DE2321693C2 - Lightening tablet suitable for use with laundry detergents - Google Patents

Description

The subject of the main patent 22 63 940 is a brightener tablet suitable for use with laundry detergents the end

a) 1 to 40 wt. o / o

at least one optical brightener,

b) 59.5 to 95% by weight
native potato starch,

c) 0.2 to 1.5% by weight

a magnesium and / or calcium soap of saturated 16 to 20 carbon atoms Fatty acids,

d) 0.3 to 3.0% by weight

at least one finely divided inorganic or mineral release agent, if necessary

e) up to 4% by weight

a surface-active wetting agent, and possibly

f) dyes or pigments.

These tablets have a number of advantageous properties, in particular a short disintegration time cold water, which is of particular importance for the use of the agent in washing machines, as for the dissolving process in the dispensing devices only limited amounts of water and dispensing properties of the The tablet may not be sufficient in the case of greater mechanical stress, especially if the potato starch used has a low binding capacity or a comparatively low water content stop, z. B. of 14% and less, it can then during the transport of the freshly compressed tablets or in the dosing and packaging devices to increased abrasion with increased powder accumulation or break the tablets. The present invention avoids this disadvantage, without adversely affecting the other properties of the tablet.

The invention relates to a brightener tablet suitable for use with laundry detergents according to patent 22 63 940, which is characterized in that it increases the strength properties

ίο additionally g) 1 to 25% by weight, if applicable contains chemically partially depolymerized, microcrystalline to fibrous cellulose

Natural and chemically partially depolymerized cellulose types are suitable, their average Fiber length 0.001 to 0.5 mm is microcrystalline and short-fiber cellulose types with an average Fiber lengths of 0.001 to 0.1 mm are preferably used in granulated form. ί \ ΐ middle The grain size of such granules is, for example, 0.005 to 03 mm, in particular 0.02 to 0.2 mm.

Long fiber varieties, d. H. those with an average fiber length of 0.1 to 0.5 mm can be used without prior Granulation of the tablet mass are added.

The fiber length of the cellulose is generally not uniform; H. fractions can also be present in the mixtures with a fiber length of less than 0.001 mm or a fiber length of more than 0.5 mm. It should however, the portions with a fiber length of less than 0.001 mm and the portions with a fiber length of less than 0.5 mm 50 Do not exceed percent by weight of the total amount of cellulose. Larger proportions of short-fiber Material ν reduces the binding capacity, larger proportions of longer fibers increase the decomposition time Tablets.

The minimum amount of cellulose required for good abrasion resistance or breaking strength is - apart from the binding capacity of the potato starch to be used according to the main patent - dependent to a certain extent on its fiber length. If long-fiber types with an average length of 0.15 to 0.5 mm are used, the required amount is 1 to 5 percent by weight of the tablet mass. Of those with an average fiber length of 0.05 to 0.15 mm, 5 to 15 percent by weight are generally required. Very short fiber types as well as microcrystalline or partially depolymerized starches with average fiber lengths of 0.001 to 0.0 ¹ J mm ko; iiTien are preferably used in amounts of 5 to 25 percent by weight. Also mixtures of

ίο short fiber or microcrystalline), and long-fiber cellulose types may be used, wherein the a ^r zuwendenden amounts result from the rule of mixtures.

From the series of types of cellulose mentioned above, there are those with an average fiber length from 0.1 to 0.5 mm preferably used, the amounts to be used 1 to 5% based on the Total amount of ingredients.

In addition to the fibrous cellulose, the tablets contain those mentioned in DE-PS 22 63 940 Ingredients, namely optical brighteners, potato starch, magnesium or calcium soaps from higher molecular weight, saturated fatty acids and mineral, fine powder ' rige release agents and optionally surface-active wetting agents. The dimensions of the tablets are the same as for the tablet according to main patent 22 63 940, d. H. the diameter is 10 to 30 mm and the thickness 2 to 20 mm, tablets with a

larger diameter for strength reasons too should have a sufficiently large thickness.

The optical brighteners contained in the tablets can be made from derivatives of aminostilbene sulfonic acid or diaminostilbene sulfonic acid, diarylpyrazoline, of carbostyril, of 1,2-di- (2-benzoxazoIy) - or 1,2-di- (benzimidazolyl) -ethylene, of benzoxazolylthiophene and coumarin.

Mixtures of optical brighteners are also suitable, especially when different textiles are used are to be washed in a washing bath or textiles made of fish fabric. Such mixtures can for example from combinations of cotton whitening agents of the aminostilbene disulfonic acid type with polyamide whitening agents of the diarylpyrazoline type or carbostyril type and / or polyester brighteners.

Examples of brighteners from the class of the diaminostilbene disulfonic acid derivatives are compounds according to formula I:

In the formula, R 1 and R 2 can denote alkoxyl groups, the amino group or residues of aliphatic, aromatic or heterocyclic, primary or secondary amines and residues of aminosulfonic acids, aliphatic residues present in the above groups preferably containing 1-4 and in particular 2-4 carbon atoms , while the heterocyclic ring systems are mostly 5- or 6-membered rings. The radicals of aniline, anthranilic acid or anilinesulfonic acid are preferred as aromatic amines. Lighteners derived from diaminostilbene disulphonic acid are mostly used as cotton lighteners. There are the following derivative of formula (I) ^Pr oducts commercially, where R ₆ represents the radical -NHC HJ and R ₂ may mean the following radicals:

-ΝΗ _Λ -NHCH ₃ , -NHCH ₂ CH ₂ OH,
-NHCH ₂ CH ₂ OCH ₃ , -NHCH ₂ CH ₂ CH ₂ OCHi,
-N (CH ₃ ) CH ₂ CH ₂ OH, -N (CH ₂ CH ₂ OH) ₂ ,
Morpholino-, -NHC ₆ H ₅ ,
-NHC ₆ H ₄ SO ₃ H ₁ -OCH ₃ .

In terms of fiber affinity, some of these brighteners are to be regarded as transition types to the polyamide brighteners, e.g. B. the whitening _{agent with R 2 = -NHC 6} Hs. The cotton whitening agents of the diaminostilbene disulfonic acid type also include the compound 4,4'-bis- (4-phenyl-1,2,3-triazol-2-yl) -2,2 '-stilbene disulfonic acid.

The polyamide brighteners include diaryl phyrazolines of the formulas (II) and (III):

Ar ₁ -N C- Ar ₂

CH ₂ -CH ₂

(III)

In formula (II), R ₃ and R5 denote hydrogen atoms, alkyl or aryl groups optionally substituted by carboxyl, carbonamide or ester groups, R4 and Re denote hydrogen or short-chain alkyl groups, An and Ar ₂ denote aryl groups such as phenyl, diphenyl or naphthyl, the other Subsü'tüeriten can sluggish, such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, carboxylic acid ester, sulfonic acids, sulfonamides and sulfonic groups or halogen atoms, commercially available brighteners of this type are derived from the Formula (III), where the radical R7 can represent the groups Cl, -SO ₂ NH ₂ , -SO ₂ CH = CH ₂ and -COOCH ₂ CH ₂ OCH ₃ , while the radical Re usually means a chlorine atom. Cyanoanthracene is one of the polyamide brighteners.

The polyamide brighteners also include aliphatic ones or aromatic substituted aminocümafine, z. B. the 4-methyl-7-dίmelhylamino- or the 4-methyl-

7-diethylaminocoumarin. Furthermore, as polyamide brighteners the compounds l- (2-benzimidazolyl) -2- (l-hydroxyethyl-2-benzimidazolyl) ethylene and 1-ethyl-3-phenyl-7-diethylämittö-carbostyfil useful. As a recording

The compounds 2,5-di- (2-benzoxazolyl) -thiophene and 2- (2-benzoxazolyl) -naphtho [2,3-b] -thiophene are lighter for polyester and polyamide fibers and 1,2-di (5-methyl-2-benzoxazolyl) -ethylene are suitable.

Furthermore, brighteners of the diphenyl distyryl type can be used of formula (IV) be present.

R ₈ -HC = CH-

= CH-R,

(IV)

wherein each of the radicals Re or R7 can represent a hydrogen atom or a sulfonic acid radical. Like the radicals R ₆ and R ₇ , the radicals R ₈ and Rq can also be identical or different from one another. Rg and Rq are phenyl radicals or substituted phenyl radicals, the following atoms or atomic groups being possible as substituents: alkyl, hydroxylalkyl or alkoxy radicals with 1-5 carbon atoms, furthermore chlorine, nitro, carboxyl, sulfonic acid, chlorosulfonyl , or sulfonamide radicals, where one or both of the amide hydrogen atoms can be replaced by alkyl radicals with 1-5 carbon atoms or hydroxyalkyl radicals with 2-4 carbon atoms, or the amide nitrogen may be part of a heterocyclic ring. Preferred radicals R ₈ or R _{9 are} the radicals chlorophenyl, nitrilophenyl, alkylphenyl, hydroxyalkylphenyl, alkoxyphenyl, carboxyphenyl and sulfophenyl, it being possible for all of these phenyl radicals to contain a sulfonic acid group as a second substituent. Like the sulfonic acid group. thus the substituents -Cl, -CN, and -COOH can also be present twice on a phenyl radical. The substituents R ₈ and Rq which are preferred also include the radicals sulfamidophenyl- (- C ₆ H4-SO2-NH ₂ ) and morpholinosulfophenyl- (- C ₆ H ₄ - SO ₂ - NC ₄ H ₄ O).

To the extent that the brighteners to be used according to the invention are sulfonic acids or carboxylic acids, they are they are preferably in the form of their water-soluble salts of alkalis, ammonium or amines or Aikylolamines with 1-6 C-atoms in the molecule are used.

In order to improve the plasticisability, the tablets contain magnesium or calcium soaps from Palmitic, stearic or arachidic acid or mixtures thereof. Magnesium stearate is preferred in quantities from 0.2 to 1.0% by weight is used. Furthermore, so-called release agents are present, which prevent the Convey tablets from the pressing tools. Suitable are e.g. B. finely divided or colloidal silica, furthermore Aluminum and magnesium oxide, phosphates, carbonates and silicates of calcium and magnesium as well Aluminosilicates or minerals containing them, e.g. B. Bentonite. as well as their mixtures. Preferably will finely divided silicon dioxide is used in amounts of 0.2 to 2% by weight.

To improve the dissolving power, the tablets can contain up to 4% by weight, preferably 0.1 to 2% by weight contain a wetting agent, for example sodium lauryl sulfate. Sodium dioctyl sulfosuccinate, sodium alkyl sulfonate with 10 to 15 carbon atoms, sodium alkylnaphthalene sulfonates or other surface-active substances like them are listed below as components of the detergent. Dyes or pigments can also be used be present to give the tablets a noticeable color or speckle or to give them an intense color tasting. ·, physiologically harmless bitter substances, to avoid confusion with medicinal tablets to prevent.

The mixing of the aforementioned constituents and pressing takes place in the usual way, without prior granulation being necessary. The pressing pressure can be 100 to 1000 · 0.0981 N / mm ³ . A

The diameter of the tablets is 10-30mm and one A thickness of 2 to 20 mm has proven to be expedient, since tablets of this size are easy to handle disintegrate in cold water with sufficient speed and are large enough to absorb the

2 »Washing 2-6 kg of laundry (usual Filling a household washing machine) to record the necessary heating amount. This crowd is like that dimensioned that for 100 g of detergent 0.01 to 1, preferably 0.05 to 0.5 g of optical brighteners for Use, for which 1 to 3 tablets are generally required.

The tablets can be packaged in such a way that they are sealed in a metal or plastic film and placed in the pack filled with detergent or attached to the outside of the pack. In the latter case, the pack preferably has correspondingly embossed depressions for receiving the tablets.
The tablets assembled in the manner according to the invention have a number of advantages in terms of manufacturing technology; In particular, difficulties that may arise from fluctuations in the quality of the native potato starch used are largely avoided. They do not tend to stick to the pressing tools and are characterized by good resistance to abrasion and breaking, which makes them particularly suitable for further processing on automatic dosing and packaging devices. Despite these improved strength properties, the disintegration times in cold water are only insignificantly greater than tablets without the addition of cellulose.

The invention is illustrated by the following examples.

example 1

To produce the tablets, the following ingredients were dried in a mixing drum for 5 minutes mixed:

1;, 6% by weight of a brightener according to the above Formula (I) in which Ri is an anilino group

and R2 represent a morpholino group,
80.85% by weight native potato starch (water content

8th%)

5.0% by weight cellulose (mean fiber length 0.4 mm)
0.45 wt% magnesium stearate
0.6% by weight colloidal silica
1.5% by weight Na ^ lauryl sulphate
The mixture was compressed under a pressure of cb. 500-0.0981 N / mm ² to form circular tablets with a diameter of 20 mm, a thickness of 4.3 mm and a weight of 1.55 g. The tablets had very good resistance to breakage and abrasion.

To test the rate of disintegration, two tablets were placed in 200 ml of water at 18 ° C and 16 ° dH, filled in a 400 ml beaker, thrown in. After a rest period of 10 seconds the solution was carried out using a magnetic stirrer-> mixes. The length of the Teflon-coated stir bar was 30 mm, the thickness 7 mm and the number of revolutions 500 per minute. The tablets were ready after a total of 20 seconds, i.e. 10 seconds after the Agitator, completely disintegrated and the ingredients dissolved or; dispersed.

DeY by abrasion in an automatic dosing device The amount of powder obtained was reduced compared to a comparative product that did not contain cellulose additive had been made And a salary äti Potato starch of 80.85%, from 6.8 to 0.6 percent by weight.

Example 2

In the drum mixer, the following ingredients were ok dry mixed:

10.0% by weight
3.0% by weight

69.5% by weight
15.0% by weight

0.4 wt%
0.6 wt%
I, 5% by weight

of the brightener used in Example 1 of a brightener according to formula (III), where R7 is the group —SO2NH2 and R ₈ = —Cl, potato starch (water content 14%), granulated cellulose (mean fiber length 0.1 mm, grain size of the granules 0, 09 to 0.25 mm),
Magnesium stearate colloidal silica ma-lauryl sulfate

The pressing was carried out in the manner indicated in Example 1. The tablets had one Diameter of 20 mm, a thickness of 4.2 mm and a Weight of U54 g. The breaking strength was 1.9 · 9.81 N, the abrasion in the automatic dosing process At 0.55%. The according to example r made A determination of the disintegration time in water gave a Value of 22 seconds.

J30 226 / T40

Claims (1)

b)
c) Patent claims: 1, Suitable for use with laundry detergents Brightener tablet off a) 1 to 40% by weight at least one optical brightener,
59.5 to 95% by weight
native potato starch, 0.2 to 1.5% by weight a magnesium and / or calcium soap of saturated 16 to 20 carbon atoms Fatty acids, 03 to 3.0% by weight at least one finely divided inorganic or mineral release agent, if necessary
up to 4% by weight
a surface-active wetting agent, and possibly Dyes or pigments, according to Patent 22 63 940, characterized in that they are used for Additional increase in strength properties 1 to 25% by weight on possibly chemically partially depolymerized, microcrystalline to fibrous cellulose contains. 2, tablet according to claim 1, characterized in that that the mean fiber length of the cellulose g) is 0.001 to 0.5 mm 3, tablet according to claims 1 and 3, characterized characterized in that the additional component g) consists of cellulose mixtures of different fiber lengths consists.