JP2001515954A - Detergents and detergent moldings exhibiting improved solubility - Google Patents

Abstract

  (57) [Summary] The present invention relates to detergent or detergent moldings comprising detergent or detergent compressed particles and exhibiting improved solubility. The compacted particles comprise one or more surfactants, additives, cellulosic disintegrants and, optionally, other detergent or detergent components, wherein in this compact all hydrophobic substances are applied to the support material. Is done.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention relates generally to compact molded articles (tablets) exhibiting detergent properties. More particularly, the present invention relates to a detergent tablet such as a tablet-type laundry detergent, a dishwashing detergent, a stain remover, and a water softener used at home, particularly for an electric washing machine.

[0002] Detergent tablets have been widely disclosed in the prior art and are becoming more and more popular among consumers because of their easy weighing. Tablet-type detergents (detergent tablets) have various advantages over powder-type detergents, and are easy to measure and handle.
The compact structure is advantageous for storage and transportation. For this reason, detergent moldings are described in detail in the patent literature. When using detergent tablets,
One problem that can often occur is that, under the conditions of use of the detergent tablet, its disintegration and dissolution rates are insufficient. Since detergent tablets with sufficient stability (ie, dimensional stability) and puncture resistance can only be manufactured by applying relatively high pressures, the components in the detergent tablets are subject to high compression. Under the force, this delays the disintegration of the detergent tablets into the wash liquor, and consequently excessively delays the release of the active substance during the washing process.

[0003] The problem of too long disintegration times for highly compressed tablets is particularly known in the pharmaceutical industry. This industry has long employed certain disintegration aids (so-called tablet disintegrants) to reduce the disintegration time. Roempp (9th edition, Vol. 6, p. 4440) and Voigt "Lehrbu
According to "ch der pharmazeutischen Technologie" (6th edition, 1987, pp. 182-184), disintegrants or disintegrants for tablets 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.

"Hagers Handbuch der pharmazeutischen Praxis" (5th edition, 1991, p. 942)
Disintegration accelerators or disintegrants are classified according to their mechanism of action, and the most important mechanisms of action are those caused by contact with water, ie, swelling mechanism, deformation mechanism, wick mechanism, repulsion mechanism, gas foaming mechanism (foamed tablet) Mechanism). In the case of the swelling mechanism, the particles come into contact with water and increase their capacity. This causes the locally formed stress to spread throughout the tablet, causing the compressed structure to collapse. The swollen particles are pre-compressed during the tableting process and then return to their original dimensions upon contact with water, in which point the deformation and swelling mechanisms differ. In the case of the wick mechanism, water is sucked into the tablet by the disintegration accelerator, thereby loosening the bonding force between the particles,
This leads to tablet disintegration. The repulsion mechanism further differs in that the particles loosened by the water sucked into the pores repel each other under the action of the formed electrical force. Effervescent tablets contain an active substance or active substance system that releases a gas on contact with water, and the released gas causes the molded body to burst, the mechanism of which is based on a completely different one . In addition, the use of hydrophilizing agents, such as to better wet the compressed particles in water and promote their disintegration, is known.

[0005] Of the above-mentioned mechanisms, substances acting by the latter two mechanisms can be easily distinguished from those by the other collapse mechanisms, but the action based on the swelling / deformation mechanism and the wick / repulsion action Mechanism-based actions are not always clearly distinguishable from each other and, for practical reasons, the classification into hydrophilizing agents, outgassing systems, and swelling disintegrators is more It is suitable.

[0006] According to the detergent tablets disclosed in the prior art, the use of disintegrants is explicitly disclosed in general, and starch and its derivatives, as disintegrants belonging to various classes,
Cellulose and its derivatives, polyvinylpyrrolidone and other polymers, and the like are exemplified, but the importance of incorporating such materials is generally not discussed in detail.

[0007] EP-A-0 522 766 (Unilever) is a surfactant, builder and disintegrant (
Disclosed are tablets of a compressed granular detergent composition comprising, for example, a cellulosic disintegrant). The particles are at least partially coated with a disintegrant that acts as a binder and as a disintegrant upon dissolution of the tablet in water. According to the disclosure of the above-mentioned documents, it is generally difficult to produce a tablet that combines sufficient stability with good solubility. Generally, it is said that the particle size of the mixture to be compressed exceeds 200 μm, and the difference between the upper limit and the lower limit of the particle size is 700 μm or less.

[0008] Other documents relating to the production of detergent tablets include EP-A-0 716 144 (Unilever), which discloses tablets having an outer shell of a water-soluble material. According to the disclosure of another document, EP-A-0 711 827 (Unilever), a citrate having only limited solubility is used as one of the tablet components.

[0009] The use of a binder (especially polyethylene glycol) which optionally forms a disintegrating action is disclosed in EP-A-0 711 828 (Unilever). According to the disclosure of this document, detergent tablets are produced by tableting the granular detergent composition at a temperature between 28 ° C. and the melting point of the binder, the tableting process always being carried out at a temperature below the melting point temperature. . As is evident from the examples of this document, tablets made according to the teachings of this document show high fracture resistance when the tableting is performed at elevated temperatures.

[0010] EP-A-0 481 793 (Unilever) discloses a detergent tablet having an independent component which is separated from other components. The detergent tablets disclosed in this document contain sodium percarbonate, a substance that is separated from all other ingredients that can adversely affect stability.

According to DE 195 30 999 (Henkel), a perfume tablet for imparting fragrance to textiles in an electric washing machine is disclosed, wherein the perfume is made of starch, silicic acid, silicate, phosphorous. It is coated on a carrier material such as acid salts, zeolites, polycarboxylate polymers, polyaspartic polymers. Perfume tablets contain the perfume disclosed in this document in doses of 8-40% by weight and are used in a given way to impart a textile aroma / fragrance.

[0012] None of the above prior art documents disclose improving the solubility of detergent tablets by selectively modifying or mixing a hydrophobizing component or a disintegrant.

[0013] Accordingly, the problem to be solved by the present invention is to provide a detergent tablet which shows further improved disintegration and dissolution properties by selective incorporation of the hydrophobizing component.

SUMMARY OF THE INVENTION [0014] The present invention is directed to a compressed granular detergent detergent tablet comprising a surfactant, a builder, a cellulosic disintegrant and optionally other detergent components, wherein the detergent tablet comprises The substance provides a tablet, characterized in that it is applied to a carrier material.

[0015] According to the detergent tablets of the present invention, the problem of insufficient tablet disintegration properties due to insufficient disintegration of the cellulosic disintegrant prevents rapid access of water to all areas of the tablet. The problem can be solved by applying a hydrophobic component to the carrier so as to reduce the disintegration properties of the tablet.

[0016] The following theory is not intended to limit the present invention, but by separating the hydrophobizing component from the other components, it is easier for water to reach the interior of the tablet, It is thought that collapse is promoted. That is, the hydrophobizing substance is not widely distributed on the tablet and is not substantially evenly distributed throughout the tablet, but is localized in a defined area, whereby moisture easily reaches the inside of the tablet. be able to.

Suitable tablets are not prepared from a mixture in powder form, but rather from a mixture in at least partially compound form, ie, in the form of several granules. The primary particles of the detergent component are agglomerated into secondary particles, which are then compressed into tablets. For the present invention, it is important that the hydrophobizing component is not evenly distributed throughout the tablet, for example by spraying on granules, and the carrier is mixed with other powders or secondary agglomerates before the tableting process Applied separately to the material. Generally, in the tablet dissolution process, the manufacturing process is reversed. That is, tablets generally disintegrate first into relatively coarse particles, which then dissolve and disintegrate rapidly in each particle, so that a significant increase in surface area is essential for good solubility. Since the hydrophobizing component is applied to the carrier material, each particle of the tablet does not come into contact with the hydrophobizing substance at all. As such, tablets can disintegrate more quickly into individual particles. The particles thus formed can be rapidly dissolved in the same manner as ordinary detergent powders, even if the individual particles contain a hydrophobizing substance. The surfactant compound is
Preferably, it is used as a carrier material for the hydrophobizing substance. Such surfactant compounds may not include a hydrophobized nonionic surfactant, but may include a hydrophobized nonionic surfactant, and may be impregnated with a hydrophobizing substance, such as a fragrance. it can. According to one preferred embodiment of the present invention, a cellulosic disintegrant is used as the carrier material for the hydrophobizing substance. However, any carrier material typically used in detergents (eg zeolites, silicates, silicic acids) can, of course, be used as a carrier material for the hydrophobizing substance. According to one particularly preferred embodiment of the invention, the carrier material impregnated with the hydrophobizing substance is present in a defined area of the tablet, comprising the carrier material impregnated with the hydrophobizing substance. Present in the form of separate layers, coatings or separate inserts.

The term “hydrophobizing substance” as used herein refers to a substance that reduces the wettability of a tablet (or rather its component particles) with water. In particular, typically, paraffins and silicones, such as those used in detergents as foam control agents, or perfume oils are used as hydrophobizing substances. Examples of other hydrophobizing substances include nonionic surfactants that show a tendency to form a gel without spontaneously dissolving in water. Not all nonionic surfactants exhibit this hydrophobizing property, and it is difficult to theoretically separate hydrophobized and non-hydrophobic substances. One of ordinary skill in the art will find, without difficulty, nonionic surfactants that significantly hydrophobize the carrier material,
This hydrophobic property can be applied to the carrier material. In this connection, reference is made to the nonionic surfactant HLB. Nonionic surfactants with an HLB value less than 10 tend to exhibit more hydrophobic properties, while nonionic surfactants with an HLB value greater than 12 are considered to exhibit non-hydrophobic properties. be able to. Preferably, all nonionic surfactants can be applied to the carrier material, since it is generally difficult to theoretically predict the hydrophobizing properties of nonionic surfactants. Suitable tablets comprise, as a hydrophobizing substance, a nonionic surfactant having an HLB value of less than 10 applied to a carrier material. Application to the carrier material can be effected, for example, by spraying with a solution or a melt. However, the introduction of a non-ionic surfactant in the granulation step to form a surfactant compound with the carrier material is another suitable method for application to the carrier material.

[0019] Seiawazai Suitable Seiawazai are, for example, soaps of natural and synthetic sources including C _{18 ~ 24} fatty acid with high content. Suitable non-surfactant type foam control agents are, for example, organopolysiloxanes and also mixtures of organopolysiloxanes with optionally silanized silica or bisstearylethylenediamine. Mixtures of different antifoams, for example mixtures of silicones, paraffins and waxes, can also be used to advantage. Mixtures of paraffin and bisstearylethylenediamine are particularly preferred. Such foam control agents, when used in tablets according to the present invention, are applied to a carrier material. Suitable detergent tablets include a foam inhibitor applied to the carrier as a hydrophobizing substance.

Dyes and fragrances (perfume oils) In accordance with the present invention, dyes and fragrances are added to detergent tablets to improve the aesthetic effect formed by the product and provide consumers with the necessary laundry properties. Not only that, it is possible to provide visually and sensory products that are “typical and non-failing”. Suitable perfume oils or fragrances include the respective perfume compounds, for example esters, ethers, aldehydes, ketones, alcohols and hydrocarbon-based compounds. Representative of the ester-based flavor compounds are benzyl acetate, phenoxyethyl isobutyrate, and pt-acetate.
Butylcyclohexyl, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexyl propionate, styralyl propionate and benzyl salicylate. Examples of the ether-based perfume compounds include linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and burgeonal. Suitable ketone-based compounds are ionone, α-isomethylionone and methylseryl ketone. Suitable alcohol compounds include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. Examples of hydrocarbon compounds are, in particular, terpenes such as limonene and pinene. Preferably, however, a mixture of different fragrances is used, which together produce an attractive aroma. Such balms can include natural fragrance mixtures, such as those obtained from vegetable sources, including pine, citrus,
Examples are jasmine, patchouli, rose or ylang-ylang oil. Preferred are clealey oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon oil, lime-blossom oil, juniper berry oil, vetiver oil, fragrance oil, galvanum oil, labodanum oil, orange brossam oil , Neroli oil, orange peel oil and sandalwood oil.

The detergent tablets of the present invention usually contain less than 0.01% by weight of the dye, and the fragrance / fragrance can constitute as much as 2% by weight of the total composition.

[0022] Dyes used in detergents can be distributed throughout the tablet as they generally dissolve readily in water and are not absorbed by the textile to be treated. According to the invention, a fragrance exhibiting high hydrophobizing properties should be applied to the carrier material. Suitable detergent tablets contain a fragrance applied to the carrier material as a hydrophobizing substance.

Disintegrant As used herein, the term "disintegrant" refers to a cellulosic disintegrant which, according to the present invention, has a significantly improved disintegration effect by being present in a defined area separated from the hydrophobizing substance. I do. Pure cellulose is represented by the empirical formula: (C ₆ H ₁₀ O ₅ ) _n , formally called cellobiose β-1,4-polyacetal, and is composed of two glucose molecules. Suitable celluloses are composed of about 500 to 5,000 glucose units, and thus have an average molecular weight of 50,000 to 500,000. Cellulose can agglomerate by granulation with other components to form secondary particles of larger size. Primary particle size of cellulose before granulation is less than 100 μm,
Preferably it is less than 70 μm, most preferably less than 50 μm. According to the present invention, a cellulose derivative obtained from a cellulose by a polymerization analog reaction can also be 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. As the cellulose derivatives of this group, alkali metal cellulose, carboxymethyl cellulose (CM
C), 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 microcrystalline cellulose can be used as another cellulosic disintegrant or as part of a cellulosic disintegrant. This microcrystalline cellulose can only attack the amorphous region and completely dissolve the amorphous, while partially hydrolyzing the cellulose under conditions that do not change the crystalline region (about 70%) (cellulose About 30 of total weight
%). 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 into particles having an average particle size of, for example, 200 μm.

As used herein, the term “cellulosic disintegrant” also refers to a disintegrant that includes a mixture of cellulose or a derivative thereof and another disintegrant (provided that the cellulose or a derivative thereof is Not more than 50% by weight based on the agent). By using such a disintegrant and separating the hydrophobized substance according to the present invention, a distinct improvement in the action of the disintegrant is obtained. Suitable swellable, water-insoluble disintegrants which can be used in mixtures with cellulose or derivatives thereof include, in particular, tens to hundreds (thousands) gm
It is a polymer material having a molecular weight of ol- ¹ . In addition to synthetic polymers such as polyvinylpyrrolidone and polyvinyl alcohol, natural and chemically modified biopolymers, such as those selected from the group consisting of alginate, starch and derivatives thereof,
Particularly preferred.

The detergent tablets of the present invention may suitably include other representative detergent ingredients, including surfactants, builders, bleaches, bleach activators, enzymes, optical brighteners and the like. Other auxiliaries and additives are mentioned. Such materials are described in more detail below.

[0028] Anionic, cationic and / or amphoteric surfactants can be used in the detergent tablets of the present invention. From the viewpoint of their properties, it is preferable to use a mixture of an anionic surfactant and a nonionic surfactant, and in this mixture, the proportion content of the anionic surfactant is higher than that of the nonionic surfactant. Should also be higher. The total surfactant content in the detergent tablet is about 5-60% by weight, based on the weight of the detergent tablet, with a surfactant content above 15% by weight being preferred.

Anionic surfactants Suitable anionic surfactants are, for example, those of the sulphonate type and of the sulphate type. Suitable surfactants of the sulfonate type are preferably C ₉ ~ C _{1 3} alkylbenzene sulfonate, olefin sulfonate (i.e., a mixture of Arukensu sulfonic acid salt and hydroxy alkane sulfonates), and double sulfonates (e.g., using a C ₁₂ -C ₁₈ monoolefins having a double bond within the terminal,
This is obtained by sulfonating this with sulfur trioxide gas and then subjecting the resulting sulfonated product to alkali or acid hydrolysis.) Other suitable sulphonate-type surfactants are alkane sulphonates obtained from C12-C18 alkanes, for example by sulfochlorinating or sulphooxidizing alkanes and then hydrolyzing or neutralizing them. Obtainable. Also suitable are esters of α-sulfo fatty acids (ester sulfonates), such as α-sulfonated methyl esters of hydrogenated coconut oil, palm kernel oil or tallow fatty acids.

Another suitable anionic surfactant is a glycerol ester of a sulfonated fatty acid. 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 sulfonated fatty acid glycerol esters, caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, such as stearic acid or behenic acid, sulfonated products of C ₆ -C ₂₂ saturated fatty acids .

Suitable alkyl (alkenyl) sulfates are C ₂₁ -C ₁₈ fatty alcohols (eg,
Coconut oil fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol) or C ₁₀ -C ₂₀ alkali metal salts, especially sodium salts of the oxo alcohol and sulfuric acid semiesters of secondary alcohols with the same chain length. 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 preferred from the viewpoint of the washing process. Other suitable anionic surfactants are 2,3-alkyl sulfates, which can be prepared, for example, by the methods described in US Pat. No. 3,234,258 or US Pat. No. 5,075,041 and are commercially available under the trademark DAN (a product of Shell Oil Company). I have.

[0032] Sulfuric acid monoesters of linear or branched C ₇ -C ₂₁ alcohols, such as sulfuric acid monoesters of 2-methyl branched C ₉ -C ₁₁ alcohols, ethoxylated with 1 to 6 mol of ethylene oxide (EO) (EO average addition mol number 3.5) or C ₁₂ -C ₁₈ fatty alcohols sulfuric acid monoester (EO average addition mol number 1-4) are also suitable. Such surfactants have a high foaming capacity and are therefore only used in detergents in relatively small amounts, for example in amounts of 1 to 5% by weight.

Another suitable anionic surfactant is a salt of an alkyl sulfosuccinic acid, which compound is known as a sulfosuccinate or sulfosuccinate, and comprises a sulfosuccinic acid and an alcohol (preferably a fatty acid). As monoesters and / or diesters with alcohols, especially ethoxylated fatty alcohols). Suitable sulfosuccinates include C ₈ -C ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates comprise fatty alcohol residues obtained 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 and their salts, preferably containing from 8 to 18 carbon atoms in the alkyl (alkenyl) chain, can also be used.

Other suitable anionic surfactants are, in particular, soaps. Suitable soaps are obtained from soaps of saturated fatty acids, for example salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and especially natural fatty acids, for example coconut oil, palm kernel oil or tallow fatty acid. 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 may suitably be present in the form of a sodium or potassium salt, in particular in the form of a sodium salt.

Suitable nonionic surfactants are alkoxylated, preferably ethoxylated, especially primary alcohols having 8 to 18 carbon atoms (an average of 1 to 12 mol of ethylene oxide (EO) per mol of alcohol). The alcohol residue may be linear or methyl-branched (position 2), and may contain linear and methyl-branched groups in a mixture typically present in oxo alcohol residues. It can be included in the form. However,
Alcohol ethoxylates containing straight-chain residues of natural alcohols having 12 to 18 carbon atoms, such as coconut oil, palm oil, tallow or oleyl alcohol, containing an average of 2 to 8 mol EO per mol of alcohol, especially It is suitable. Suitable ethoxylated alcohols, for example C ₁₂ -C ₁₄ alcohol (3EO or 4EO containing), C ₉ -C ₁₁ alcohol (7 EO content), C ₁₃ -C ₁₅ alcohol (3EO, 5 EO, 7 EO or 8EO containing) , C ₁₂ -C _{1 8} alcohol (3EO, 5 EO or 7EO containing) and mixtures thereof, for example mixtures of C ₁₂ -C ₁₄ alcohol (3EO containing) and C ₁₂ -C ₁₈ alcohol (5 EO content), and the like . The degree of ethoxylation described above can be indicated by a statistical average and may be an integer or a fraction for a particular product. Suitable alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylate, NRE). In addition to the above nonionic surfactants, fatty alcohols containing more than 12 mol of EO can also be used, such as tallow alcohols containing 14EO, 25EO, 30EO or 40EO.

In addition, the formula: RO (G) _X [wherein R is an aliphatic group of a primary, straight-chain or methyl-branched chain, especially a 2-methyl-branched chain (C 8-22, preferably 12 ~ 18), G is an alkylglycoside represented by a glucose unit having 5 to 6 carbon atoms, preferably glucose] can be used as a further nonionic surfactant. The degree of oligomerization x is
It means the distribution of mono-oligoglycosides and oligoglycosides, and is 1 to 10, preferably 1.2 to 4.

Another class of suitable nonionic surfactants that can be used alone or in combination with other nonionic surfactants is alkoxylation, preferably ethoxylation or ethoxylation. And propoxylated fatty acid alkyl esters (preferably containing 1 to 4 carbon atoms in the alkyl chain), especially fatty acid methyl esters, such as those described in JP 58/217598, or WO-A- 90
/ 13533.

Non-ionic surfactants of the amine oxide type, such as N-coconut alkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and fatty acid alkanolamide-type surfactants Activators are also suitable. The dose of such nonionic surfactant is preferably no more than the dose of ethoxylated fatty alcohol, and is preferably less than half.

[0040] Other suitable surfactants are of formula (I):

Embedded image Is a polyhydroxy fatty acid amide represented by In the formula, RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ¹ is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, and [Z] is 3 to 10 carbon atoms / 3 to 10 hydroxyl groups. Is a linear or branched polyhydroxyalkyl group. Polyhydroxy fatty acid amides are known substances, which are usually produced by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine, followed by an acylation reaction with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. Let me get it.

The group of polyhydroxy fatty acid amides has the formula (II):

Embedded image Wherein R is a linear or branched alkyl or alkenyl group having 7 to 12 carbon atoms, and R ¹ is a linear, branched or cyclic alkyl group or aryl group having 2 to 8 carbon atoms. R ² is a linear, branched or cyclic alkyl or aryl or hydroxyalkyl group having 1 to 8 carbon atoms, preferably a C _1-4 alkyl group or a phenyl group, and [Z] is an alkyl It is a linear polyhydroxyalkyl group in which at least two hydroxyl groups are substituted in the chain, or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof. ] The compound shown by these is also included.

[Z] is preferably obtained by reductive amination of a reducing sugar, and examples of the reducing sugar include glucose, fructose, maltose, lactose, galactose, mannose and xylose. The N-alkoxy or N-aryloxy-substituted compound is prepared by reacting the required polyhydroxy fatty acid amide with a fatty acid methyl ester (in the presence of an alkoxide catalyst, for example, by the method described in International Patent Application WO-A-95 / 07331). ).

As mentioned above, the nonionic surfactant is preferably not distributed throughout the tablet,
Alternatively, it applies to a carrier, for example a disintegrant. The non-hydrophobated nonionic surfactant can be used in other compounds or areas, but preferably the nonionic surfactant alone is distributed throughout the tablet.

Builders Builders which may be present in the detergent tablets of the invention are, in particular, silicates, aluminum silicates (especially zeolites), carbonates, salts of organic di- and polycarboxylic acids, and mixtures of these builders. .

Suitable crystalline layered sodium silicates have the formula: Na ₂ MSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen and x is a number from 1.9 to 4. Where y is a number from 0 to 20, and a preferred value for x is 2, 3 or 4. Such crystalline layered silicates 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 preferred are both β- and δ-sodium silicates represented by the formula: Na ₂ Si ₂ O ₅ .yH ₂ O, and β-sodium silicate is, for example, an international patent application WO-A-91 / 0817
It can be obtained by the method described in 1.

Other useful builders include a factor (ratio of Na ₂ O: SiO ₂ ) of 1: 2 to 1: 3.3, preferably 1:
Amorphous sodium silicate having a ratio of 2: 1 to 2.8, more preferably 1: 2 to 1: 2.6, which dissolves with a delay and exhibits multiple wash cycle characteristics. For conventional amorphous sodium silicate, delayed dissolution can be obtained in various ways, such as by surface treatment, compounding treatment, compression or overdrying. The term "amorphous" as used herein refers to X-ray amorphous. That is, the silicate is X
In a line diffraction experiment, it did not show any sharp X-ray reflections typical of crystalline materials,
At best, they show only one or more maxima of scattered X-rays with a range of diffraction angles of several degrees. 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 product is between 10 and several hundred nm, up to 50 nm
Is interpreted to mean having a crystallite area of dimensions up to
Particularly, those having a maximum of 20 nm are suitable. The so-called X-ray amorphous silicates exhibiting dissolution characteristics that are slower than ordinary water glass are described in DE-A-44 00 024 (Henkel
)It is described in. Compressed amorphous silicate, compounded amorphous silicate and overdried X
Linear amorphous silicates are particularly preferred.

The microcrystalline synthetic zeolite containing bound water used according to the invention is preferably zeolite A and / or zeolite P. As zeolite P, for example, Zeolite MAP (trademark) (Crosfield) is used. However, zeolites X and mixtures of zeolites A, X and / or P are also suitable. The zeolites may be used in the form of a spray-dried powder or in the form of a wet stabilized suspension which is wet after production. If the zeolite is used in the form of a suspension, the suspension may be used as a stabilizer in small amounts of nonionic surfactants, such as 1-3% by weight, based on zeolite, of ethoxylated _C12-18 fatty alcohol. (ethylene oxide groups 2-5), ethoxylated C _{12 ~ 1 4} fatty alcohols (ethylene oxide groups 4-5), or may contain ethoxylated Isotorideka Nord. Suitable zeolites have an average particle size of less than 10 μm (determined by volume distribution, Coulter counter method) and preferably contain 18 to 22% by weight of bound water, more preferably 20 to 22% by weight.

Known phosphates can, of course, be used as builders if they are ecologically acceptable. Suitable phosphate builders are the sodium salts of orthophosphoric acid, pyrophosphoric acid and especially tripolyphosphoric acid.

Useful organic builders, 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.

If desired, the abovementioned builders can be used as carriers for hydrophobizing substances. However, cellulosic disintegrants are preferably used as carriers for such substances.

Bleaching agents, bleach activators and bleaching catalysts Among the compounds which produce hydrogen peroxide (H ₂ O ₂ ) in water, sodium perborate tetrahydrate and sodium perborate monohydrate But of particular importance. 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.

When performing washing at a temperature of 60 ° C. or lower, a bleach activator can be introduced as component (b) itself or as a single component in order to obtain an improved bleaching action. The bleach activator may be a compound that forms an aliphatic peroxocarboxylic acid, preferably containing 1 to 10 carbon atoms, preferably 2 to 4 carbon atoms, and / or perhydrogenated optionally substituted perbenzoic acid. It may be a compound formed under decomposition (perhydrolysis) conditions. Materials containing O- and / or N-acyl groups with the above number of carbon atoms and / or optionally substituted benzoyl groups are preferred.
Suitable bleach activators include polyacrylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5- Triazine (DADHT), acylated glycoluril, especially tetraacetyl glycoluril (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.

In addition to or instead of the usual bleach activators, so-called bleach catalysts can be introduced into the detergent tablets according to the invention. Bleaching catalysts are salts of transition metals or complexes of transition metals which enhance bleaching, for example manganese-, iron-, cobalt-, ruthenium- or molybdenum-selenium complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes (including nitrogen-containing tripodal ligands) and cobalt-, iron-, copper- and ruthenium-amine complexes may also be used as bleach catalysts. it can.

In addition to the soil release agent , the detergent tablet of the present invention may contain a component (so-called soil release agent) that promotes the removal of fats and oils from textiles during washing. This accelerating effect is particularly evident when textiles already containing such a fat-soluble component and already repeatedly washed with the detergent tablets of the present invention become soiled. Suitable oil dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose (15-30% by weight of methoxy groups and 1-1
5% by weight of hydroxypropyl groups, based on the amount of nonionic cellulose ether), and known polymers of phthalic acid and / or terephthalic acid, especially polymers of ethylene terephthalate and / or polyethylene glycol terephthalate and their anionic properties And / or non-ionic modified derivatives. Of these, the sulphonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Enzymes Suitable enzymes are those selected from the group consisting of proteolytic enzymes, lipolytic enzymes, starch hydrolases, cellulases and mixtures thereof. For example, Bacillus subtilis, Bacillus licheniformis (Bacillus)
licheniformis) and Streptomyces griseus
) Are particularly preferred, such as enzymes obtained from bacterial strains or fungi. Subtilisin-based proteolytic enzymes are preferably used and Bacillus lentus (Bacillus lens) is used.
tus) are particularly preferred. An enzyme mixture, for example, a mixture of proteolytic enzyme and starch hydrolase or a mixture of proteolytic enzyme and lipolytic enzyme or a mixture of proteolytic enzyme and cellulase or a mixture of cellulase and lipolytic enzyme or proteolytic enzyme. Mixtures of amylolytic enzymes and lipolytic enzymes or mixtures of proteolytic enzymes, lipolytic enzymes and cellulases, especially cellulase-containing mixtures, are particularly suitable. Peroxidases (peroxidases) and oxidases (oxidases) have also proved to be suitable in some cases. The enzyme is absorbed on the support and / or encapsulated in a shell-forming substance, thereby protecting the enzyme from premature degradation. The proportion content of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1-5% by weight, preferably about 0.1-2% by weight.

Fluorescent Whitening Agent The detergent 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 salt of a similar compound containing a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group. Substituted diphenylstyryl-based brighteners such as 4,4'-bis- (2-sulfostyryl) diphenyl, 4,4'-bis- (4-chloro-3-sulfostyryl) diphenyl or 4- (4-chloro Styryl) -4 '-(2-sulfostyryl) diphenyl can also be used. Mixtures of the above optical brighteners can also be used.

According to a preferred embodiment of the present invention, the granular detergent composition is compressed at a temperature of less than 30 ° C. and a pressure of less than 15 N / cm ² . The actual production of the detergent tablet of the present invention is carried out as follows. First, the components, which may be completely or partially pre-granulated, are mixed, and the resulting premix is then converted into tablets using known methods, especially by tableting. To make the tablets of the present invention, the premix is compressed between two punches in a die to form a solid compact. This process (hereinafter referred to as tableting for simplicity) comprises four steps: weighing, compression (elastic deformation), plastic deformation and extrusion.

The premix is first introduced into a die. The filling level, and thus the weight and shape of the formed tablet, is determined by the position of the lower punch and the shape of the die. Even at high tablet throughputs, uniform metering is preferably achieved by metering the compound volume. As the tableting process proceeds, the top punch comes into contact with the premix and continues descending to the bottom 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 and form a tablet, which starts at a predetermined position of the top punch (and thus at a predetermined pressure on the premix). Depending on the physical properties of the premix, its constituent particles are partially milled and the premix is sintered at high pressure. As the tableting speed increases (i.e., at high throughput), the elastic deformation phase becomes shorter and shorter, so that the formed tablets may have more or less large pores. In the final step of the tableting process, the tablets are forcibly ejected from the die by a bottom punch and conveyed by a subsequent conveyor. 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 top punch used to build pressure, but also the bottom punch moves toward the top punch during the tableting process, and the top punch compresses downward. For small production volumes, an eccentric press for tablets is preferably employed. In this press, a punch is fixed to an eccentric disk, and the starch is placed around a rotating shaft at a predetermined speed.
Such a punch movement is comparable to the operation of a normal four-stroke engine. Compression can be performed with a top punch and a bottom punch, but several punches can be fixed on 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.

[0060] Due to the higher throughput, rotary tablet presses are commonly used. In rotary tablet presses, a relatively large number of dies are circular and placed on a so-called die table. The number of dies varies between 6 and 55, depending on the model, but larger numbers are also commercially available. The top and bottom punches are in communication with each die on a die table, and again, the tableting pressure is effectively formed by both the punches, not just the top or bottom punches. The die table and punch move about a common vertical axis, and the punch is carried by curved guide rails to filling, compression, plastic deformation and extrusion positions. Particularly in locations where a die up or down movement is required (filling, compression, extrusion), to a significant extent, such curved guide rails are provided by additional push-down members, push-down rails and extrusion paths. Supported. The die is filled from a fixed feeding device (so-called filling shoe), which is connected to a storage container for the compound. The pressure applied to the compound can be adjusted independently by means of top and bottom punches, the pressure being formed by the rotation of the shank head of the punch past an adjustable pressure roller.

For increased throughput, the rotary press can also be equipped with two filling shoes such that only half of the circle is required for the tablet manufacturing operation. For the manufacture of bilayer or multilayer tablets, several filling shoes are arranged one behind the other, and the lightly compressed first layer is not extruded before further filling. Certain suitable process controls, jackets and "bovine eyes" -like tablets, which have a structure similar to onion skin, can be formed in this manner. In the case of "bovine eyes" -like tablets, the upper surface of the core or rather the core layer remains visible because it is not coated. The rotary tablet press can also have single or multiple punches, so that, for example, an outer circle of 50 holes and an inner circle of 35 holes can be used simultaneously for tableting. Modern rotary tablet presses have a throughput of over one million tablets per hour.

Suitable tableting machines can be obtained, for example, from the following companies: Apparate
bau Holzwarth GbR, Asperg, Wihelm Fette GmbH, Schwarzenbec, Hofer GmbH,
Weil, KIKIAN, Cologne, KOMAGE, Kell am See, KORSCH PRESS GmbH, Berlin, M
apag Maschinenbau AG, Bern (Switzerland) and Couroy NV Halle (BE / LU).
An example of a particularly suitable tablet press is the model HPF 630 hydraulic (hydraulic) dual pressure press (manufactured by LAEIS, D). Tablets can be manufactured in a predetermined form and in predetermined dimensions. Suitable forms may be virtually any easily manipulable form, for example slabs, bars, cubes, flat plates and corresponding forms having flat sides, especially round or oval cross sections. It is cylindrical. This last embodiment includes from tablet form to compact cylindrical form with a height / diameter ratio of more than one.

Partial compacts (press compacts) can be formed as separate components corresponding to a given detergent dose. However, it is possible to form a shaped body in which several units are combined in a single shaped body, in which case each split unit can be easily separated, in particular from a predetermined weak spot setting. To use laundry detergent in a standard European horizontal washing machine,
Advantageously, the split mouldings are manufactured as cylindrical or flat tablets, preferably for tablets, the diameter / height ratio is from about 0.5: 2 to 2: 0.5. Commercially employed hydraulic, eccentric and rotary presses are particularly suitable for the production of such compacts.

Another aspect of the three-dimensional form of the tablet according to the invention is that its dimensions are adapted to the distribution chamber of a commercial household washing machine, whereby the tablet can be directly, ie, using a weighing aid. Instead, it can be introduced into a dispensing chamber (detergent charging chamber) where the tablets dissolve upon contact with water. However, it is of course possible with the present invention to easily use the cleaning tablets with the aid of a weighing aid.

Other preferred tablets that can be manufactured have a plate-like or slab-like structure with alternating thick and thin portions and short and thin portions, so that the individual portions are at predetermined weak points ( This "bar" (corresponding to a short, thin section) can be cut off and introduced into the machine. Also, the principle of this "bar" can be embodied in other geometries, for example, vertical triangles which are connected to each other only on one of their longitudinal sides.

However, in other possible embodiments, the various components are not compressed and form a single tablet, and the resulting tablet instead comprises several layers, ie at least two layers.
These various layers have different dissolution rates. This can provide tablets with favorable performance characteristics. For example, when a tablet contains components that adversely affect each other, one component may be miscible in the faster dissolving layer because the first component may have already reacted by the time the second component dissolves. While you can
Other components can be incorporated in the slower dissolved layer. The various layers of the tablet can be arranged in a stacked form, wherein the inner layer can dissolve at the edge of the tablet before the outer layer has completely dissolved. However, alternatively, the inner layer can be completely surrounded by a further outer layer so as to prevent premature dissolution of the components of the inner layer.

In another preferred embodiment of the invention, the tablet consists of at least three layers (ie two outer layers and at least one inner layer) and the peroxy bleach is present in at least one of the inner layers, The two cover layers in the case of a stack-like (stack-like) tablet and the outermost layer in the case of an envelope-like tablet are free of peroxy bleach. In another possible embodiment, the peroxy bleach and bleach activator or bleach catalyst and / or enzyme can be spatially separated from each other in one and the same tablet. Such multilayer tablets can be used not only by passing them through a dispensing chamber where they are added to the washing liquid, but also by passing them through a metering unit, as well as fiberizing the tablets without any danger, for example spotting with bleach etc. It has the advantage that it can be introduced into the washing machine in direct contact with the product.

A similar effect can also be obtained by coating the individual components of the cleaning composition to be compressed or the whole tablet. For this purpose, the tablets to be coated may be sprayed on, for example, by aqueous solutions or emulsions, or the coating may be obtained by a method known as melt coating.

After compression, the washed tablets have a high stability. The puncture resistance of cylindrical tablets can be measured from diametral fracture stress. It has the following formula:

Σ = 2P πDt [where σ is the breaking stress of the diameter in Pa (DFS, Pa), P is the force (N) that causes the tablet to break when pressed, and D is the tablet Is the diameter (m), and t is its height. ] Can be measured.

EXAMPLES Three detergent tablets Examples 1, 2 and 3 (having the same composition as shown in Table 1) were prepared by tableting a granular detergent composition. Examples 1 and 2 correspond to the invention,
Comparative Example 3 is a tablet for comparison.

[0071]

Table 1 Composition of detergent tablets (% by weight)

[0072]

Table 2 Composition of surfactant granules (% by weight)

In Tablet 1 of the present invention, the flavor was added separately from the other ingredients in the form of a flavor / cellulose compound. In tablet 2 of the present invention, the fragrance was applied to the surfactant compound separately from the other ingredients, and after mixing with the remaining ingredients, the resulting mixture was compressed into tablets. In the tablet of Comparative Example 3, the flavor was distributed evenly throughout the tablet by spraying the flavor onto the tableted mixture.

Tablet hardness was measured by deforming the tablet until it broke. Force was applied to the side of the tablet and measured the maximum force that the tablet could withstand.

To determine the disintegration properties of the tablets, the tablets were placed in a glass beaker (600 ml water,
At a temperature of 30 ° C.) and the time required for the tablet to completely disintegrate without mechanical stress was measured.

For the detergent dispensing test, three 40 g tablets were placed in the detergent input compartment of a washing machine. After the detergent charging stage, the residue in the detergent charging chamber was dried and weighed. The results are shown in Table 3 below.

[Table 3] Detergent tablets (physical property data)

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hans-Friedrich Kluse, Federal Republic of Germany Day 41352 Korschen Bloich, Am Hallenbad 44 (72) Inventor Fret Shamville Federal Republic of Germany Day 40789 Monheim, Niederstrasse 96 No. F term (reference) 4H003 AB03 AB18 AB27 AC08 BA01 BA09 DA01 DA03 DA17 EA15 EA16 EA28 EB09 EB16 EB32 EB42 ED02 EE05 FA32

Claims (8)

[Claims] 1. A compressed granular detergent detergent tablet comprising a surfactant, a builder, a cellulosic disintegrant and optionally other detergent components, wherein all the hydrophobizing substances are applied to the carrier material. Tablets. 2. The tablet according to claim 1, wherein a surfactant compound is used as the carrier material. 3. The tablet according to claim 1, wherein a cellulosic disintegrant is used as the carrier material. 4. The tablet according to claim 1, which comprises a nonionic surfactant applied to the carrier material as a hydrophobizing substance. 5. An antifoaming agent applied to a carrier material as a hydrophobizing substance.
The tablet according to any one of 1 to 4. 6. The tablet according to claim 1, which comprises a flavoring agent applied to the carrier material as a hydrophobizing substance. 7. A tablet according to any of claims 1 to 6, wherein the hydrophobizing substance applied to the carrier material is a separate layer, coating or a separate insert. 8. The tablet according to claim 1, wherein the hydrophobizing substance applied to the carrier material is granulated with other detergent components to form a compound before the tableting process.