JPS63399A - Stable liquid diperoxy acid bleaching agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD This invention relates to stable liquid diperoxy acid bleach compositions useful for bleaching fabrics, hard surfaces and other substrates. The composition comprises water-insoluble fatty acid diperoxy acid particles, a C11-CI3 linear alkylbenzene sulfonate surfactant, and cumene sulfonate as an optional ingredient.
Contains magnesium sulfate, sodium sulfate or potassium sulfate as an optional component, and water. The composition also has a pH of about 2 to about 4.5 and a viscosity of about 50 to about 1000 cps at 20°C. The components, when combined in carefully balanced amounts and proportions as described below, provide a composition exhibiting good physical and chemical stability.

Background Art European Patent Application No. 160. ．． No. 342 discloses an aqueous liquid bleaching composition containing organic peroxyacid particles suspended in an acidic surfactant constituent liquid.

US Pat. No. 3,996,152 discloses stable low pH gels containing peroxyacid bleach particles and a non-starch thickener.

U.S. Pat. No. 4,100,095 discloses a method of stabilizing peroxyacid bleaches through the use of exotherm control agents.

Despite the above attempts to stabilize liquid diperoxy acid bleach compositions, there is a continuing need to develop physically and chemically stable liquid diperoxy acid bleaches that accommodate large amounts of diperoxy acid and low precision. exist.

SUMMARY OF THE INVENTION The present invention provides, by weight, (a) water-insoluble diperoxy acid particles of the formula HOOOC(CH2), C00OH, where n is from about 7 to about 14, the particles having an average size of about 0. 5 to about 15 μ)) about 100 to about 25%, (b) 011 to about 25% on acid basis
about 2% to about 6% C13 linear alkylbenzene sulfonate surfactant; (C) about 0% to about 8% cumene sulfonate on an acid basis; (d) about 5% to about 15% magnesium sulfate; )
Sodium sulfate or potassium sulfate 09 to about 7%,
and (f) a stable liquid bleach composition comprising from about 40% to about 78% water, the composition comprising (
b) +<C,> about 3% to about 14%, (d) +(e)
about 5% to about 16%, and (b) ten (e) + (d)
+(e) from about 100 to about 3096, and (a) versus (
The weight ratio of d) is less than about 3:1, and the composition has a weight ratio of 20
℃, pH about 2 to about 4.5, viscosity about 50 to about 1000 cp
The present invention relates to a stable liquid bleach composition characterized in that it has s.

DETAILED DESCRIPTION OF THE INVENTION The liquid bleach composition of the present invention comprises water-insoluble aliphatic diperoxy acid particles, a C1 to C13 linear alkylbenzene sulfonate surfactant, optional cumene sulfonate, and magnesium sulfate. Contains sodium sulfate or potassium sulfate as optional ingredients and water.

These essential ingredients are combined in carefully balanced amounts and proportions to yield a composition with high peroxy acid bleach, low product viscosity, and good physical and chemical stability. The compositions generally remain as stable suspensions with little or no separation of components upon long-term storage, preferably at room temperature, for as long as two months. The compositions also have a chemical (ie, peroxyacid) stability of at least 80%, with preferred compositions having at least about 90% stability after two months of storage at room temperature.

The compositions of the present invention have a pH of about 2 to about 4.5, preferably about 2.5 to about 4, most preferably about 3 to about 4.5, when measured at 20°C, for optimal peroxyacid bleach stability. Approximately 3.
5.

The composition also has a viscosity of about 50°C to about 10'00c at 20°C as measured on an LTV Brookfield viscometer using a No. 3 spindle and a setting of 5Q rpm.
ps, preferably about 60 to about 750 cps, more preferably about 75 to about 500 cps.

Most preferably it has about 100 to about 350 cps. This relatively low viscosity is desirable for convenient dosing from a container by the user.

The compositions of the present invention comprise substantially water-insoluble diperoxy acid particles of the formula HOOOC(CH2)nCOOOH, where n is about 7 to about 14, preferably about 8 to 12, about 10 to about 25% %, preferably about 12 to about 22%, more preferably about 14%
Contains ~20%.

The particles have an average size of about 0. 5 to about 15, preferably about 05 to about 10μ. Particularly preferred substances are 1,
12-diperoxide dodecanedioic acid (DPDA).

The composition is water soluble (e.g. alkali metal, ammonium or alkylolammonium) with an acid group content of C1
1 to about 6% linear alkylbenzene sulfonate surfactant, preferably about 2% to about 4% linear alkylbenzene sulfonate surfactant. The alkylbenzene sulfonate contributes to physical stability by dispersing the peroxyacid particles. However, alkylbenzene sulfonates are
The type and amount of the alkylbenzene sulfonate depends on the desired viscosity, since the product viscosity also increases, especially when used within the scope of the present invention, and when short carbon chain (e.g. C or Cl2) alkylbenzene sulfonates are chosen. together with the other ingredients of the invention so as to provide the desired effect. C13 alkylbenzene sulfonates are particularly preferred.

The compositions of the present invention also contain from 0 to about 8% by weight, preferably from about 1 to about 6% by weight, most preferably from about It can contain from 2% to about 5%. Cumene sulfonate also acts as a dispersant for peroxyacids and significantly reduces viscosity. Thus, cumene sulfonate is used as a thinni
ng agent) and as a partial replacement for C11-C13 alkylbenzene sulfonate surfactants.

Additionally, the bleach compositions of the present invention contain about 5% of magnesium sulfate.
to about 15% by weight, preferably about 8 to about 12% by weight. Magnesium sulfate is about 1615 to about 1.22g
Matching densities within the range of /ml helps suspend the diperoxy acid particles. Magnesium sulfate also functions as an effective exotherm control agent in the present compositions.

Additionally, the composition contains an amount of sodium sulfate or potassium rAate from 0 to about 7'TT, preferably from about 2 to about 6%. sodium sulfate and potassium sulfate,
and to a lesser extent cumene sulfonate can be used to help match the density of the peroxyacid particles and thereby suspend the peroxyacid particles. A mixture of sodium or potassium sulfate, cumene sulfonate, and 7 gn sulfate is preferred to avoid adding excessive magnesium hardness to the wash water. Mixtures of these salts also appear to be more q-effective in physically stabilizing peroxyacid particles, as they require less failure to stabilize the composition than when using magnesium sulfate alone. However, sodium sulfate and potassium sulfate significantly increase viscosity and therefore their use must be limited to meet the desired viscosity range.

Finally, the composition contains about 40 to about 78 weight percent water, preferably about 50 to about 70 weight percent.

In addition to the above, the 011-013 alkylbenzene sulfonate + cumene sulfonate preferably comprises about 3 to about 14 weight percent of the composition to provide sufficient dispersant to the peroxyacid particles while maintaining the desired low viscosity. Approximately 4~
It should comprise about 12% by weight, most preferably about 4 to about 10% by weight.

Magnesium sulfate plus sodium or potassium sulfate may be present in an amount of about 5 to about 16%, preferably about 10 to about 15%, of the composition to adequately suspend the peroxyacid particles.
It should be 2%.

The weight ratio of magnesium sulfate to sodium or potassium sulfate is preferably from about 1:1 to about 4=1, more preferably about 2 for the desired combination of exothermic stability and low wash water hardness and low viscosity. ;1 to about 3=1.

C11-013 alkylbenzene sulfonate + cumene sulfonate + magnesium sulfate + sodium or potassium sulfate in an amount of about 12 to about 30% by weight of the composition, preferably about 14 to about 25% by weight of the composition to provide sufficient dispersing/suspending agent. % should be achieved.

Also, the weight ratio of diperoxy acid particles to magnesium rA acid should be less than about 3:1, preferably less than about 2.5:1 for best exothermic stability.

Of course, the bleaching composition of the present invention can also be used as a bleaching agent. However, such compositions will more commonly be used as one element of a total bleach or laundry composition.

The bleaching compositions of the present invention can contain any of the optional ingredients known for use in such compositions.

The composition may also contain other synthetic surfactants known in the art, such as other anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, or complexes thereof. @Q, generally less than about 5 wt.96, preferably less than about 2 wt.96, most preferably about 1"l', W90. However, such additional surfactants,
In particular, nonionic surfactants and cationic surfactants are
It has been found to increase viscosity and cause phase separation when used in large amounts and is therefore not preferred for use in the present invention. Preferably, the composition is substantially free of such other surfactants.

Since the peroxy acid compounds used in the compositions of the present invention are susceptible to loss of available oxygen when contacted by heavy metals, it is desirable to incorporate chelating agents into the compositions. Such chelating agents preferably account for 0.0% of the composition.
0.005 to about 1.0% by weight. Chelating agents are described in U.S. Pat. No. 3,442,937, U.S. Pat. No. 2,838,459, and U.S. Pat.
It can be any of the well known chelating agents, including those described in US Pat. No. 1,92,255. Preferred chelating agents are picolinic acid and dipicolinic acid.

The bleaching compositions of the present invention contain them in solution with an oxygen content of 1.
It is utilized by adding to water with enough seedlings to provide 0 ppm to 1100 ppm. Generally, this is a total of 0.01-0.4% compositionally in the solution. The fabric to be bleached is then contacted with such an aqueous bleach solution.

The compositions of the present invention can also be used in conjunction with conventional fabric laundry detergent compositions. Such compositions may include standard detergent ingredients such as surfactants and builders as described in US Pat. No. 4,100,095. Preferred detergent compositions are disclosed in U.S. Pat. No. 4,561,998 and U.S. Pat.
, 507, 219.

Preferably, detergent compositions formulated for use with the bleaching compositions of the present invention have a pH of about 9 to about 12, preferably about 9.5 to about 11.5, more preferably about 10 to about 11. have They preferably contain about 2% to about 15% by weight monoethanolamine, more preferably about 4% to about 10% by weight9
Contains 6. The combination of such alkaline compositions and the bleaching compositions of the present invention preferably provides a wash water pH of about 7.8 to about 9, preferably about 7.9 to about 8.5;
Such a pH is desirable for good bleaching performance, minimal fabric yellowing, and minimal bleach degradation by monoethanolamine.

The following examples provide a detailed explanation of the invention.

All parts, 96 and proportions used herein are on a die basis unless otherwise specified.

EXAMPLE I The following composition was prepared by Nilapenbach (E) when in a water bath.
ppcnbach) prepared by high shear mixing of the ingredients in a mixer. Before operating the mixer, DPDA
and water were added to the mixer. Foam suppressants were added to minimize foaming during mixing and to minimize air trapping in the finished composition. After turning on the mixer, the other ingredients were added in the order indicated after the indicated times.

Ingredients g Weight%
Time 1.12-diperoxidedecanedione IO
,821,618,00 acid (DPDA) (26,68
% active slurry) main water (additional)
1.896 11.8 0 Foam inhibitor
12.8 0.08
1 minute C13'-alkylbenzene sulfone 4
17.8 2.5 3 minute acid (96% active ingredient*) Sodium cumene sulfonate 4[1i
3.4 1.45 3 minutes (active ingredient 50%*) Dipicolinic acid 1.8
0.01 3 min sodium sulfate
1341.6 4.0 111+i 25
Magnesium sulfate 1,684
,2 10.5 2 hours 10 minutes Sodium hydroxide 1 dose (active ingredient 5096") 104 0.32
After 3 hours and 30 minutes, the pH of the composition was measured to be 20.
It was 3.20°C. After 4 hours and 10 minutes, the pH was measured again and was 3.20- at 20°C. I stopped the mixer. The composition was a stable suspension of ingredients.

It has a dryness of about 350 cps at about 20°C. DP
The DA had an average diameter of about 2-5μ.

The above describes the high shear mixing of the ingredients in a water bath, the order of their addition and the body time of addition, all of which have been found to be important in obtaining the desired physical stability of the composition. A preferred method of preparation is described.

After 9 days, there was still no physical separation of the composition.

A 951 g sample of the composition was removed from the bottom and weighed.

It contained 18.29% DPDA and 10.81% magnesium sulfate.

The chemical stability was very good as the evaporative composition was 18.0% DPDA.

After 11 days, 48 g of the aqueous layer was removed from the bottom of the composition. The physical stability was very good as it only constituted about 0.3% of the composition.

After 18 days, the original composition was transferred to a 55 gallon drum along with five other samples of similar composition and preparation;
Mixed by hand. Analysis of the mixture revealed that DPDA
18.29% was in storage.

It is all measured at 20℃, and the drying temperature is 350CpS.
, a density of 1.187 g/ml, and a pH of 3.20. The next day, 40 samples of the mixture (4.44℃)
Stored at 50°F (10°C), 70'F (21,1°C), 90'F (32,2°C), and 100'F (37,8°C).

After 17 days, the samples had very good physical and chemical stability, as described below.

Physical Stability 40'F (4,44°C) 2 (each. Very slight 6 clear water layer on top 50°F (10°C): Passed. min 3 no 70°F (2
1.1℃) Second pass. No separation 90'F (32,2°C)
Two passes. Clear water layer on bottom less than 100°F (37,8°C): Clear water layer on bottom, layer approx. 506
Chemical stability less than 50°F (10°C): DPDA 18.25% 70
°F (21,1 °C): DPDA 18.21% 90 °F
(32.2°C): DPDA 18.28% The above composition is
Preferably, it is used in combination with the following detergent composition. A detergent composition was prepared by adding the following ingredients to a mixing vessel in the order indicated with continuous mixing.

Certified product material components (%) (
(wt%) (wt%) 014-15 alkyl polyethoxylate (2,25) 48,8 11.3 23.
Sodium 2sulfate CI3 Linear alkylbenzenesulfonic acid 91
3.0 8.0 8.33 Sodium diethylenetriaminepentaacetate 41.0 0.35 0.7
Brobylene glycol 100
．． 0 10.5 10.5 Monoethanolamine
100.0 5.0 3.0 Brightener mixture 100.0
- 8.212C alcohol polyethoxylate 100.0 9.0 7.012~13 (8,5) ' Ethanol 9
2.0 10.48 7.3 Potassium hydroxide
45.0 2.4111 5.
51 Sodium hydroxide 5
0.0 2 (945, gs boric acid
100.0 1.25 1.25
water −
Sodium -5,052-dodecenyl succinate
80.0 5.53 G, 9C12-14 fatty acid 100.0 3.5
3.5 citric acid
50.0 4.0 8.0 Calcium formate
10.0 0.12
1.2 material TEPA-E15~, 880.0 3.0 3.75p
Adjust H to 10.5 --- Protease enzyme (2,0 AU/g)
100.0 1.18 1.16 amylase enzyme
(375AM, U/g) 100.0
0.16 0.113 Fragrance
100.0 0.25 0.25 Dye 100.
0 0.08 0.0g water
- Remainder 3.25% 100% 1 Paste consists of 16.296% ethanol and 35% water
Also contains %2 monoethanolamine 32.2%, water 32.2%,
C alcohol polyethoxylate 12-13-t(6,5)” 32.2%, and brightener 3.36
Contains % alcohol and monoethoxylated alcohols removed* 15-18% of ethylene oxide at each hydrogen site
The molar (average) ethoxylated tetraethylene pentimene composition is preferably used in a detergent composition to liquid bleach volume ratio of about 5.5:1. The detergent composition is designed for approximately 0.55 cup use 2 in a typical US laundry regimen. This gives a product temperature in the wash water of approximately 0.22% by weight. Liquid bleach 0. 1 cup (i.e. approximately 25 m
Use of 1) will provide approximately 10 ppm of available oxygen to the wash water.

The detergent composition and liquid bleach are preferably codispensed simultaneously from a three-compartment bottle at a detergent to bleach volume ratio of about 5.5:1.

Mixtures of succinate and fatty acid bilgo in the detergent compositions are preferred because they produce less fabric yellowing and measure cup residue than all-fatty acid formulations when used in combination with the liquid bleaches.

Example 2 Other compositions of the invention that can be prepared similarly to Example 2 are as follows.

Weight 96 Ingredients ABCD
12.
5-25.0 21.01.9-diperoxyazelaic acid'-15,0--water
73.0 83.0 5B, 0
65.0C13 linear alkylbenzenesulfonic acid
4.0 3.0 4.0 -C11,4-linear alkylbenzenesulfonic acid ---3,0 Sodium cumenesulfonate - 2.0--Magnesium sulfate G,G
13.0 10.5 9.2 Sodium sulfate
3.1 - 2.5 - Potassium sulfate - --
1,0 Foam inhibitor −
0,10,020,02 dipicolinic acid
0.01 0.02 0.010.
01 Sodium hydroxide to the specified pH 3.
8 3.2 3453.25 Viscosity (cps, 20℃
) 450 **
900*** Average particle size after preparation: approx. 2~5μ Zero* Within the range of 50~1000
After approximately 8 months of storage at 0.degree. C., a clear aqueous layer (approximately 6 kg) was removed from the bottom of the sample and the remainder was analyzed and found to contain the following:

Ingredients Weight%1.1
2-diperoxide dodecanedio 1B,triphosphoric acid (DPD
A) Water 57
．． 0 foam inhibitor 0,11C
Alkylbenzenesulfonic acid 3,4Sodium cumenesulfonate 1.8Dipicolinic acid
0.01 sodium sulfate
3.5 Magnesium sulfate
9.2 Miscellaneous components
The remainder of the composition had a viscosity of 850 cps as measured at 20°C. An additional 6.4 parts of sodium cumene sulfonate (50% active ingredient) was added to the composition 1.
00 parts, the viscosity at 20° C. was lowered to about 240 cps. This composition had a pH of approximately 2.6. The pH was adjusted to about 3.15 by adding a 50% solution of sodium hydroxide to prepare a finished liquid bleach composition containing about 15.5% DPDA.

The above liquid bleach composition is preferably used in conjunction with the following liquid detergent composition prepared by adding the ingredients to a mixing tank in the order indicated under continuous mixing.

Certification product material CI4-15 alkyl polyethoxylate (2,25)
48.4 11.88 24.51 Sodium sulfate propylene glycol 100
．． 0 8.3g 3.53 Sodium diethylenetriaminepentaacetate 41.0 0.30 0.7
3 brightener mixture 10
0.0 - 8.703 Monoethanolamine
100.0 4.5 2
．． 50C alcohol polyethoxylate 100
．． 0 4.93 2.9312~13 (8,5) *Ethanol 92
．． 0 3.94 - Sodium hydroxide
50.0 4.19 5.38 Potassium hydroxide 45.0 1
．． 18 2.62C12-14 fatty acids
100.0 9.86 9.88 Citric acid 50.0
3.94 7.88 Calcium formate
10.0 0.12 1.20 Sodium formate 30.0
0.8B 2.77012 Alkyltrimethylammonium chloride 37.0 0.6 1.62”
80.0 1.97 2
．． 4BTEPA-E15-18 pH adjusted protease enzyme to 10.5 (2, OAU/g)
100.0 0.74 0.74 Amylase enzyme
(375AM, U/g) LOo, O
O,160,16 dye
100.0 [), 08 0.08 fragrance
100.0 0
．． 25 0.25 water - remainder 6.
59100% 1 Paste contains 1.4% sodium hydroxide, 8.44% monoethanolamine, 25% propylene glycol,
The paste also contains 1662% ethanol, 5.12% sodium hydroxide, and 20.16% water2.
Also contains 0.3% 3 monoethanolamine 7.46%, C alcohol polyethoxylate 12-13 (6,5) *29.82%, water 59.65%, and whitening agent 3.07%. Nail-containing* Alcohol and monoethoxylated alcohol removed** Ethylene oxide 15-18 at each hydrogen site
The molar (average) ethoxylated tetraethylene pentimene composition is preferably used in a 4:1 volume ratio of detergent composition to liquid bleach. The detergent composition is designed for a usage of about 0.5 cup in a typical American laundry regimen.

This means that the product concentration in the wash water is approximately 0. Give 2% by weight. Approximately 0.125 cups (i.e. approximately 30ml) of liquid bleach
The use of will give 10 ppm available oxygen to the wash water.

The detergent composition and liquid bleach are preferably co-dispensed simultaneously from a single-dose three-compartment cup at a 4:1 volume ratio of detergent to bleach.

Claims (1)

Claims: 1. Water-insoluble diperoxy acid particles of the formula HOOOC(CH_2)_nCOOOH, where n is from about 7 to about 14, by weight, having an average size of about 0. (b) about 2% to about 6% C_1_1 to C_1_3 linear alkylbenzene sulfonate surfactants on an acid basis; (c) about 0% cumene sulfonate on an acid basis; (d) about 5% to about 15% magnesium sulfate; (e) 0% to about 7% sodium or potassium sulfate
, and (f) about 40% to about 78% water, the composition comprising (
b) + (c) about 3% to about 14%, (d) + (e) about 5%
and (b) + (c) + (d) + (e) from about 12% to about 30%, and the weight ratio of (a) to (d) is less than about 3:1. , the above composition has a pH of about 2 to 20°C at 20°C.
4.5, and a viscosity of about 50 to about 1000 cps. 2. The composition according to claim 1, wherein the diperoxy acid is 1,12-diperoxide dodecanedioic acid. 3. The composition of claim 1, wherein the diperoxyacid particles have an average size of about 0.5 to about 10 microns. 4. The composition of claim 1, wherein (b) is a C_1_3 linear alkylbenzene sulfonate. 5. The composition of claim 1, wherein the composition has a viscosity of about 75 to about 500 cps at 20<0>C. 6. The composition of claim 2, wherein (b) is a C_1_2 linear alkylbenzene sulfonate. 7, C_1_3 linear alkylbenzene sulfonate approx. 2
% to about 4% and about 1% to about 6% cumene sulfonate. 8. The composition of claim 7, comprising about 8% to about 12% magnesium sulfate and about 2% to about 6% sodium sulfate. 9,1,12-diperoxide dodecanedioic acid approximately 14%
9. The composition of claim 8, comprising up to about 20%. 10. The composition of claim 9 having a viscosity of about 100 to about 350 cps at 10.20<0>C. 11. The composition of claim 10 having a pH of about 3 to about 3.5 at 20<0>C. 12. The composition of claim 1, comprising about 1% to about 6% cumene sulfonate. 13. The composition of claim 12 having a viscosity of about 100 to about 350 cps at 20<0>C. 14,1,12-diperoxide dodecanedioic acid approx. 14
14. The composition of claim 13, comprising from % to about 20%.