Chlorinated solid bleaching composition which protects the fibre

Abstract

The present invention relates to a solid bleaching composition comprising at least one chlorinated bleaching and detergent agent selected among the dichloroisocyanurates and at least one optical brightener, characterised in that the pH of said composition is between 5 and 9, and in that the dissolution time of said composition in an aqueous solution is between 30 seconds and 20 minutes. The present invention likewise relates to the use of such a composition for bleaching a fabric, while protecting the textile fibres, as well as disinfecting and washing same.

Claims

1. A method for bleaching a textile while protecting the fibre, said method comprising dissolving in a washing solution a solid bleaching composition, wherein said composition comprises 50 to 99.9% by weight of a chlorinated bleaching and detergent agent selected from dichloroisocyanurates and 0.1 to 10% by weight of an optical brightener, and wherein the pH of said composition is between 5 and 9, and the dissolution time of said composition in aqueous solution is between 30 seconds and 20 minutes.

2. The method of claim 1, wherein the pH of said composition is between 6 and 8.5.

3. The method of claim 1, wherein the dissolution time of said composition in aqueous solution is between 3 minutes and 15 minutes.

4. The method of claim 1, wherein said chlorinated bleaching and detergent agent is sodium dichloroisocyanurate, potassium dichloroisocyanurate, or a mixture thereof.

5. The method of claim 1, wherein the pH of said composition is between 6.5 and 8.

6. The method of claim 4, wherein said solid bleaching composition is in the form of a solid tablet, granules, or powder.

7. The method of claim 1, wherein said solid bleaching composition is in the form of a solid tablet.

8. The method of claim 1, wherein said optical brightener is selected from disulphonic acid derivatives, bis-(triazinylamino)-stilbene derivatives, flavonic acid derivatives, naphthalimide derivatives, pyrene derivatives, diaminostilbene (DAS) derivatives, mono- or polysulphonated 4-4-distyryl-biphenyl (DSBP), 4,4-bis-(4-chloro-2-sulphostyryl)diphenyl, sodium 4,4-bis(2-sulphostyryl)biphenyl, methylumbelliferone, coumarin, dihydroquinolinone, 1,3-diaryl-pyrazoline, benzoxazole, and benzimidazole, benzisoxazole.

9. The method of claim 1, wherein said solid bleaching composition further comprises at least one additional additive.

10. The method of claim 1, wherein said solid bleaching composition comprises, by weight based on the total weight of the composition: between 50% and 99.9% of a chlorinated bleaching and detergent agent selected from dichloroisocyanurates, from 0.1% to 10% of at least one optical brightener, between 0% and 40% of at least one agent acting on the dissolution of the composition, between 0% and 0.30% of fragrance; and less than 10% of another additional additive.

Description

DESCRIPTION OF THE FIGURES

(1) FIG. 1 shows the E-pH diagram of chlorine.

(2) FIG. 2 shows the chlorine release profile in a washing solution comprising bleach (.diamond-solid.), composition 3 (.square-solid.), composition 4 (.box-tangle-solidup.), composition 1 (x) and composition 5 ().

(3) FIG. 3 shows the influence of pH on washing efficiency (.diamond-solid.), bleaching efficiency (.square-solid.), and chemical wear (.box-tangle-solidup.) of a fabric for a liquid bleach solution and a sodium dichloroisocyanurate (NaDCC) solution.

(4) FIG. 4 shows the influence of the tested compositions on the protection of a fabric's fibre.

(5) The following examples are intended to illustrate the present invention.

EXAMPLES

Example 1: Preparation of Solid Compositions of the Invention

(6) The following compositions are prepared by mixing the various ingredients listed in Table 1 below:

(7) TABLE-US-00001 TABLE 1 composition of the mixtures prepared according to the invention Ingredient 1 2 3 4 5 8 Chlorinated agent NaDCC NaDCC NaDCC NaDCC NaDCC NaDCC (64.1%) (64.1%) (64.1%) (64.1%) (64.1%) (64.1%) Optical brightener Distyryl- Distyryl- Distyryl- Distyryl- Distyryl- Tetrabenzo- biphenyl derivative biphenyl derivative biphenyl derivative biphenyl derivative biphenyl derivative tetraazaporphine (0.3%) (0.5%) (0.3%) (0.3%) (0.3%) derivative (0.3%) Effervescent agent Sodium Sodium Sodium Sodium Sodium Sodium 1 bicarbonate bicarbonate bicarbonate bicarbonate bicarbonate bicarbonate (32.8%) (32.6%) (32.8%) (32.4%) (33.4%) (32.8%) Effervescent agent Adipic acid Adipic acid Adipic acid Adipic acid Adipic acid Adipic acid 2 (2%) (2%) (2%) (2%) (2%) (2%) Disintegrating Croscarmellose Croscarmellose Croscarmellose Croscarmellose Croscarmellose Croscarmellose agent sodium sodium sodium sodium sodium sodium (0.6%) (0.6%) (0.6%) (1%) (0%) (0.6%) Fragrance Silica/fragrance Silica/fragrance Silica/fragrance Silica/fragrance Silica/fragrance Silica/fragrance premix premix premix premix premix premix (0.2%) (0.2%) (0.2%) (0.2%) (0.2%) (0.2%) Format 5-g tablet 5-g tablet Powders 5-g tablet 5-g tablet 5-g tablet pH 7.5 7.5 7.5 7.5 7.5 7.5
Percentages are Expressed as Mass Relative to the Total Mass of the Composition

(8) When the solid composition is in tablet form, the mixtures obtained are then compressed using a 20-mm-diameter cylindrical tool on a 100-MPa hydraulic press.

(9) The pH of the solid compositions is measured according to the following method:

(10) Preparation: the solid composition is dissolved in 20 C. tap water, at 10% by mass.

(11) Equipment: 1 IMMO LABO 008 pH meter Standard solutions (buffer solution) at pH 7 and 4 and/or 10. A magnetic bar, a magnetic stirrer

(12) Procedure: Calibrating the pH meter with the pH 7, pH 4, then pH 10 standard solutions Measuring the desired solution Recording the pH value read on the display after stabilization.

(13) The pH values obtained from these measurements are as follows:

(14) TABLE-US-00002 Composition 1 2 3 4 5 8 pH 7.5 7.5 7.5 7.5 7.5 7.5

Example 2: Tests of the Effectiveness of the Compositions of the Invention

(15) In order to measure the effectiveness of the compositions of the invention, the following tests are performed: Bleaching test; Test of chemical wear of the fabric; Washing efficiency test; Colour preservation test; and Dissolution test.

(16) These tests are carried out on the 5 compositions cited in Example 1. The results are then compared with the results obtained for the 5 control compositions described in the following Table 2:

(17) TABLE-US-00003 TABLE 2 control compositions Ingredient 6 7 9 10 Chlorinated ACE NaDCC NaDCC NaDCC agent bleach (64.1%) (64.1%) (64.1%) Optical with 3% 0% Distyryl- Distyryl- brightener active biphenyl biphenyl chlorine derivative derivative (0.3%) (0.3%) Effervescent Sodium Metasilicate Sodium agent 1 bicarbonate (32.8%) bicarbonate (33.1%) (5.8%) Effervescent Adipic acid Adipic acid Adipic acid agent 2 (2%) (2%) (29%) Dis- Croscarmellose Croscarmellose Croscarmellose integrating sodium sodium sodium agent (0.6%) (0.6%) (0.6%) Fragrance Silica/ Silica/ Silica/ fragrance fragrance fragrance premix premix premix (0.2%) (0.2%) (0.2%) Format Liquid 5-g tablet 5-g tablet 5-g tablet pH 11-12 7.5 11 3 Percentages are expressed as mass relative to the total mass of the composition

(18) Bleaching and Fabric Wear Test Conditions: Washing machine: Miele Softtronic W5794 front-loading drum washing machine with a maximum capacity of 7 kg. Cycle used: 30 C. Number of washes: 25 washes with cumulative effect. Water hardness: 252 French degrees. Laundry load: 4.5 kg of cotton tea-towels. Introduction method: The products are introduced into the machine's detergent dispenser at the beginning of the wash cycle. Fabric tests: Two oversewn cotton samples (40 cm30 cm) meeting the specifications developed in standard ISO 2267 are introduced into the machine: nature: pure cotton, minimum commercial length: 27 mm weave: cloth number of warp threads: 252 threads per centimetre number of weft threads: 252 threads per centimetre single yarn measurement: 302 tex (tex=weight in g of 1 km of yarn) twist: 70025 twists/m weight per square meter: 17010 g

(19) Measurement Method: Chemical WearDegree of Polymerization

(20) Chemical wear results from the degrading action of certain products on the cellulose macromolecules of the fibres and of the fabric during washing.

(21) The determination of the average degree of polymerization of cellulose is performed by measuring the viscosity at 25 C. of a solution of a cotton sample tested in a suitable solvent relative to the viscosity of the solvent itself.

(22) Two measurements are taken per strip, i.e., 4 measurements per product.

(23) The higher the value obtained, the less the fabric wear. The lower the value obtained, the greater the fabric wear.

(24) A difference of 100 points is considered significant.

(25) Measurement Method: Whiteness According to the Ganz Formula (with UV)

(26) Whiteness (W) and tint deviation (TV) are calculated according to the equations:
W=DY+P+x+Qy+C
with:
D, P, Q and C: spectrophotometer constants
Y, x, y: colorimetric values
TV=mx+ny+k
with:
m, n and k: spectrophotometer constants
x and y: colorimetric values

(27) If TV is between:

(28) 0.5 and 0.5: TD=N no deviation in tint

(29) 0.5 and 1.5: TD=R1 slight deviation in tint in the red

(30) 1.5 and 2.5: TD=R2 visible deviation in tint in the red

(31) 2.5 and 3.5: TD=R3 large deviation in tint in the red

(32) 0.5 and 1.5: TD=G1 slight deviation in tint in the green

(33) 1.5 and 2.5: TD=G2 visible deviation in tint in the green

(34) 2.5 and 3.5: TD=G3 large deviation in tint in the green

(35) A difference of 10 points is considered significant.

(36) Tests Conditions for Washing Efficiency on Oxidizable Stains: Washing machine: Miele Novotronic W980 front-loading drum washing machine with a maximum capacity of 5 kg. Cycle used: Washing: Rise in temperature: 5 minutes Plateau at 30 C.: 30 minutes Water volume: 15 litres Rinses: Three: 11, 11, 11 minutes Water volume: 14 litres Spins: Three: 2, 4, 7 minutes Total cycle time: 81 minutes Number of washes: Removal of dirt and stains: 3, without cumulative effect. Whiteness: 3, with cumulative effect. Water hardness: 252 French degrees. Laundry load: 3 kg of cotton tea-towels. Note: loads were pre-washed at 60 C. with brightener-free ECE detergent. Introduction method: The products are introduced into the machine's detergent dispenser at the beginning of the wash cycle. Fabric tests: Per wash, the following 2 series of fabrics (cotton) are introduced by pinning to the tea-towels: EQUEST tea EQUEST tomato sauce EQUEST red wine CFT CS15 blueberry CFT CS08 grass Additional soiling: 4 WFK-SBL 2004 samples per wash.

(37) Measurement Method: Removal of Dirt and Stains

(38) Spectrophotometric measurements (measurements of the amount of light reflected by the fabric) are used to calculate the percentages of dirt removal.

(39) Dirt removal is expressed by the formula:

(40) $\mathrm{Removal}\mathrm{in}\%=\frac{C-B}{A-B}100$
A=reflectance of the white control sample
B=reflectance of the soiled control sample
C=reflectance of the soiled sample after washing

(41) Reflectances are determined using the green trichromatic component, without the action of optical brighteners.

(42) Number of measurements per sample=2

(43) Number of samples per wash=2

(44) Number of washes=3

(45) Therefore, 223=12 measurements per stain and per product.

(46) In the classifications below, two products are deemed significantly different if the difference between them is 2 points or more.

(47) Colour Preservation Test Conditions: Washing machine: Miele Novotronic W838 front-loading drum washing machine with a maximum capacity of 7 kg. Cycle used: 30 C. Number of washes: 6 washes with cumulative effect. Water hardness: 252 French degrees. Laundry load: 4.5 kg of cotton tea-towels. Introduction method: The products are introduced into the machine's detergent dispenser at the beginning of the wash cycle. Fabric tests: Two oversewn cotton samples (40 cm30 cm) are introduced into the machine:

(48) TABLE-US-00004 Fabric 475 pink cotton Fabric 130 purple cotton Fabric 497 orange cotton Fabric 134 orange cotton Fabric 132 black cotton Fabric 133 blue cotton Fabric 476 blue cotton Fabric 496 blue cotton

(49) Measurement Method: Colour Preservation

(50) Spectrophotometric measurements (measurements of the amount of light reflected by the fabric) are used to calculate the percentages of dirt removal.

(51) Dirt removal is expressed by the formula:

(52) $\mathrm{Removal}\mathrm{in}\%=\frac{C-B}{A-B}100$
A=reflectance of the white control sample
B=reflectance of the soiled control sample
C=reflectance of the soiled sample after washing

(53) Reflectances are determined using the green trichromatic component, with the action of optical brighteners.

(54) Number of measurements per sample=4

(55) Number of samples per wash=2

(56) Therefore, 24=8 measurements per coloured fabric.

(57) In the classifications below, two products are deemed significantly different if the difference between them is 2 points or more.

(58) Procedure for Measuring the Dissolution Time:

(59) This method is applicable to the measurement of the dissolution time of tablets or powders for washing machines. Principle: The method used makes it possible to simulate the dissolution of a tablet or powder in a washing machine drum and, in parallel, to monitor changes in the level of active chlorine released into the water. Procedure: Filling a beaker with 1.8 L of 301 C. tap water Placing the beaker on a magnetic stirrer and place a medium-sized magnetic bar in the bottom of the beaker Placing a cage in the top of the beaker so that the cage is submerged while being as high as possible.fwdarw.only for a tablet Setting the stirring speed between 150 and 250 rpm. Placing the electrode for monitoring active chlorine release into the water so that it is sufficiently soaked to take the measurement. Placing the tablet in the cage at the top of the beaker, or the powder directly into the water, while starting the stopwatch Observing the melting of the pellet in the cage and/or the disappearance of residues in the bottom of the beaker In parallel with the dissolution, the active chlorine is measured by iodometric determination with thiosulfate and monitored over time on the computer connected to the electrode. Recording the time when there are no more residues in the cage and in the beaker Stopping the measurement and the stopwatch when the amount of active chlorine in the water stabilizes (meaning that the dissolution is complete) or reaches a maximum and then begins to decrease.

(60) Results:

(61) The results of the above-mentioned tests are grouped in the following Table 3:

(62) TABLE-US-00005 TABLE 3 results Composition 1 1 2 3 4 5 6 7 8 9 10 Parameters (4*5 g) (2*5 g) (2*5 g) (20 g) (4*5 g) (4*5 g) (170 ml) (4*5 g) (4*5 g) (4*5 g) (4*5 g) Dissolution (min) 5 5 5 30 s 2 12 <5 ms 5 5 5 5 pH 7.5 7.5 7.5 7.5 7.5 7.5 11-12 7.5 7.5 11 3 Washing efficiency 61.8 41.9 41.9 61.7 61.7 61 28.6 61.1 61.5 44.1 45.2 Whitening 167 157 168 165 165 160 174 110 125 162 135 Chemical wear 1748 1708 1698 1363 1431 1750 1127 1725 1710 1255 1723 Colour wear 17.96 17.25 17.32 23.26 20.23 16.5 28.56 19.87 18.9 22.45 15.02

(63) For the tests concerning fibre protection, bleaching, and washing efficiency on oxidizable stains, the higher the results, the better. Respectively, the higher the results, the more the product bleaches, removes oxidizable stains, and is gentle to fabrics. For the colour preservation test, the higher the results, the more the colour is worn, and the lower the results, the better the colours are preserved.

(64) FIG. 2 shows the chlorine release profile in the washing solution. FIGS. 3 and 4, respectively, show the influence of pH on washing and bleaching efficiency and on chemical wear of the fabric, and the influence of the compositions studied on fibre protection.

(65) It can be seen from these graphs that the bleach immediately releases its amount of active chlorine into the washing bath. The composition of the invention in powder form releases the active chlorine very rapidly but, owing to its composition (pH and nature of the chlorine), the fabrics are preserved better than by washing with bleach. The compositions of the invention in solid tablet form allow a more gradual release of the active chlorine and therefore preserve fabrics better. All this for the same result in terms of bleaching.

Example 3: Examples of Solid Compositions of the Invention

(66) The solid compositions of the invention may in particular correspond to the following compositions:

(67) TABLE-US-00006 Name Mass in %* Sodium dichloroisocyanurate 80.77 Sodium bicarbonate 18.93 Disodium 2,2-([1,1-biphenyl]-4,4- 0.30 diyldivinylene)bis(benzenesulphonate) Total 100.00 pH 7.5 Dissolution time 5 minutes

(68) TABLE-US-00007 Name Mass in %* Sodium dichloroisocyanurate 64.10 Sodium bicarbonate 32.80 Adipic acid 2.00 Disodium 2,2-([1,1-biphenyl]-4,4- 0.30 diyldivinylene)bis(benzenesulphonate) Croscarmellose sodium 0.60 Fragrance premix 0.20 Total 100.00 pH 7.5 Dissolution time 5 minutes

(69) TABLE-US-00008 Name Mass in %* Sodium dichloroisocyanurate 64.10 Sodium bicarbonate 32.60 Adipic acid 2.00 Disodium 2,2-([1,1-biphenyl]-4,4- 0.50 diyldivinylene)bis(benzenesulphonate) Croscarmellose sodium 0.60 Fragrance premix 0.20 Total 100.00 pH 7.5 Dissolution time 5 minutes

(70) TABLE-US-00009 Name Mass in %* Sodium dichloroisocyanurate 64.10 Sodium bicarbonate 13.40 Adipic acid 19.00 Disodium 2,2-([1,1-biphenyl]-4,4- 0.50 diyldivinylene)bis(benzenesulphonate) Sodium laurylsulphoacetate 3.00 Total 100.00 pH 5.5 Dissolution time 5 minutes *Percentages are expressed as mass relative to the total mass of the composition