CZ136096A3 - Process for preparing a detergent and the detergent per se - Google Patents

Abstract

A process for the production of a high bulk density particulate detergent composition containing a fluorescer which comprises mixing the fluorescer with a liquid component of the composition to form a fluorescer mixture and mixing the fluorescer mixture with a solid component, preferably non-spray-dried, of the composition whereby a particulate detergent composition is produced.

Description

Technical field

The invention relates to a process for the manufacture of a detergent composition. In particular, the invention relates to a process for the manufacture of a high bulk density detergent composition containing a fluorescent substance.

BACKGROUND OF THE INVENTION

In addition to detergent active agents, typical detergent powders contain ingredients which give the powder properties that can be regarded as desired by the market; for example, perfume and fluorescent. Fluorescent substances have been used in conventional and spray-dried powders for many years to improve bleaching.

In the manufacture of dried powders, the fluorescent substance is usually added to the components in the form of a slurry, which must be spray dried to obtain the powder.

With the advent of high bulk density powders, such as bulk densities of more than 750 g / l, new manufacturing processes have been proposed which include spray-drying powder post-mixing and densification or mixing and densification of components without the use of a spray drying step (" non-tower procedure "), for example as described in EP-A-367339 (Unilever).

The production of a detergent composition in a blending manner typically involves mixing the liquid components with the solid components of the composition such that the liquid binds to the solid material to form particles of the composition. Further mixing of the particles increases their size to form granules,

The ratio of liquid to solid components must be high enough to promote binding, but not so high that discrete particles are not obtained.

In the "non-tower" procedure, the fluorescent substances were added to the powder in a solid state in the mixing / concentration step. However, the fluorescent substances may have an undesirable color. The admixture of such fluorescent substances in solid form can damage the color quality of the final product.

SUMMARY OF THE INVENTION

It has now been found that it is possible to produce powders of high bulk density with excellent color properties by including a fluorescent substance in the liquid component of the detergent composition, thereby forming a premix fluorescent substance, which is then combined with the solid components in a mixing step to obtain a granular composition. .

According to a first aspect of the invention there is provided a method for producing a granular detergent or detergent component comprising a fluorescent agent, which comprises mixing the fluorescent agent with the liquid component of the composition to form a fluorescent agent mixture and mixing the fluorescent agent composition with the solid component of the composition. means.

According to the present invention, high bulk density compositions having a bulk density of at least 750 g / l can be produced.

The process of the present invention may be continuous or batch as desired.

The components of the detergent composition will be selected to provide the desired properties, and will generally include a wetting agent and builder, in addition to the fluorescent agent.

The composition comprises at least one liquid component to effect binding of the solid components to one another. The fluorescent substance is mixed with the liquid component to form a fluorescent substance mixture, which may be in the form of a slurry, dispersion or suspension. In such cases stirring may be necessary to prevent undesirable sedimentation.

It is particularly advantageous if the fluorescent substance mixture is in the form of a solution, since a particularly good color of the powder can then be ensured.

Any liquid components of the composition can be used to obtain the fluorescent composition, although synthetic anionic surfactants and precursors thereof are generally not suitable for use herein. However, as desired, it can be used to produce a mixture of a fluorescent substance of natural fatty acids. Preferably, the fluorescent composition comprises a liquid nonionic surfactant. The fluorescent agent composition further comprises even more preferably a mixture of a nonionic surfactant, a fluorescent agent, and water and optionally a fatty acid.

Suitable nonionic surfactants have an average degree of alkoxylation of 3 or more, preferably 5 or more, and suitably less than 20.

- - Suitable "mixture" fluoresccenční substance j ~ _e ~ roztokr 'order - ₀ 25 E _NSURING homogeneous dispersion of the fluorescer in the composition and the nonionic | the surfactant has an average degree of alkoxylation of 6 or more. (

Ethoxylated alcohols are particularly preferred. Suitable examples include SYNPERONIC A3, SYNPERONIC A7 (ICI) and coconut oil ethoxylates with an average degree of ethoxylation of 6.5. Examples of other liquid components that may be included with the nonionic

4 surfactants, including polyethylene glycols such as PEG 1500, and glycerol.

The fluorescent agent may include a fluorescent agent known in the art, such as a biphenyl compound, for example with a distyryl biphenyl compound. A particularly preferred fluorescent substance is TINOPAL CBS-X (Ciba Geigy). Preferably, the fluorescent substance is present in the fluorescent substance mixture in an amount of 0.001 to 1%, preferably 0.005 to 0.5%, even more preferably 0.01 to 0.4%, in particular 0.01 to 0.25% by weight, on the overall device.

The liquid component and the fluorescent substance are present in the fluorescent substance mixture in a suitable ratio of 10: 0.01 to 5 by weight, preferably 10: 0.06 to 4, particularly preferably 10: 0.1 to 4. a nonionic surfactant such as SYNPERONIC A7 (ICI), water and a fluorescent such as TINOPAL CBS-X (Ciba Geigy). The nonionic surfactant and water are suitably present in a weight ratio of 50: 1 to 1: 10, preferably 20: 1 to 3: 8 and even more preferably 10: 1 to 3: 8. Excellent powder whiteness (low 'b' values) are obtained at a high content of nonionic surfactant in the fluorescent mixture. Suitably, the fluorescent substance represents 1 to 25%, preferably 5 to 15% and even more preferably 6 to 12% by weight of the fluorescent substance mixture.

To achieve a higher bleaching effect on fabrics, a larger amount of fluorescent substance, for example up to 0.5% by weight based on the total powder, can be added, but this advantage can be compensated by a poorer color of the powder with greater amount of colored fluorescent substance.

Advantageously, other fluorescent substances can be included in the composition to improve fabric whiteness, thus avoiding the need for high concentrations of a colored fluorescent substance such as TINOPAL

CBS-X. Preferably, a dimorpholine fluorescent substance is present in the mixture with the powdered fluorescent substance.

The fluorescent substance mixture is suitably prepared by mixing the fluorescent substance with the liquid component under stirring to obtain preferably a solution. For nonionic surfactant / water / fluorescent systems, it is preferred that the fluorescent substance is mixed with the surfactant and water is then added.

Additionally, or the fluorescent substance is added to the mixture of nonionic surfactant and water. Preferably, the fluorescent substance mixture is prepared so as to prevent the settling of the fluorescent substance and ‘" gelling "of the liquid at room temperature.

The solid component may contain all of the components of the detergent composition except the fluorescent substance mixture, or the solid component may optionally contain at least one of said components and the other components may be added to the mixture during or after mixing the solid component and the fluorescent substance mixture.

The solid component of the composition may comprise solid particles of the individual components or solid particles comprising a plurality of components, hereinafter referred to as "auxiliary mixtures". Detergent components which are liquid (except for the fluorescent substance mixture) may be added to the solid component during or after the mixing step;

-. . . ! they may be included as desired through the auxiliary mixture. |

The solid component may be a spray-dried powder but preferably contains materials which are not spray-dried directly, especially when a high bulk density is required. |

Accordingly, a second aspect of the invention provides a method of making a detergent or detergent component comprising a fluorescent agent, which comprises mixing the fluorescent agent with the liquid component of the composition to form a fluorescent blend.

6 of a composition and mixing said mixture with a solid component of the composition which is not a spray-drying product to produce a granular detergent composition.

The mixing of the fluorescent substance mixture with the solid component of the non-spray drying composition is preferably carried out in a high speed mixer, where the fluorescent substance mixture is sprayed onto the solid surface. The obtained particles can be further processed as desired.

Optionally, the particles may be passed directly to a cooling and / or drying step with the final particles of the base powder being discharged, to which further additives may then be admixed. Alternatively, the particles may be transferred to a second, preferably slow-speed, mixing step to increase the bulk density of the particles and then be cooled and / or dried as necessary.

Where a continuous process is used, mixing and thickening steps can be performed simultaneously using a high speed mixer, suitable examples include the Shugi ™ Granulator, the Drais ™ K-TTP 80 Granulator, and the Lodige ™ CB30 Recycler. The residence time in the mixing step is suitably from 5 to 30 seconds and a suitable mixing speed in the apparatus is from

100 to 2500 min ^-1, depending on the desired densification and the particle size. If a granulation step is present, it can be carried out on a low speed mixer, for example Drais ™ K -T-160 and Lodige ™ KM300. A suitable residence time in the granulation step is about 1 to 10 minutes and the stirring speed is about 40 to 160 min ^-1 . - - - - -

A batch arrangement may be used in which the solid components of the composition are metered into the mixer and the fluorescent substance mixture is sprayed onto the solid in a suitable manner. Mixers of the FUKAE series are suitable mixers. Additional materials may be added as needed. Delay in the apparatus is selected according to the desired degree and granulation, for example, 1 to 20 minutes.

The fluorescent composition is preferably sprayed onto the solid component of the composition to ensure uniform distribution of the composition over the entire solid component.

It has been found that by the process according to the first or second aspect of the invention it is possible to provide high bulk density detergent compositions having excellent color properties.

A third aspect of the invention provides a detergent composition comprising a fluorescent substance obtainable by the method of the first aspect of the invention.

A fourth aspect of the invention provides a high bulk density detergent composition comprising a surfactant, a detergency builder, and a fluorescent having a Pc R460 of at least 3.5, preferably at least 5.5, and even more preferably at least 6.5.

The fluorescent substance is added to the composition according to the method of the first or second aspect of the invention.

Delta R460 values are determined by measuring light reflectance from a sample at 460 nm under irradiation with a tungsten lamp without a filter and measuring the reflectance of a sample under irradiation with a tungsten lamp with a UV filter and calculating the difference between two measurements. The sample to be analyzed is a sieve fraction from 355 to 500 µm. The method gives an indication of the contribution of the fluorescent substance to the reflectance of the sample.

- - Means produced according to the invention and its findings? will generally contain detergent active substances and detergency builders, and may optionally contain bleaching components and other active ingredients to enhance performance and improve performance. The detergent active (surfactant) may be selected from soaps and non-soap anionic, cationic, nonionic, zwitterionic, and zwitterionic detergent actives and mixtures thereof. Many available

8 detergent actives are fully described in the literature, for example in "Surface-Active Agents and Detergents", Parts I and II, Schwartz, Perry and Berch.

Suitable detergent actives which can be used are soaps and synthetic non-soap anionic and nonionic compounds.

Anionic surfactants are well known to those skilled in the art. Examples include alkylbenzene sulphonates, especially linear alkylbenzene sulphonates having a C ₃ -C ₁₅ alkyl chain length; primary and secondary alkyl sulfates, especially C12-C15 primary alkyl sulfates, alkyl ether sulfates; olefin sulfonates; alkylxylene sulfonates; dialkyl sulfosuccinates; and fatty acid ester sulfonates. Sodium salts are generally preferred.

In addition to the nonionic surfactants that may be present in the fluorescent composition, the nonionic surfactants may be included in any auxiliary composition used in the composition. Suitable nonionic surfactants include ethoxylates of primary and secondary alcohols, especially C ₃ C ₂ q aliphatic alcohols, ethoxylated on average from 1 to 20 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxyamides (glucamide).

The choice of detergent-active compound (surfactant) and the amount present will depend on the intended use of the detergent composition. For example, for dishwashing in dishwashers, a relatively low amount of low foaming nonionic surfactant is generally preferred. A variety of surfactants for handwashing and for washing in various types of automatic washing machines can be selected in fabric washing compositions, as is well known to those skilled in the art of making these compositions.

The total amount of surfactant present will also depend on the intended end use and may be only 0.5% by weight, for example for dishwashers, and up to 60% by weight, for example, in a handwashing composition. In laundry compositions. The amount of laundry in the washing machine is generally from 5 to 40% by weight.

Detergents suitable for use in most automatic washing machines typically contain an anionic non-soap surfactant, or a nonionic surfactant, or a combination of these two types in any ratio, optionally together with soap.

The detergent compositions of the invention will usually also contain one or more detergency builders. A suitable total amount of detergency builders in the compositions will range from 10 to 80% by weight, preferably from 15 to 60% by weight.

Inorganic builders that may be present include sodium carbonate, if desired, with calcium carbonate crystallization centers as described in GB 1 437 950 (Unilever); crystalline and amorphous aluminosilicates, for example zeolites as described in GB 1 473 201 (Henkel), amorphous aluminosilicates as described in GB 1 473 202 (Henkel), and mixed crystalline / amorphous aluminosilicates as described in GB 1 470 250 ( Procter &Gamble); and layered silicates as described in EP 164 514B (Hoechst). Inorganic phosphate builders such as sodium orthophosphate, pyrophosphate and sodium tripolyphosphate may also be present.

Zeolite builders may advantageously be present in amounts of from 10 to 45% by weight, amounts of from 15 to 35% by weight being particularly preferred for fabric washing compositions. The zeolite used in most commercial granular detergent compositions is zeolite A. Preferably, however, zeolite P having a maximum xi aluminum content (zeolite MAP) described in EP 384 070A (Unilever) may be used.

Zeolite MAP is an alkali metal aluminosilicate of type P which has a silicon to aluminum ratio not greater than 1.33, preferably greater than 1.15 and more preferably greater than 1.07.

Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic / maleic copolymers, acrylic phosphinates; monomeric polycarboxylates such as citrates, giuconates, oxydisuccinates, glycerol mono-, di- and trisuccinates; and sulfonated fatty acid salts. This list is not intended to be exhaustive.

Particularly preferred organic builders are citrates, nitrolotriacetic acid and oxydisuccinates and their suitable amounts are from 5 to 30% by weight, preferably from 10 to 25% by weight; and acrylic polymers, especially acrylic / maleic copolymers, the suitable amount of which is from 0.5 to 15% by weight, preferably from 1 to 10% by weight.

Builders, both inorganic and organic, are preferably present as alkali metal salts, especially sodium salts.

The detergent compositions of the invention may also preferably contain a bleaching system. Dishwashing detergent compositions suitably comprise a chlorine bleach system, while peroxygen bleach systems, such as inorganic peroxygen salts of organic peracids, capable of releasing hydrogen peroxide in aqueous solutions are better suited for washing powders. —— · ·· · - - = - - “™

Suitable peroxygen bleach systems include organic peroxides such as urea, and inorganic peroxy salts such as alkali metal perborates, percarbonates, perphosphates, per silicates and persulphates. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate and sodium percarbonate.

Sodium percarbonate having a protective coating against moisture destabilization is particularly preferred. Sodium percarbonate with a protective coating composed of sodium silicate and sodium metaborate is described in G8 2 123 044B (Kao).

The peroxygen bleach is suitably present in an amount of from about 35% by weight, preferably from about 10% to about 25% by weight.

The peroxygen bleach can be used in conjunction with a bleach activator (bleach precursor) to improve bleaching efficiency at low wash temperatures. The bleach precursor is present in an appropriate amount of from 1 to 8% by weight, preferably from 2 to 5% by weight.

Suitable bleach precursors are those of peroxycarboxylic acids, especially peracetic and perbenzoic acids; and percarbonic acid precursors. A particularly preferred bleach precursor suitable for the present invention is Ν, Ν, Ν ', Ν', - tetraacetylethylenediamine (TAED).

Also of great interest are the novel quaternary ammonium and phosphonium bleach precursors described in US 4,751,015 and US 4,818,426 (Lever Brothers Company) and EP 402,971A (Unilever). Especially preferred are percarbonate precursors, especially cholyl 4-sulfophenyl carbonate. Also of interest are perbenzoic acid precursors, particularly zvláště, Ν, Ν-trimethylammoniumtoloxybenzenesulfonate; and the cationic bleach precursors described in EP 284 292A and EP 303

- - 520A - (Kao) .. — _______________ _________________.________________

A bleach stabilizer (heavy metal sequestrant) may also be present. Suitable bleach stabilizers include ethylenediaminetetraacetic acid (EDTA) and polyphosphonates such as Dequest ™, EDTMP.

A particularly preferred bleach system comprises a peroxygen bleach (preferably sodium percarbonate, optionally together with a bleach activator) and a transition metal bleach catalyst as described in EP 458 397A, EP 458 398A and EP 509 787A (Unilever).

The compositions of the invention may contain an alkali metal carbonate, preferably sodium, to enhance detergency and facilitate processing. Sodium carbonate may be with λ

preferably present in amounts of from 1 to 60% by weight, more preferably from 2 to 40% by weight. However, compositions containing little or no sodium carbonate are also included within the scope of the invention.

The flow properties of the powder can be improved by including a small amount of a powder structurant, for example a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate / maleate copolymer, or sodium silicate.

A preferred powder structurant is a fatty acid soap suitably present in an amount of from 1 to 5% by weight.

Other materials that may be present in the detergent compositions of the invention include sodium silicate and sodium metasilicate; antifouling agents such as cellulosic and polymers; inorganic salts such as sodium sulfate; appropriate means for controlling or increasing mythicity; proteolytic and iipolytic enzymes; dyes; colored particles; perfumes; suds controlling agents and fabric softening agents. This list is not intended to be exhaustive. '- - - - 25

Examples of embodiments of the invention

The invention is illustrated by the following examples, which are not to be construed as limiting. All numbers in the examples refer to parts by weight unless otherwise indicated.

Examples 1-6

Λ

Six blends were formed by mixing a blend of the fluorescent agent with the other ingredients in a FUKAE FS-30 mixer to form a granular detergent composition. The fluorescent substance mixture was also varied for each example as shown in Table 1. The other ingredients of the formulation are as follows:

At LAS 20 May Sodium tripolyphosphate 25 15 Dec Zeolite 4A 23 Sodium carbonate 19 Dec

The final mixture had the following components:

- 14 Table 1

Example Mixture of fluorescent substances 1 0,02 TINOPAL CBS-X, suspension in 2 µl * (0.18 TINOPAL CBS-X added to the mixer as a solid substance) 2 0.2 TINOPAL CBS-X, suspension was 2 µl 3 0.5 NI: 0.05 TINOPAL CBS-X: 0.05 water (solution) (1.5 µl added to the mixer as liquid) 4 1.0 NI: 0.1 TINOPAL CBS-X: 0.1 water (solution) (1.0 µl added to the mixer as liquid) 5 1.5 NI: 0.15 TINOPAL CBS-X: 0.15 water (solution) (0.5 µl added to the mixer as liquid) 6 2.0 NI: 0.2 TINOPAL CBS-X: 0.2 water (solution)

* NI is nonionic surfactant SYNPERONIC A7 (IC!)

Fluorescent mixtures were prepared by mixing the fluorescent TINOPAL CBS-X and the nonionic surfactant to form a suspension. Water, if present, was added to this suspension. The mixture was then stirred slowly (for 30 minutes) to prevent sedimentation and then allowed to stand for 1 hour.

The final product was sieved to obtain a fraction of 355 to 500 µm. Under UV light and excluding UV light, the reflectance at 460 nm was measured from which the F value was calculated as described above. The results are shown in Table 2.

Comparative Example

A comparative composition was prepared from the same components as in Examples 1 to 6 by mixing a solid fluorescent agent (0.2 part) and a nonionic surfactant (2 parts) under the same conditions as in Examples 1-6.

-¾

The F value of this composition was calculated and included in Table 2.

io Table 2

Example Value F 1 3.9 2 5.5 3 6.9 4 7.1 5 7.5 6 7.2 AND 3.0

The results show that the inclusion of a fluorescent substance in the form of a fluorescent substance mixture, which is then mixed with the solids, results in an increased brightness of the powder compared to the process.

16 according to the prior art. In addition, Examples 3 and 6 show that a further improvement in whiteness is achieved when the mixture of fluorescent substances is a solution.

Example 7-14 s A series of powders having a solid content of CBS-X fluorescent substance was produced and introduced into a fluorescent substance mixture consisting of a fluorescent substance and various ratios of SYNPERONIC A7, a nonionic surfactant and water. The compositions contained the following components (parts by weight):

Sodium carbonate 16 Sodium tripolyphosphate 40 ZEOLIT 4A 11 At LAS 27 Mar: TINOPAL CBS-X 0.2 SYNPERONIC A7 2 Water 1,8 Other do 100Π

The solids (except for the fluorescent substance) were mixed together and dosed into a FUKAE FS-30 batch mixer. The fluorescent mixture, which contained 0.2 parts of the fluorescent substance in a mixture with the nonionic surfactant and water of Table 3, was then sprayed to the solid with stirring and then added to a solid.

- 17 mixer dosed with residual nonionic surfactant, NaLAS and water.

Zeolite r was finally added to form the surface layer

and.

Table 3

Example NI * Fluoresc. substance Water 7 3 1 ⁸ 8 4 1 7 9 5 1 6 10 6 1 5 11 7 1 4 12 8 1 3 13 9 • 1 2 14 10 1 1

* NI is a nonionic surfactant

Results:

^'_ BylanjrčoTáňa "OTA Ro ^ ^ F" Frary ^^ ASI? Uó'VeriKďsfr3S0 ^ 1' ~ ^^^ 5'00 "io pm for the fresh powder and after two weeks at room conditions. |

The results are shown in Table 4. b.

- 18 Table 4

Example 7 8 9 10 11 12 13 14 F value (fresh) 4 4.8 5.0 4.9 7.8 8.5 7.8 8.5 F value (2 weeks) 6.8 8.5 7.8 8.0 8.8 8.8 8.5 8.0

The powders produced in these examples show excellent color characteristics both in the case of fresh powder and after two 5 weeks. A higher proportion of nonionic surfactant has been shown to be advantageous in obtaining improved whiteness (lower 'b' value).

Examples 15 to 18

Powders were prepared by the same procedure and with the same composition as the powders of Examples 7 to 14 with the following composition of a mixture of fluorescent substances:

Example NI * Fluoresc. substance Water 15 Dec 10 1 1 16 10 1 2 17 10 1 3 18 10 1 4

* NI is a nonionic surfactant

The F values of the 350-500 µm fraction were determined and found to be greater than 8 for both fresh powder and after 9 days. The 'b' values were also determined and found to be between 2.5 and 4 for fresh powder and between 4 and 5 after 9 days. The 'b' and F values show that in the process according to the invention powders with excellent color properties.

Claims (6)

PATENT CLAIMS CLAIMS 1. A method for producing a granular detergent composition or a high bulk density detergent composition, comprising a fluorescent agent, comprising mixing, a fluorescent agent with a liquid component of the composition or a component comprising a nonionic surfactant and optionally water, wherein: forming a mixture of a fluorescent substance which is mixed with the solid component of the composition to produce a granular detergent composition. The method of claim 1, wherein the fluorescent substance mixture is a solution. Method according to any one of the preceding claims, characterized in that the liquid component and the fluorescent substance are present in a weight ratio of 10: 0.01 to 5. The method according to any one of the preceding claims, characterized in that the solid component comprises an anionic surfactant and / or a surfactant. - ^{20 21} detergency builder as separate components and / or adjuncts. Method according to any one of the preceding claims, characterized in that the solid component is not 5 'product of the spray-drying process. AND An ol / high bulk detergent composition, characterized in that it is not a product of a spray-drying process and is obtainable by a process as defined in any one of claims 1 to 5, comprising a surfactant, a detergency builder and a fluorescent and having a value of. Delt? Hfi / n of at least 3.5. A detergent composition according to claim 6, wherein the fluorescent agent is present in an amount of 0.01 to 0.25% by weight of the total composition. The composition of claim 7, wherein the surfactant comprises a nonionic surfactant.