JP2001526305A - Laundry detergent or detergent product tablet showing improved disintegration properties - Google Patents

Abstract

  (57) [Summary] The present invention discloses detergent moldings characterized by high hardness and high stability during transport / handling and excellent disintegration properties. These advantageous properties are obtained by tablets characterized in that they are essentially free of nonionic surfactants having a melting point below 60 ° C.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD [0001] The present invention relates to a compression-molded article exhibiting laundry activity / detergent activity. The present invention, in particular,
The present invention relates to a laundry detergent / detergent product tablet used in washing textiles by a home washing machine. The term tablet is commonly used for this type of molding.

[0002] Laundry detergent and detergent product tablets are well known in the art and are becoming more and more popular among consumers because of their easy metering. Tablet-type laundry detergent / detergent products have various advantages over detergents in powder form, are easy to measure and handle, and have a compact structure, which is advantageous for storage and transportation.
For this reason, laundry detergent / detergent products are described in their entirety in the patent literature. Often the use of laundry active / detergent active tablets
One problem is that under the conditions of use of the tablet, its disintegration and dissolution rates are insufficient. Tablets with sufficient stability (ie, dimensional stability) and puncture resistance can only be manufactured by applying relatively high pressure. For this reason, the components in the tablet are subjected to a large compressive force, which delays the disintegration of the tablet into the washing liquid and, consequently, excessively delays the release of the active substance during the washing and washing processes.

[0003] The disintegration phenomenon of tablets too long has another disadvantage. That is, a typical laundry detergent / detergent product tablet cannot be washed out of the detergent input chamber of a home washing machine. This is because such tablets cannot be broken down at a sufficient rate into small secondary particles that are large enough to be washed out of the detergent hopper into the washing tub.

As described above, the tablet hardness (ie, transport / handling stability) and the easy disintegration property of the tablet are conflicting problems, and in order to solve this problem,
A number of solutions have been proposed in the prior art. One solution is that which is known in particular in the pharmaceutical field, but has also been extended to the field of laundry detergent / detergent product tablets. According to this solution, certain disintegrants are incorporated, which promote water entry or swell by water entry, which release substances in the form of gases and the like, It has a disintegration effect. Other solutions have also been proposed in the patent literature, such as compressing a premix of a particular particle size, separating one component from the other, or coating each component or the entire tablet with a binder. .

For example, EP-A-0 522 766 (Unilever) discloses tablets of a compressed, granular laundry detergent composition comprising a surfactant, a builder, and a cellulosic disintegrant. And at least some of the particles are coated with a disintegrant. This disintegrant exerts both a binder action and a disintegrant action when the tablet is dissolved in water. This reference points out the overall difficulty in producing tablets that combine sufficient stability with effective solubility. In this case, it is disclosed that the particle size of the mixture to be compressed is 200 μm or more, and the intention is that the difference between the upper and lower limits of the particle size should be 700 μm or less.

As a patent document relating to the manufacture of laundry detergent tablets per se, EP-A-0 716 144 (Un
ilever) and EP-A-0 711 827 (Unilever), the former disclosing a tablet having an outer shell of a water-soluble material, the latter comprising citrate with a certain solubility as one component Disclose a tablet.

[0007] EP-A-0 711 828 (Unilever) discloses a laundry detergent tablet using a binder (particularly polyethylene glycol) capable of exerting a disintegrating action. The laundry detergent tablets are produced by compressing the granular laundry detergent composition at a temperature between 28 ° C. and the melting point of the binder material, and the compression process is always carried out at a temperature below the melting point. If the compression treatment is performed at a high temperature as disclosed in the examples of the patent document, the tablet manufactured by the method disclosed in the patent document has a high breaking strength.

[0008] Laundry detergent tablets, in which each component is present separately from the other components, are disclosed in particular in EP-A-0 481 828 (Unilever). The laundry detergent tablets disclosed in this document contain sodium percarbonate separated from all other ingredients that may affect its stability.

[0009] The above prior art documents all disclose in detail tablets of laundry detergents or cleaning products which contain high amounts of nonionic surfactants. Also, none of the prior art documents improve the solubility of laundry detergent or detergent product tablets by intentionally removing certain components that adversely affect the hardness or disintegration properties of the tablet. Is not disclosed in detail.

It is therefore an object of the present invention to provide a laundry detergent or detergent product tablet that combines the desired high hardness and mechanical stability with a suitable disintegration rate.

DISCLOSURE OF THE INVENTION According to the present inventors, when formulating a laundry detergent or cleaning product composition, a temperature of 60 ° C.
It has been found that by substantially avoiding the use of nonionic surfactants having a melting point below, laundry detergent tablets having high hardness and capable of achieving very high disintegration rates can be produced.

[0012] Accordingly, the present invention is a compressed granular laundry detergent or detergent product laundry detergent or detergent product tablet comprising a surfactant, a builder, and optionally a laundry detergent or detergent product component. Tablets which are essentially free of nonionic surfactants having a melting point below 60 ° C.

Nonionic surfactants having a melting point below 60 ° C. In accordance with the present disclosure, nonionic surfactants of the type that should not be present in the tablet are nonionic surfactants having a melting point below 60 ° C. It is a surfactant. Such non-ionic surfactants are alkoxylated alcohols, especially primary alcohols such as fatty alcohols of animal or vegetable origin. In addition to such fatty alcohol alkoxylates, an example of a group of nonionic surfactants is an alkyl glycoside represented by the formula: RO (G) _x . Wherein, R, primary, straight-chain or methyl-branched chain (especially, 2-methyl-branched) C _{8 ~ 22,} preferably Ri C _{12 ~ 18} aliphatic group Der, G is carbon 5 or 6 Is a glucose unit (preferably a glucose unit).

[0014] Another class of nonionic surfactants are the alkoxylated fatty acid alkyl esters and polyhydroxy fatty acid amides. Further, amine oxide type nonionic surfactants are not used in the present invention, and examples thereof include N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide. Also, nonionic surfactants of the fatty acid alkanolamide type are not used in the present invention.

According to the present invention, a nonionic surfactant having a melting point of 60 ° C. or higher can be used, but the whole tablet contains the nonionic surfactant regardless of its melting point. The absence is preferred.

The term “essentially non-ionic surfactant free” as used herein refers to a non-ionic surfactant content in a laundry detergent or detergent product tablet of up to 1% by weight. Means that The reason for such an upper limit is that certain components in a laundry detergent or detergent product tablet may be contaminated by non-ionic surfactants, but it is desirable to avoid the use of such components. This is because there may be no case. For example, in producing a spray-dried base powder containing zeolite,
A small amount of a non-ionic surfactant is added to the slurry to be spray dried. This type of soiling builder, i.e., a soiling builder in which nonionic surfactants do not contribute substantially to the washing performance of the detergents produced, even in the laundry detergent or detergent product tablet of the present invention. Can be used. However, in preferred tablets, the total nonionic surfactant content is significantly lower than the upper limit of 1% by weight. In particular, the content of nonionic surfactant in the tablet is less than 0.5% by weight, more preferably less than 0.2% by weight. Most preferably, the tablets of the present invention do not contain any non-ionic surfactants. That is, the content of the nonionic surfactant is lower than the analytical detection limit.

[0017] As used herein, the term "nonionic surfactant" excludes polyalkylene glycols, such as polyethylene glycol (PEG) and polypropylene glycol (PPG). Such materials exhibit virtually no surface-active properties and can therefore be incorporated as a binder adjuvant and a disintegrant in laundry detergent or detergent product tablets. The content of polyethylene glycol and / or polypropylene glycol in the laundry detergent or cleaning product tablet of the invention is up to 5% by weight, preferably up to 2% by weight.

Surfactant The tablet of the present invention can contain a surfactant substance selected from the group consisting of anionic, zwitterionic and cationic surfactants in order to exert a washing action. For economic reasons and in view of the performance spectrum, anionic surfactants are very suitable.

Anionic surfactants Suitable anionic surfactants are, for example, sulfonate type surfactants and sulfate ester type surfactants. Suitable anionic surfactants of the sulfonate type are preferably C ₉ -C ₁₃ alkylbenzene sulfonates, olefin sulfonates (ie a mixture of alkene sulfonates and hydroxyalkane sulfonates),
And a disulfonic acid salt, which may, for example, using a C ₁₂ -C ₁₈ monoolefins having a double bond at the internal and terminal, which was sulfonated with sulfur trioxide gas, then the resulting sulfonation products The product can be obtained by alkali hydrolysis or acid hydrolysis. Other suitable sulfonate-type surfactants, with C ₁₂ -C ₁₈ alkanes,
This is, for example, an alkane sulfonate obtained by sulfochlorination or sulfonation followed by hydrolysis or neutralization. Further, esters of α-sulfofatty acids (ester sulfonates) such as hydrogenated coconut oil, palm kernel oil or tallow fatty acid α
-Sulfonated methyl esters are also suitable.

Other suitable anionic surfactants are sulfated fatty acid glycerol esters. As used herein, the term "fatty acid glycerol ester" is obtained by esterifying monoglycerol with 1-3 mol of fatty acids or transesterifying triglycerol with 0.3-2 mol of glycerol. Such monoesters, diesters and triesters and mixtures thereof. Suitable fatty acid glycerol esters of sulfuric acid, a sulfated product of C _{6 ~ 22} saturated fatty acids, as the saturated fatty acids include caproic acid, capric acid, capric acid,
Examples include myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid.

Suitable alkyl (alkenyl) sulfates are the alkali metal salts, especially the sodium salts, of sulfuric acid semi-esters of fatty alcohols,
C ₁₂ -C ₁₈ fatty alcohols, for example, coconut oil fatty alcohols, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol and the like,
Further, C ₁₀ -C ₂₀ oxo alcohols and secondary alcohols having the same chain length are exemplified.
Other suitable alkyl (alkenyl) sulphates are those having the above-mentioned chain length and containing synthetic straight-chain alkyl chains of petrochemical systems and exhibiting similar disintegration behavior to the corresponding compounds of fat and oil chemistry raw material systems. It is. C ₁₂ -C ₁₆ alkyl sulfates, C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are especially preferred in view of the washing performance. Other suitable anionic surfactants are 2,3-alkyl sulfates, for example,
It can be manufactured by the method described in US 3,234,258 or US 5,075,041 and has the registered trademark DAN (S
hell Oil Company).

Also, a linear or branched chain ethoxylated with 1 to 6 mol of ethylene oxide (EO)
Sulfuric acid monoesters of C ₇ -C ₂₁ alcohols, such as sulfuric acid monoesters of 2-methyl branched C ₉ -C ₁₁ alcohols (EO average 3.5 mol) or C ₁₂ -C ₁₈ fatty alcohols (EO1
~ 4 mol) are also suitable. Due to their high foaming capacity, such surfactants are used only in relatively small doses in detergents, for example in doses of 1 to 5% by weight.

Other suitable anionic surfactants are salts of alkyl sulfosuccinates, which are also known as sulfosuccinates or sulfosuccinates. The surfactant may be sulfosuccinic acid and an alcohol (preferably a fatty alcohol, especially an ethoxylated fatty alcohol).
And a monoester and / or a diester. Suitable sulfosuccinates, C ₈ -C ₁₈ fatty alcohol residues or mixtures thereof are exemplified. Particularly preferred sulfosuccinates comprise fatty alcohol residues derived from ethoxylated fatty alcohols, which, when considered alone, can also be referred to as nonionic surfactants (see description below). And). Of these sulfosuccinates, those whose fatty alcohol residues are obtained from a narrow range of ethoxylated fatty alcohols are particularly preferred. Alkyl (alkenyl) succinic acids having preferably an alkyl (alkenyl) chain having 8 to 18 carbon atoms and salts thereof can also be used.

[0024] Another suitable anionic surfactant is soap. Particularly suitable soaps are those of saturated fatty acids, such as salts of lauric, myristic, palmitic, stearic, hydrogenated erucic and behenic acids, and especially natural fatty acids, such as coconut oil, palm kernel oil or tallow fatty acid. The resulting soap mixture.

The anionic surfactant, including the soap, can be in the form of a sodium, potassium or ammonium salt and can be in the form of a soluble salt of an organic base such as mono, di or triethanolamine. The anionic surfactant can preferably be present in the form of a sodium and / or potassium salt, particularly preferably in the form of a sodium salt.

The tablets of the laundry detergent or cleaning products according to the invention preferably contain 5-60% by weight, more preferably 10-50% by weight, especially 15% by weight, based on the tablet weight, of an anionic surfactant. It can be included in doses of ~ 30% by weight.

According to the laundry detergent or detergent product tablets of the present invention, there is no restriction on the choice of anionic surfactant. However, suitable laundry detergent or detergent product tablets have a soap content of more than 0.2 weight, based on the tablet weight. Anionic surfactants which are preferably used are alkyl benzene sulphonates and fatty alcohol sulphates. Suitable laundry detergent or cleaning product tablets contain from 2 to 20% by weight, preferably from 5 to 15% by weight, in particular from 7.5 to 12.5% by weight, based on the tablet weight, of fatty alcohol sulphate.

In addition to the surfactant material above the builder , the most important component in the tablets of a laundry detergent or cleaning product is the builder. According to the laundry detergent or detergent product tablet of the present invention, all ordinary builders can be used, for example, zeolites, silicates, carbonates, organic cobuilders, as long as they do not cause ecological damage, Phosphates can be used as well.

A suitable crystalline layered sodium silicate has the formula: Na ₂ MSi _x O _{2x + 1} yH ₂ O Wherein M is sodium or hydrogen, x is a number from 1.9 to 4, y is a number from 0 to 20, and a preferred value for x is 2, 3 or 4. Crystalline sheet silicates of this kind are described, for example, in European Patent Application EP-A-0 164 514. Preferred crystalline layered silicates of the above formula are those wherein M is sodium and x is a number of 2 or 3. Particularly preferably, both β- and δ-sodium silicates of the formula Na ₂ Si ₂ O ₅ yH ₂ O are used, and β-sodium silicate can be obtained by methods described in the literature. (See, for example, WO-A-91 / 08171).

Other useful builders include a factor (ratio of Na ₂ O: SiO ₂ ) of about 1: 2 to about 1: 3.3, preferably about 1: 2 to 1: 2.8, more preferably about 1: 2. Amorphous sodium silicate with 2-1: 2.6, which exhibits secondary detergent properties due to delayed dissolution. In the prior art amorphous sodium silicate, delayed dissolution can be obtained in various ways, such as surface treatment, compounding treatment, compression or overdrying. The term "amorphous" as used herein refers to X-ray amorphous. That is, silicates show no sharp X-ray reflections typical of crystalline materials in X-ray diffraction experiments, and at best, the maximum of scattered X-rays with a range of diffraction angles of several degrees. Shows only one or more values. However, particularly good builder properties can be achieved in electron diffraction experiments, even when the silicate particles form a bent or sharp diffraction maximum. This means that the crystallite region of the product has a size of 10 to several hundred nm (up to 5
0 nm) and its dimensions are, in particular, at most
20 nm is preferred. So-called X-ray amorphous silicates, which exhibit dissolution properties that are slower than ordinary water glass, are described in DE-A-44 00 024.
Compressed amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are particularly preferred.

The synthetic zeolite containing microcrystals and bound water that can be used in the present invention is preferably zeolite A and / or P. Commercially available zeolite MAP® (Crosfield)
Is a particularly preferred zeolite P. However, zeolites X and mixtures of zeolites A, X and / or P are also suitable. A eutectic of zeolite X and zeolite A (about 80% by weight of zeolite X) is also suitable for the present invention, for example, as a commercial product (VEGOBOND AX®, CONDEA Augusta S. p. A.) And the formula:
_{nNa 2 O · (1-n} ) k 2 O · Al 2 O 3 · (2-2.5) SiO 2 · (3.5-5.5) represented by H ₂ O.

Zeolites can be used as builders in granular compound compositions and also as powdering agents for the compressed mixture itself. Usually, zeolites are incorporated into the premix in the two aspects described above. Suitable zeolites have an average particle size of less than 10 μm (volume distribution measured by the Coulter Counter Method) and preferably comprise 18 to 22% by weight, more preferably 20 to 22% by weight of bound water.

The known phosphates can, of course, be used as builder substances if they are ecologically sound. Preferred phosphate builders are sodium salts such as orthophosphoric acid and pyrophosphoric acid, and particularly preferred phosphate builders are sodium salts of tripolyphosphoric acid.

Useful organic builders are provided that they are ecologically safe for use, for example:
Useful polycarboxylic acids (e.g. in the form of the sodium salt), examples of which are citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and the like. And mixtures thereof. Suitable salts are salts of polycarboxylic acids, examples of carboxylic acids include citric, adipic, succinic, glutaric, tartaric, sugar acids and mixtures thereof.

[0035] According to the disintegrant present invention, disintegrant (for so-called tablet disintegrators) was incorporated into the high-compression tablet, to promote disintegration of the tablet, it is possible to shorten the disintegration time. Reference [Roempp (9th edition, Vol. 6, p. 4440) and Voight "Lehrbuch der pharma
According to Zeutischen Technologie "(6th edition, 1987, pp. 182-184), tablets or disintegrators can rapidly disintegrate tablets into water or gastric juice to absorb pharmaceutically active ingredients. It is an auxiliary agent for releasing in a suitable form.

[0036] Disintegrants such as those described above increase their capacity by ingress of water. That is,
On the one hand the intrinsic volume is increased (swelling) and on the other hand a pressure is created by the release of gas, which causes the tablet to disintegrate and form small particles. An example of an established disintegrant is the carbonate / citric acid system, in which other organic acids can also be used. Swellable disintegrants are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers and / or modified natural substances such as cellulose and starch and their derivatives, alginate or casein derivatives.

The tablets of a suitable laundry detergent or cleaning product contain one or more disintegrants, the dose of which is 0.5 to 10% by weight, preferably 3 to 10% by weight, based on the tablet weight. 77% by weight, especially 4-6% by weight.

According to the present invention, suitable disintegrants are cellulosic disintegrants. Therefore,
Suitable laundry detergent or detergent product tablets comprise such cellulosic disintegrants, the dosage of which is 0.5 to 10% by weight, preferably 3 to 7% by weight, based on the tablet weight, Especially 4 to 6% by weight. Pure cellulose has the empirical formula: represented by _{(C 6 H 1 0 O 5} ) n, formally, is called beta-1,4 polyacetal cellobiose, composed of two glucose molecules. Suitable cellulose is from about 500 to 5.0
Of glucose units, thus its average molecular weight is between 50,000 and 500,00
It is 0. According to the present invention, a cellulose derivative obtained by a polymerization analog reaction starting from cellulose can also be suitably used as a cellulosic disintegrant. Examples of such a chemically modified cellulose include an esterification or etherification reaction product obtained by substituting a hydrogen atom of hydroxy. However, cellulose in which a hydroxy group is substituted by a functional group to which an oxygen atom is not bonded can also be used as a cellulose derivative. Examples of this group of cellulose derivatives include alkali metal cellulose, carboxymethyl cellulose (CMC), cellulose esters and ethers, and aminocellulose.

The above-mentioned cellulose derivative is suitably used in the form of a mixture with cellulose, without being used alone as a cellulosic disintegrant. The content of the cellulose derivative in the mixture is preferably less than 50% by weight, more preferably less than 20% by weight, based on the cellulosic disintegrant. According to a particularly preferred embodiment, pure cellulose without cellulose derivatives is used as cellulosic disintegrant.

The cellulose used as disintegrant is preferably not used in finely divided form, but instead may be granulated or compressed before being mixed into the premix to be compressed. Can be converted to a coarse particle form. Laundry detergent or detergent product tablets contain the disintegrant in granular form or optionally in co-granulated form as described in the following literature: DE 197 09 991 (Stefan Herzog), DE 197 10 254 (Henkel)
And PCT / EP 98/1203 (Henkel). These references disclose details about the preparation of granulated, compressed or co-compressed cellulose disintegrants. The particle size of such disintegrants is at least 90% by weight, usually above 200 μm, preferably in the range from 300 to 1,600 μm, in particular in the range from 400 to 1,200 μm. The relatively coarse cellulosic disintegrants described in this specification and the above-mentioned patent documents are suitable for use as the disintegrant of the present invention, and these are commercially available products (for example, registered trademark: Arbocel TF-30-HG). , Rettenmaier).

Further, microcrystalline cellulose can be used as a cellulosic disintegrant or as a component of this disintegrant. This microcrystalline cellulose can only attack the amorphous regions and completely dissolve the amorphous regions, while partially hydrolyzing the cellulose under conditions that do not alter the crystalline regions (about 70%) ( About the total weight of cellulose
30%). Subsequent non-agglomeration of the microcrystalline cellulose formed by the hydrolysis results in microcrystalline cellulose having a primary particle size of about 5 μm, which can be compressed to particles having an average particle size of 200 μm, for example.

The tablets of the laundry detergent or cleaning product of the present invention comprise a disintegrant, preferably a cellulosic disintegrant, preferably in granular, co-granulated or compressed form, the dosage of the disintegrant being: It is from 0.5 to 10% by weight, preferably from 3 to 7% by weight, especially from 4 to 6% by weight, based on the tablet weight.

General Tablet Manufacturing Process Tablets of the laundry detergent or cleaning products of the present invention are manufactured by placing the mixture to be compressed into the cavity of a press and compressing it. In the simplest case of tablet manufacture (hereinafter simply referred to as "tabletting"), the mixture to be compressed is compressed directly (ie, without prior granulation). This so-called direct compression method is simple and cost-effective. This is because no other steps (and thus no additional equipment) are required. However, such advantages are accompanied by the following disadvantages. For example, a powder mixture to be compressed directly needs sufficient plastic deformation properties and good flow properties. In addition, the powder mixture should not show any tendency for phase separation during storage, transport, filling of dies, and the like. For many mixtures, these three requirements can only be achieved with significant difficulty. For this reason, direct compression, especially for tablet production of laundry detergents or cleaning products, has hardly been adopted. That is, for tablets of laundry detergents or detergent products, the usual manufacturing route starts with the fine powder component ("primary particles"), which are conventionally agglomerated or granulated to form larger particle sizes. Form secondary particles. The granules or granule mixture obtained are then mixed with a milling aid and fed to the tableting process.

Premix Tablets of the preferred laundry detergent or detergent products of the present invention are prepared by compressing a granular premix comprising at least one set of surfactant-containing granules and at least one post-mixed milled component. It is obtained by doing. For later laundry detergent or detergent product tablets, it is advantageous for the bulk density of the premix to be compressed to approach that of a conventional compressed laundry detergent. Particularly preferably, the bulk density of the premix to be compacted is at least 500 g / l, preferably at least 600 g / l, especially 700 g / l.
It is a numerical value exceeding l.

Powdering of the Premix Prior to compressing the granular premix to form a laundry detergent or cleaning product tablet, the premix may be "pulverized" with a comminuted surface treatment. This is advantageous for both the premix (storage, compression), and the final laundry detergent or cleaning product tablet, due to their structure and physical properties. The finely pulverized powdering agent is conventionally known, and usually, an inorganic salt such as zeolite and silicate is used. Preferably, however, the premix is pulverized with a finely divided zeolite, preferably a faujasite type zeolite.

As used herein, the term “faujasite-type zeolite” refers to all three zeolites that constitute the faujasite subgroup of zeolite structure group 4 [Don
ald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, p. 92]. Therefore, according to the present invention,
In addition to zeolite X, zeolite Y and faujasite and mixtures of these compounds can also be used, but zeolite X alone is preferred.

The co-crystallized mixture of faujasite-type zeolite and another zeolite is:
Although not necessarily belonging to zeolite structure group 4, according to the present invention, it can be used as a powdering agent. It is advantageous if at least 50% of the powdered material consists of faujasite-type zeolites.

According to the invention, preferably, the tablets of the laundry detergent or cleaning product are composed of a granular premix, which comprises the granule component and the post-mixed ground material. In this case, the post-mixed and ground material is a faujasite-type zeolite having a particle size of less than 100 μm, preferably less than 10 μm, especially less than 5 μm, and the dose is based on the premix to be compressed. Preferably, it is at least 0.2% by weight, preferably at least 0.5% by weight, in particular more than 1% by weight.

Other Detergent Components In addition to the surfactants, builders, disintegrants and the like described above, the tablets of the laundry detergent or detergent product of the present invention may contain bleaching agents, bleaching activators, enzymes, pH regulators, fragrances, Washing agents selected from the group consisting of agents, fragrance-containing substances, fluorescent agents, dyes, antifoaming agents, silicone oil, anti-redeposition agents, optical brighteners, glazing inhibitors, dye transfer inhibitors and anticorrosives Comprising representative ingredients in detergent or cleaning products.

Bleaching Agents, Bleaching Activators and Bleaching Catalysts Among the bleaching compounds that produce hydrogen peroxide (H ₂ O ₂ ) in water, sodium perborate tetrahydrate and sodium perborate monohydrate Things are particularly important. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphate, citrate perhydrate and hydrogen peroxide producing persalts or peracids, such as perbenzoates, peroxophthalates, Diperazellaic acid, phthaloiminoperic acid or diperdocanedioic acid.

In order to improve the bleaching effect when washing at a temperature of 60 ° C. or lower, the bleaching activator can be incorporated alone or in the form of a mixture. Bleach activators which can be used are the perhydrolysis (perhydro lysis) conditions, aliphatic peroxocarboxylic acids, preferably C _{1 ~ 10} (preferably C _{2 ~ 4)} aliphatic peroxocarboxylic acids and / or Or compounds which form unsubstituted or substituted perbenzoic acids. Substances containing O- and / or N-acyl groups and / or unsubstituted or substituted benzoyl groups having the stated number of carbon atoms are preferred. Suitable bleach activators include polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED)
, Acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro
-1,3,5-triazine (DADHT), acylated glycoluril, especially tetraacetylglycoluril (TAGU), N-acylimide, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonate, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, and 2,5-diacetoxy-2,5- Hydrofuran and the like can be mentioned.

In addition to or instead of the usual bleach activators, so-called bleach catalysts can be introduced into the tablets according to the invention. Bleach catalyst refers to a salt or complex of a transition metal that enhances bleaching, such as a manganese-, iron-, cobalt-, ruthenium- or molybdenum-selenium complex or carbonyl complex. In addition, manganese complexes, iron complexes, cobalt complexes, ruthenium complexes, molybdenum complexes, titanium complexes, vanadium complexes, copper complexes, and the like containing a nitrogen-containing tripod ligand, and cobalt-, iron-, copper-, and ruthenium- Amine complexes can also be used as bleach catalysts.

Enzymes Suitable enzymes are selected from the group consisting of proteolytic enzymes (proteases), lipolytic enzymes (lipases), starch hydrolases (amylases), cellulases and mixtures thereof. Particularly preferred enzymatically active ingredients are those obtained from bacterial or fungal strains, such as Bacillus S.
ubtilis), Basillus licheniformis, Streptomyces gtiseus and the like. Subtilisin-based proteolytic enzymes are preferably used and Bacillus lentus (Bacillus l.
entus) are particularly preferred. Of particular interest in this regard are enzyme mixtures, such as mixtures of proteolytic enzymes and starch hydrolases, mixtures of proteolytic enzymes and lipolytic enzymes, mixtures of proteolytic enzymes and cellulases, and cellulases. Examples thereof include a mixture of lipolytic enzyme, a mixture of proteolytic enzyme, amylolytic enzyme and lipolytic enzyme, and a mixture of proteolytic enzyme, lipolytic enzyme and cellulase. Particularly preferred is a mixture containing cellulase. In some cases, peroxidases (peroxidases) and oxidases (oxidases) have also proven suitable.

The enzyme can be absorbed by the carrier material and / or embedded in the coating material, thereby protecting the enzyme from premature degradation. The proportion content of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5% by weight, preferably about 0.1 to 2% by weight, based on the tablet weight.

Ingredients for Grease Removal In addition, the tablets of the laundry detergent or cleaning products of the present invention can contain ingredients that promote the removal of grease from textiles (also called soil release agents). . This accelerating effect is particularly evident when textiles already containing such an oil-soluble component and already repeatedly washed with the detergent of the present invention become soiled. Suitable oils and fats dissolving components include nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose (15-30% by weight of methoxy groups and 1-15% by weight of hydroxypropyl groups; And the known polymers of phthalic acid and / or terephthalic acid, in particular the polymers of ethylene terephthalate and / or polyethylene glycol terephthalate and their anionic and / or nonionic modified derivatives. Of these, the sulphonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Fluorescent Whitening Agent The tablet of the present invention can contain a derivative of diaminostilbene disulfonic acid or an alkali metal salt thereof as a fluorescent whitening agent. Suitable optical brighteners are, for example, salts of 4,4′-bis- (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2′-disulfonic acid Or a compound having the same structure and having a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group. Substituted diphenylstyryl type brighteners can also be used, such as 4,4'-bis- (2-sulfostyryl) biphenyl, 4,4'-bis- (
4-chloro-3-sulfostyryl) biphenyl or 4- (4-chlorostyryl) -4 '-(2
-Sulfostyryl) biphenyl alkali metal salts are exemplified. Mixtures of the above whitening agents can also be used.

Dyes and Fragrances (Perfume Oils) According to the present invention, dyes and fragrances are added to detergent tablets to improve the aesthetic effect formed by the product, thereby providing consumers with the necessary Not only the washing properties, but also visually and sensorially "typical and non-failure" products can be provided. Suitable fragrance oils or fragrances include perfuming compounds, such as esters,
Examples include ether, aldehyde, ketone, alcohol and hydrocarbon-based compounds. Representative of ester-based flavoring compounds are benzyl acetate, phenoxyethyl isobutyrate, pt-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate , Allylcyclohexyl propionate, styralyl propionate and benzyl salicylate. As ether-based perfuming compounds,
Benzyl ethyl ether is exemplified. 8 to 1 as aldehyde-based perfuming compounds
Examples include linear alkanals having 8 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial, burgeonal and the like. Suitable ketone-based compounds are ionone, α-isomethylionone and methylseryl ketone. Examples of alcohol compounds include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol, terpineol and the like. Examples of the hydrocarbon compound mainly include terpenes such as limonene and pinene. Preferably, however, a mixture of different fragrances is used, which together produce an attractive aroma. Such perfume oils can include natural flavor mixtures such as those obtained from plant sources, examples of which include pine oil, citrus oil, jasmine oil, patchouli oil, rose oil, ylang ylang oil and the like. . Preferred are cleary sage oil, chamomile oil, clove oil, balsam oil, mint oil, cinnamon oil, lime-blossom oil, juniper berry oil, vetiver oil, olive oil, galbanum oil, labodanum oil, orange brossam oil , Neroli oil, orange peel oil, sandalwood oil and the like.

The detergent tablets of the present invention usually contain less than 0.01% by weight of a dye and the fragrance (perfume oil) can be constituted in an amount of up to 2% by weight of the total amount of the tablet.

A fragrance can be directly incorporated into the tablets of the present invention. In another advantageous embodiment, the fragrance is applied to a carrier that enhances the attachment of the fragrance to the laundry, and the slow release of the fragrance ensures long-lasting perfume on the laundry. . An example of a carrier material that has been found to be suitable is cyclodextrin,
In this case, the cyclodextrin-perfume complex can be coated with additional auxiliaries.

Dye According to the present invention, the carrier material of the present invention can be colored with a dye to improve the aesthetic appearance of the tablet. Suitable dyes are selected from those which do not cause any problems in the art, exhibit a high storage stability and a high insensitivity to other components and light in tablet detergents, and to the textile of textiles. On the other hand, it does not show remarkable dyeability, and therefore does not dye such fibers.

Tablet Production Method The tablet production method of the present invention comprises the steps of first dry-mixing each component (some or all of these components may be pre-granulated) and then molding the resulting mixture by a conventional method. / Formation, especially tableting. To produce the tablet of the present invention, the premix is
Compress between two punches in a die to form a solid compact. Hereinafter, this process will be referred to as a tableting process for simplicity, and includes four stages (weighing, compression (elastic deformation)).
, Plastic deformation and extrusion).

First, the premix is introduced into a die. The level of filling, and thus the weight and shape of the formed tablet, is determined by the location of the lower punch and the shape of the die. Even at high tablet throughputs, uniform metering is preferably achieved by metering the premix volume. As the tableting process proceeds, the upper punch comes into contact with the premix and descends toward the lower punch.
During this compression phase, the particles of the premix are compacted together and the pore volume of the filling between the punches continues to decrease. In the plastic deformation stage, the particles become coarse particles to form a tablet, but when the plastic punch reaches a predetermined position of the upper punch, and thus the pressure on the premix reaches a predetermined value, Be started. Depending on the physical properties of the premix, its constituent particles are partially milled,
The premix is sintered at high pressure. As the compression rate increases (i.e., at high throughput), the elastic deformation phase becomes shorter and shorter, so that the formed tablet may have more or less large pores. In the final step of the tableting process, the final tablet is forcibly ejected from the die by the lower punch and transported by the subsequent transport device. At this stage, only a limited weight of the tablet is achieved. This is because tablets still change shape and size as a result of physical processes (redrawing, crystallographic action, cooling, etc.).

The tableting process can be carried out on a commercial tableting press, which is generally equipped with single or double punches. In the latter case, not only is the upper punch used to form the compression force, but the lower punch also moves toward the upper punch during the tableting process, and the upper punch compresses downward. For small-scale production, an eccentric press for tablets is preferably employed. In this press, a punch is fixed to an eccentric disk, which is mounted around a shaft that rotates at a predetermined speed. Such a punch movement is comparable to the operation of a normal four-stroke engine.
Tableting can be performed by upper punch and lower punch, but some punches
It can be fixed to a single eccentric disk, in which case the number of die holes is correspondingly increased.
Depending on the type of eccentric press, the throughput varies from several hundred up to 3,000 tablets / hour.

For large-scale production, a rotary tablet press is generally employed. In a rotary tablet press, a relatively large number of dies are arranged on a circular die table. The number of dies varies between 6 and 55, depending on the model, but more dies are commercially available. The upper punch and the lower punch communicate with each die on the die table, and the tablet compression force is effectively formed by both the punches as well as the upper punch or the lower punch as described above. The die table and the punch move around a common vertical axis, and the punch is carried by a rail-like cam track to a filling, compression, plastic deformation and extrusion position during rotation. In locations where large die up or down movements are required (filling, compression, extrusion), such cam tracks are supported by additional low pressure members, low tension rails and discharge channels. The die is filled from a fixed feeding device (so-called filling shoe), which is connected to a storage container for the premix. The compression force on the premix can be adjusted independently via the compression path by the upper and lower punches, the compression force being formed by the rotation of the shaft head of the punch through an adjustable pressure roller. .

For increased throughput, a rotary press with two filling shoes is used. These filling shoes suffice in a circle that moves only half to make one tablet. For the production of two-layer or multi-layer tablets, several filling shoes are arranged in series and the lightly compressed first layer is not discharged before further filling. With certain preferred process controls, laminated tablets and inlay tablets having a structure similar to the onion skin can be formed in this way. In the case of an inlay tablet, the core layer or the top surface of the core is not covered and therefore remains visible. Rotary tablet presses can also include forming tools such as single or multiple punches, such that, for example, an outer circle of 50 holes and an inner circle of 35 holes can be simultaneously used and compressed. it can. Modern rotary tablet presses have a throughput of over one million tablets per hour.

A tableting machine suitable for the present invention can be obtained from, for example, the following production companies. Apparatebau Holzwarth GbR, Asperg, Wihelm Fette GmbH, Schwarzenb
ec, Hofer GmbH, Weil, KIKIAN, Cologne, KOMAGE, Kell am See, KORSCH Press
en GmbH, Berlin, Mapag Maschinenbau AG, Bern (Switzerland) and Couroy N
.V. Halle (BE / LU). An example of a particularly suitable tablet press is the HPF 630 hydraulic double press (LA
EIS, D).

Tablet Form and Dimension Tablets can be manufactured in a predetermined three-dimensional form and predetermined dimensions.
Suitable three-dimensional forms can take virtually any form that is feasible, for example, bar, rod or ingot forms, cubes, blocks, corresponding forms with flat sides Especially in the form of a cylinder having a circular or oval cross section. This last example includes a tablet configuration to a compact cylindrical configuration with a height / diameter ratio of more than one.

In each of the above embodiments, a split compact can be designed consisting of components separated from each other, each component corresponding to a predetermined dose of a laundry detergent or cleaning product.
However, it is possible to design a compact in which such mass units (elements) are combined in a single compact, and in this case, a smaller divided unit can be easily formed, especially from a predetermined weak spot setting portion. Can be separated. To use laundry detergent in a standard horizontal washing machine in Europe, it is advantageous to manufacture such a split compact as a tablet in the form of a cylinder or a block, preferably a diameter The / height ratio is from about 0.5: 2 to about 2: 0.5. Commercially available hydraulic, eccentric and rotary presses are particularly suitable for the production of such compacts.

For the tablet of the present invention, a three-dimensional form of another embodiment is such that its dimensions are adapted to the detergent chamber of a commercial household washing machine, whereby the tablet can be directly
That is, the tablet can dissolve during the water dispensing operation without the use of a weighing tool and can be weighed into the detergent dispensing chamber. However, it is, of course, possible to use a laundry detergent tablet with a measuring instrument, and this embodiment is suitable for the present invention.

Other suitable tablets that can be manufactured are tablets having a sheet-like or rod-like structure with alternating thick and long portions and thin and short portions. Each part breaks at a predetermined break point (thin and short part) and is cut off from the "slab"
Can be introduced into the machine. Also, the principle of this "bar" of laundry detergent can be embodied in other geometries, for example, a vertical triangle which joins each other only at one of their longitudinal sides.

According to the present invention, it is further possible to produce a tablet having at least two layers without compressing each component into a uniform tablet. In this case, the multiple layers can be manufactured to have different dissolution rates. This can provide tablets that exhibit favorable performance characteristics. For example, if the tablet contains components that may adversely affect each other, the first component will be trapped in the more rapidly dissolving layer while the second component will be trapped in the more slowly dissolving layer, When the second component is dissolved in the solution, the first component can terminate the reaction. The layer structure of the tablet can take the form of a deposition, the inner layer of which can be dissolved at the edge of the tablet before the outer layer has completely dissolved. However, as an alternative, another layer may be placed on the outside of the side of the inner layer to completely surround the inner layer, thereby preventing the components of the inner layer from prematurely dissolving. be able to.

According to another preferred aspect of the invention, the tablet consists of at least three layers (ie two outer layers + at least one inner layer). In this case, the peroxy bleach is present in at least one of the inner layers, while no peroxy bleach is present in the two outer layers (stacked tablets) or the outermost layer (shell tablets). In another possible embodiment, the peroxy bleach and bleach activator or bleach catalyst and / or enzyme can be present in the same tablet, spatially separated from each other. Such a multi-layer tablet can be used not only through a detergent charging room or a measuring tool to be poured into the washing liquid, but also by putting the tablet into the washing machine without incurring the danger of spotting due to bleach or the like. Has the advantage that it can be directly contacted.

A similar effect can be achieved by coating the components in the laundry detergent or cleaning product, which are compressed, or the tablets themselves. For this purpose, the tablets to be coated can be sprayed on with aqueous solutions or emulsions, or can be applied by melt coating.

After compression, the laundry detergent or detergent product tablets show high stability. The fracture resistance of the cylindrical tablet can be confirmed from the diametral fracture stress. It has the following formula:

Σ = 2P / πDt In the above formula, σ is a fracture stress in the diameter direction (DFS, Pa), P is a force (N) that causes the tablet to be broken by compression, and D is a tablet. Is the height (m), and t is its height.

Example A surfactant-containing granule was mixed with the milled ingredients to prepare a premix, which was compressed by a Korsch tablet press to produce a laundry detergent tablet. In this case, the compression force was adjusted so that two series of tablets having different hardnesses were obtained.

The surfactant granules for the tablets E1 and E2 according to the invention do not contain non-ionic surfactants. On the other hand, the comparative granules for comparative tablets V1 and V2 contain 5.7% by weight of nonionic surfactant (a dose of 3.5% by weight based on the tablet weight). Tablets E1 and E2 differ only in hardness from V1 and V2, respectively, and do not differ in other compositions. The composition of the surfactant granules and the composition of the premix to be compressed (and therefore the composition of the tablet) are shown in Tables 1 and 2 below.
Shown in

[0077]

TABLE 1 Composition of surfactant granules (% by weight)

[0078]

Table 2: Premix composition (% by weight) ☆ Compressed cellulose (particle size: 90% by weight> 400μm)

Hardness Test and Disintegration Test Tablet hardness was measured by deforming the tablet until it disintegrated. In addition, the force measured the maximum force which the tablet can endure in addition to the side surface of the tablet. For the disintegration test, the tablets were placed in a glass beaker filled with water (temperature 30 ° C., 600 ml) and the time required for the tablets to completely disintegrate was measured.

[0080]

[Table 3]: Physical property data of tablets

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 11/00 C11D 11/00 (72) Inventor Andreas Rietzmann Federal Republic of Germany Day-44805 Bochum, Am Nordbad No. 88 (72) Inventor Hans-Friedrich Kluse Federal Republic of Germany Day 41352 Korschen Bloich, Am Hallenbad No. 44 (72) Inventor Fred Shamville Federal Republic of Germany Day 40789 Monheim, Niederstrasse 96 (72) Inventor Gerhard Blazey Federal Republic of Germany Day 40599 Düsseldorf, Würstenberger Strasse No. 21 (72) Inventor Heinke Jevens Germany-Day 40589 Düsseldorf, Itterstrasse 35 (72) Inventor Christian Brock Germany Day-Day 50733 Cologne, Wartburgplatz 12 Number (72) Inventor Bernhard Müller Federal Republic of Germany Day-40724 Hilden, Titianweg 9th F term (reference) 4H003 AB03 AB19 AB27 AC08 BA17 DA01 EA15 EA16 EA20 EA28 EB12 EB22 EB24 EB30 EB32 EE05 FA32 FA42

Claims (10)

[Claims] 1. A compressed granular laundry detergent or detergent product laundry detergent or detergent product tablet comprising a surfactant, a builder, and optionally a laundry detergent or detergent product component, comprising: Tablets characterized in that they are essentially free of non-ionic surfactants having a melting point below ℃. 2. The tablet according to claim 1, which is essentially free of a nonionic surfactant. 3. The composition of claim 1, wherein the anionic surfactant is present in a dose of 5 to 60% by weight, based on the tablet weight, preferably 10 to 50% by weight.
Tablet as described. 4. Fatty alcohol sulfate, based on tablet weight,
2. The composition according to claim 1, comprising a dose of 2 to 20% by weight, preferably 5 to 15% by weight, in particular 7.5 to 12.5% by weight.
The tablet according to any one of to 3. 5. The disintegrant according to claim 1, comprising 0.5 to 10% by weight, preferably 1 to 6% by weight, especially 3 to 5% by weight, based on the weight of the tablet. Tablet. 6. A disintegrant, preferably a cellulosic disintegrant, preferably in granular, co-granulated or compressed form, wherein the dose of disintegrant is 0.5 to 10% by weight, based on the tablet weight. The tablet according to claim 5, which is preferably 3 to 7% by weight, especially 4 to 6% by weight. 7. A process according to claim 1, wherein the granulated premix comprises at least one set of surfactant-containing granules and at least one post-mixed comminuted component. Tablet. 8. The tablet according to claim 7, wherein the premix to be compressed has a bulk density of at least 500 g / l, preferably at least 600 g / l, in particular more than 700 g / l. 9. The finely divided component of the post-mix is a faujasite-type zeolite having a particle size of less than 100 μm, preferably less than 10 μm, especially less than 5 μm, the dose of which is at least based on the premix to be compressed. 0.2% by weight, preferably at least 0.5% by weight
9. Tablet according to claim 7 or 8, in particular in an amount exceeding 1% by weight. 10. A builder, a bleach, a bleach activator, an enzyme, a pH regulator, a fragrance, a fragrance-containing substance, a fluorescent agent, a dye, a foam inhibitor, a silicone oil, a redeposition inhibitor, a fluorescent brightener. The tablet according to any one of claims 1 to 9, comprising one or more substances selected from the group consisting of a graying inhibitor, a dye transfer inhibitor and an anticorrosive.