of a first dispersed phase dispersed in about 50 to about 99.5% aqueous phase. 2. A liquid formulation according to claim 1 comprising from about 0.5 to about 30% of a second dispersed phase comprising a textile tempering material. 3 Claim 2 in which the textile tempering material is a textile softener
Liquid formulation by. 4 The cationic material in the first dispersed phase is about 2 to about 10% of the phase.
% of the liquid formulation according to any of the preceding claims. 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. A liquid formulation according to 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, in which the sensually perceivable material is visually perceptible. 9. A liquid formulation according to any one of claims 1 to 7 above, wherein the sensually perceivable material is olfactory perceivable. 10. A liquid formulation according to any one of claims 1 to 7, wherein the sensually perceivable material is tactilely perceptible. 11. A liquid formulation according to any one of claims 1 to 10, wherein the organic matrix material provides a second sensory perceptible effect. 12. A liquid formulation according to any one of claims 1 to 11, wherein the organic matrix material is a non-cationic material. 13. A liquid formulation according to any one of the preceding claims, wherein the matrix material is a non-ionic material. 14. Liquid formulation according to any one of claims 1 to 13, wherein the organic matrix material has a solubility in the aqueous phase of not more than 200 ppm. 15. Liquid formulation according to claim 14, in which the solubility of the organic matrix material is not greater than 50 ppm. 16. A liquid formulation according to any one of claims 1 to 15, wherein the cationic material in the first dispersed phase has a solubility in water of not more than 5 g per liter at 25°C. 17. A liquid preparation according to any one of claims 1 to 16, wherein the sensually perceivable material is a fragrance. 18. A liquid formulation according to any one of claims 1 to 17, wherein the cationic material in the first dispersed phase is a fabric softener. 19 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 (
20. A liquid formulation according to any one of claims 1 to 19, wherein R and R^1 are each an alkyl or alkanyl group containing from about 8 to about 22 carbon atoms. 20 i a about 25 to about 99% substantially water-insoluble organic matrix material; b about 0.5 to about 25% cationic material; and c about 0.5 to about 50% dispersed organoleptic material. from about 0.5 to about 5 particles that are a mixture of discernible materials
A process for preparing a liquid textile treatment formulation comprising ii. 0% by weight of a first dispersed phase dispersed in an aqueous phase of from about 50% to about 99.5%, wherein A process for the preparation of a liquid formulation for treating textiles, which is dispersed in a phase or in one of its components while in the molten state. 21. The method of claim 20, wherein the components of the first dispersed phase are i melted together, ii allowed to solidify, and iii dispersed in the aqueous phase or a component thereof.