JPH06509369A - Method for making high bulk density detergents with improved dissolution rates - Google Patents

Abstract

The invention concerns the production of high-bulk-density solid washing and cleaning agents with improved dissolving speed, produced by mixing solid and liquid washing-agent raw materials and, at the same time or subsequently, modifying the form of the particles in the mixture and, if required, drying it. Anionic surfactants, builders and alkalisation agents are added as the solid components, and non-anionic surfactants as the liquid components. To improve the dissolution behaviour and to facilitate mixing, the liquid non-ionic surfactants are used intimately mixed with a structure breaker in the ratio by wt. of non-ionic surfactant: structure-breaker of 10:1 to 1:2. Preferred structure-breakers are poly(ethylene glycol) or poly(propylene glycol) with a relative molecular weight between 200 and 12,000, addition products produced by reacting about 20 to 80 moles of ethylene oxide with 1 mole of an aliphatic alcohol with substantially 8 to 20 carbon atoms, and mixtures thereof.

Description

[Detailed description of the invention] Process for making high bulk density detergents with improved dissolution rate The present invention relates to a process for making solid detergents. and also concerning detergents obtained by this process which exhibit improved dissolution rates, especially at low temperatures. do.

High bulk density solid detergents (i.e. detergents with a bulk density of 500g// or more) are The density and resulting surface area are relatively small, especially at low temperatures (approximately 15 ~60°C), for example, compared to a comparative detergent formulation with a bulk density of only 300 g/l. Solving speed is often slow.

Also, some surfactants have a It is also known that some substances form gel phases.

By adding an ethoxylated alkanediol, the gel is reduced when diluted with water. Being able to reduce the viscosity of the ethoxylated fatty alcohols that form is known from European Patent Application No. 7049.

European Patent No. 208534 discloses that an aqueous suspension that is spray-dried is made of polyacrylate. , especially polyacrylates, polyethylene glycols and nonionic surfactants. spray with improved dissolution behavior due to containing a mixture of Mist-dried granules are described.

International patent application W091102047 describes a method for producing compressed granules for use in detergents. Are listed. In this process, after adding plasticizers and/or lubricants, high pressure (25-200 bar), the homogeneous compound is extruded into strands. This patent application According to Ru. The plasticizers and/or lubricants used have relatively high boiling points and, if desired, Or polyethoxylated alcohol, polyalkoxy, which flows even at a certain high temperature. contain limited amounts of auxiliary fluids, including Can be done. However, by using a certain amount of auxiliary liquid, dissolution of compressed granules can be achieved. It was not clear that behavior could reliably be affected.

When detergents are used in machines, a reduction in detergent dissolution rate is not a significant problem. However, if the detergent is to be used manually, e.g. in a hand washing machine, , not accepted by consumers.

Therefore, the problem of the present invention is to use ethoxylated alcohol as a nonionic surfactant. A high bulk density solid detergent containing typical formulations comprising: The object of the present invention was to provide a high bulk density solid detergent having an improved dissolution rate at temperatures of .

By the way, to my surprise, during the manufacturing process used to manufacture detergent, nonionic Addition of some form of liquid ethoxylated alcohol used as a surfactant results in that the dissolution rate of high bulk density solid detergents of typical compositions can be improved; was found.

Therefore, the present invention provides solid and liquid detergent raw materials with anionic compositions that are used as solid components. surfactants, builders and alkalizing agents, and additives used as liquid components. Combined with the ionic surfactant or after granulation if desired after drying. A method for producing high bulk density solid detergents by improving dissolution behavior and increasing capacity. Contains a structural decomposition agent for easy combination with liquid nonionic surfactants. liquid nonionic interface in a homogeneous mixture in which the weight ratio of decomposers is 10=1 to 1:2. The present invention relates to a method for producing a high bulk density solid detergent, characterized in that it uses an activator.

Liquid nonionic surfactants are ethoxylated fatty alcohols containing 8 to 20 carbon atoms. Average of 1-15 mol of ethylene oxide per coal and alcohol IIIOl In particular, primary alcohols and alkaline alcohols preferably containing from 9 to 18 carbon atoms. Derived from an average of 1 to 12 IIlO1 of ethylene oxide per mol of coal It is preferable that the alcohol group is linear or 2-methyl branched. or mixed as is normally present in oxoalcohol groups. These may include straight chain and methyl branched groups. But for example , derived from coconut oil fatty alcohol, beef tallow fatty alcohol or oleyl alcohol Linear alcohol residues of natural origin containing 12 to 18 carbon atoms are particularly preferred. Delicious. The above ethoxylation degree is a statistical average value, and for each product, It may be a number or a fraction. Preferred alcohol ethoxylates is a narrow range of homolog distributions. w range ethoxylates) N RE). Average 2-8 Alcohol ethoxylates containing ethylene oxide groups are particularly preferred. preferred Examples of ethoxylated alcohols include C-11 alcohol and 7-ethylene alcohol. oxide (EO), C15-+s oxo alcohol, 3 ethylene oxide, 5 ethylene oxide lene oxide or 7 ethylene oxide, especially C12-14 alcohol 3 Ethylene oxide or 4 ethylene oxide, C12-14 alcohol 3-ethyl A mixture of ren oxide and CD-l11 alcohol/5 ethylene oxide. Like C12-11! Alcohol/3 ethylene oxide, 5 ethylene oxide or 7 ethylene oxide and mixtures thereof.

Suitable destructuring agents are hydrophilic and compatible with many solid and liquid substances that dissolve or disperse in water. Either of both body substances. Suitable structural decomposition agents include, for example, 2 to 6 Lower polyalcohols derived from linear or branched glycols containing carbon atoms Kylene glycol, preferably polyethylene glycol or polypropylene glycol pyrene glycols, which have a relative molecular weight of 200 to 12,000 . Particularly preferred are polyethylene glycols having a relative molecular weight of 200 to 4,000. liquid polyethylene with a relative molecular weight of up to 2.000, especially from 200 to 600. Len glycol shows particularly advantageous properties.

Also lower polyalkylene glycol ethers, especially polyethylene glycol and sulfates, especially disulfates, of 1,2-polypropylene glycol is also appropriate. Of these, 600 to 6,000. Especially 1,000~4° Polyethylene glycol and polypropylene glycol with a relative molecular weight of 000 Sulfates and/or disulfates derived from kohl are particularly suitable. Ru. Disulfates are commonly known as alcoholic compounds due to the presence of trace amounts of water. Produced from polyglycol ethers that can be formed by xylation.

Other suitable destructuring agents include lower polyalkylene glycol ether monosulfates. Consisting of water-soluble salts of fosuccinate and/or disulfosuccinate. this In this regard, the polyethylene glycol ether and the polypropylene glycol ether Cole ether compounds are particularly important compounds, with 600 to 6,000, especially Polyglycol ether sulfur having a relative molecular weight of 1,000 to 4,000 Particularly preferred are fosuccinate and disulfosuccinate.

Anionically modified polyalkylene glycol ether used as a structural decomposition agent Any salt may be used, but preferably an alkali metal salt (especially a sodium salt). ammonium salts and/or organic amines (e.g. For example, salts of triethanolamine) are suitable. The most important salt to apply is polyethylene glycol and polypropylene glycol sulfate, Sodium disulfate, sulfosuccinate and disulfosuccinate salt and potassium salt.

In a preferred embodiment, polyalkylene glycol ether and anionic Mixtures with their modified derivatives are used in any ratio. Polyalkyre Sulfosuccines of glycol ethers and polyalkylene glycol ethers Particular preference is given to mixtures with esters and/or disulfosuccinates. But also , polyalkylene glycol ethers and corresponding sulfates and/or or mixtures with disulfates, as well as polyalkylene glycol ethers. The corresponding sulfate and/or disulfate and the corresponding sulfonate Mixtures of succinates and/or sulfosuccinates are also suitable.

Other suitable and preferred destructuring agents for use in the present invention include the basic 1 This is about 20-80 per aliphatic alcohol IIIOl containing 8-20 carbon atoms. The ethylene oxide adduct of IIIOl is mentioned, which is a long-established detergent. It is a combination drug.

Particularly important are 20~(3Qmol, especially 25~45mol). Tyrene oxide and primary alcohols (e.g. coconut oil fatty alcohol or beef tallow) adducts with fatty alcohols), adducts with oleyl alcohol, oxoalcohols or primary alkyl compounds containing 8 to 18 carbon atoms, preferably 12 to 18 carbon atoms. Examples include additions to call. Weight retention derived from highly ethoxylated alcohols Examples of preferred structural decomposition agents include beef tallow fatty alcohol, 30 ethylene oxy and tallow fatty alcohol/40 ethylene oxide. Also high school Mixtures containing toxylated alcohols (e.g. beef tallow fatty alcohol 40 ethylene) mixture of carbon oxide and water, or tallow fatty alcohol/40 ethylene oxide and 200~2. with polyethylene glycol having a relative molecular weight of 0.00. It is also preferred to use mixtures).

Other suitable destructuring agents include 8 to 18 carbon atoms and 4 to 4 to 1 mol of diol. 15moj! internal vicinal ethoxylation, with a carbon chain of ethylene oxide It is an alkanediol or an alkane-1,2-diol. Alkanediol Of the two hydroxyl groups (OH), only one or both hydroxyl groups can be used. Can be ethoxylated.

Modified nonionic surfactants containing acid end groups are also suitable destructuring agents.

The nonionic surfactant has one hydroxyl group substituted with a group containing a carboxyl group. nonionic surfactants, especially fatty alcohols. Therefore, the acid root is the terminal Nonionic surfactants include nonionic surfactants and polycarboxylic acids or anhydrous polymers. Includes esters or partial esters with recarboxylic acids. No. with an acid root at its end Examples of ionic surfactants include the known polyether carboxylic acids, and C11 -1m alcohol and succinic anhydride, maleic anhydride, maleic acid or citric acid Examples include esters or semi-esters of

Other suitable destructuring agents have the general formula R　O　(C　H　　　C　H　2 ) n H [wherein R is C.

-8 group, or n is a number from 1 to 8] Consists of kill ether. Examples of these additives include ethylene glycol Monoethyl ether and diethylene glycol monobutyl ether are mentioned. Ru.

In principle, water is also a suitable destructuring agent. However, in most cases, Keep the free water content of the detergent as low as possible so that active substances are present in high concentrations It is desirable to use water as a structural decomposition agent, so . Anhydrous formulations that can combine with free water (e.g. anhydrous soda or less Zeolite (some of which does not contain water) is often used for these purposes. stomach. During storage, detergents lose water under the internal drying effect they undergo; When used after storage for a period of time, the substantial effects of improved dissolution rate can be fully exploited. may not be expressed at all, and therefore water is not very suitable for structural components. It is clear that it is a detoxifier.

According to the invention, liquid nonionic surfactants, especially ethoxylated fatty alcohols, is used in the form of a homogeneous mixture with a destructuring agent. This homogeneous mixture is Either a homogeneous solution or dispersion of the liquid nonionic surfactant used and the hydrophilic It can be obtained by blending it with a structural decomposition agent that dissolves or disperses in water.

Surprisingly, very small amounts (e.g., the combination of liquid nonionic surfactant and destructuring agent) (approximately 8% by weight), the final detergent dissolution rate may vary depending on the additive. The weight ratio of liquid nonionic surfactant and destructuring agent is 8:1. Preferably, a ratio of from 1 to 1.5 of additives is used.

As nonionic surfactants, liquid ethoxylated alcohols according to the definition of the present invention are used. high bulk density detergents (i.e. bulk density of 500 g/n or more, preferably 6 00g/j! More preferably 700 to 1,000 g//! detergent) In the production of liquid nonionic surfactants, all known methods Solutions or dispersions of decomposition agents can be used. such known and preferred An example of a manufacturing method that can be used is granulation, in which detergent formulations or spray Mist-dried detergent formulations or spray-dried detergent formulations and non-spray-dried detergent formulations At the same time when either of the mixtures with the agent formulation is compressed in the high-speed mixer, this mixer during treatment with the solution or dispersion of the invention or after compaction in a high speed mixer. and then processed in other equipment (e.g. fluidized bed). Another preferred manufacturing method is spray drying The detergent formulations that have been spray dried and/or the detergent formulations that have not been spray dried are added to the carrier, especially the Granules together with the solution or dispersion used in the present invention to which a zeolite-containing carrier is added. This is the manufacturing method.

However, the manufacturing method described in detail in international patent application W091102047 is Particularly preferred. This process involves the addition of homogeneous plasticizers and/or lubricants. The solid compound (premix) is mixed under high pressure (25-200 bar) into the intended granules. It is extruded into a strand through a perforated extrusion die with a hole diameter corresponding to the size of the extrusion die. put out. Immediately after exiting the extrusion die, a cutting device is used to cut the strands to the intended size. Cut into granules. High working pressure is applied to the powder during the granulation process. This is to plasticize the material so that the newly extruded strand can be cut.

Special table 16-509369 (4) The compound is a typical cleaning compound that is at least partially solid, preferably particulate. A liquid component can be added if desired. Its hardness The shaping agent may be a coarse powder obtained by spray drying or an agglomerate. Each mixture component selected as a pure substance may be prepared in fine particulate form and mixed together in the form of a mixture. Thereafter, liquid formulations were added as desired. Thereafter, a plasticizer and/or lubricant selected in the present invention is combined therewith. preferred Aqueous solutions of polycarboxylate polymers and High concentration anionic surfactant paste as well as nonionic surfactant. compound pow Detailed descriptions of suitable formulations and suitable plasticizers and/or lubricants for the Found in what is disclosed in international patent application WO91102047 Can be done.

According to the present invention, a liquid nonionic surfactant, which is hydrophilic and is dissolved or dispersed in water, is used. Solutions or dispersions of destructuring agents can be used as liquid formulations or as plasticizers and dispersions. Added to solid compounds as a lubricant and/or as a lubricant, or added to solid compounds in compounds. may be part of a mixture component, in which case the solid mixture component is part of the solution. or from carrier beads impregnated with a dispersion. Become. at any stage of the manufacturing process (e.g., while making the compound, as well as during plasticization) During the production of chemical compounds and before passing through an extrusion die (perforated plate)), The bright solution or dispersion is in liquid form, that is, it is not supported on carrier beats. It can be added in the form of

The solution or dispersion of the present invention can be used in the production of detergents by extrusion under high pressure. It is preferred that the liquid nonionic surfactant and structural decomposition in the solution or dispersion be The weight ratio of the agents is from 10.2 to 1:1, especially from 10:3 to 10:8. .

As a homogenizing device, mixer having any structure (e.g. two-wheel screw kneader) machine) can also be used. Desirable for the kneading machine itself due to the intense mixing process A temperature rise occurs. During the vigorous mixing process, moderately elevated temperatures (e.g. (e.g., 60-70°C) or higher. In a preferred embodiment, the compound It is preferable to continuously feed the powder into a twin-screw kneader (extruder). The housing and extrusion/granulation head of the clew kneader (extruder) The extrusion temperature is heated and maintained at a set extrusion temperature, for example, 40 to 60°C. extruder screen The compound is compressed and plasticized under the shear effect of 25-200 bar. , preferably under a pressure of 30 bar or more, more preferably 50 to 180 bar, It is extruded into a strand through the perforated plate of the extruder head, and finally, using a rotating blade. , the extruded strands are preferably cut into spherical or cylindrical granules. push The hole diameter of the exit die (perforated plate) and the length at which the extruded strand is cut are determined according to the intended Adapt to the size of the granules. In this aspect, it is possible to predetermine , the production of granules having a substantially uniform particle size is provided, each of which has an absolute particle size of It is possible to adapt the particle size required in the application. Generally, the particle size is large It is preferable that the height is up to 0.8 cm. In important aspects, within the millimeter range (e.g. uniform condyles having a diameter of, for example, within the range of 0.5 to 5 mm, especially approximately 18 to 3 m; Characterized by the production of grains. In one important aspect, the The length to diameter ratio of the primary granules ranges from about 1=1 to about 3:1. other preferences In a preferred embodiment, the wet, still plastic primary granules do not require other granulation process steps. The key point is that at this stage, all the corners on the granules fall off and become rounded. Ultimately, spherical or at least substantially spherical granules are obtained.

If desired or necessary, add a small amount of dry powder (e.g. zeolite) at this stage. Zeolite powders such as NaA powders) can be used. commercially available In a spheronizer (e.g. a spheronizer with a rotating lower mounting disc), these A further granulation step can be carried out. The granules are then dried, for example in a fluidized bed dryer. Preferably, it is dried. Surprisingly, peroxy compounds (e.g. Extruded granules containing perborate (perborate hydrate) do not lose any active oxygen. It has been found that drying can be performed at an inlet air temperature of 80-150°C. dried The free water content in the granules is preferably up to about 3% by weight, more preferably 0.1% by weight. -1% by weight. If desired, - immediately after extruding the next rank, i.e. the ball A drying step may be performed before any final granulation step in the shaping machine. .

If desired, dry the dried granules again in finely divided form to obtain a high bulk density. It is advantageous to dust the powder. An example of such a dry powder is again Zeo Light NaA powder, as well as precipitated or pyrogenic silica, commercially available Examples of products include Aerosil (trademark) or Gibernatsu. Stpernat (Trademark) (both Degussa AG) products). Again, a high fat concentration of at least 90% by weight Preferably, alcohol sulfate powders are used, and most of these, i.e. At least 90% consist of particles with a size smaller than 100j■. with zeolite Particular preference is given to mixtures with fatty alcohol sulfate powder.

In another important aspect, the present invention provides a solid detergent produced by the method of the present invention. Regarding. These detergents are improved at temperatures of 15-60°C, especially 20-45°C. It has a high dissolution rate. Produced by the production method of the present invention, with a surfactant content of 20 to 45% by weight. Particularly preferred are detergents containing sex agents.

Suitable anionic surfactants include, for example, sulfonates and sulfates. types of surfactants. Suitable sulfonate type surfactants are: Alkylbenzene sulfonate (CI-I11 alkyl), olefin sulfone (i.e., C12-II monomers with terminal and internal double bonds) After sulfonating the olefin with sulfur dioxide gas, the sulfonated product is treated with an alkali. Alkenes and hydrolyzates of the type obtained by hydrolysis or acid hydrolysis mixtures with xyalkanesulfonates and disulfonates). other suitable Sulfonate-type surfactants convert C12-Il+ alkanes into sulfochlorinated surfactants. After hydrogenation or sulfoxidation, hydrolysis or neutralization are olefins, especially α-sulfo fatty acid esters (sulfonate esters) (e.g. For example, hydrogenated coconut oil, palm kernel oil and alpha-sulfonic acid methyl esters of tallow fatty acids. A sialkane sulfonate obtained by adding bisulfite to be.

Suitable sulfate-type surfactants include primary alcohols of natural and synthetic origin. alcohols, especially fatty alcohols (e.g. coconut oil fatty alcohols, beef tallow fatty alcohols) alcohol, oleyl alcohol, lauryl alcohol, myristyl alcohol, cetiyl alcohol alcohol powder or stearyl alcohol), or Cl11-1゜oxoa alcohol, and sulfuric monoesters of secondary alcohols with similar chain lengths. . In addition, 2-methyl branched C1l+ containing an average of 3.5 mo/ethylene oxide Ethoxylation with 1-5 mad ethylene oxide, such as alcohol sulfated monoesters of alcohols (e.g., sulfated fatty acid monoglycerides) Appropriate.

Also suitable are, for example, natural or synthetic, preferably saturated fatty acid soaps.

Soaps derived from natural fatty acids (e.g. coconut oil, palm kernel oil or tallow fatty acids) Particular preference is given to mixtures. 50-10% of them are CI! -111 saturated fatty acids Preference is given to mixtures consisting of soap and from 0 to 50% oleic soap.

Anionic surfactants include their sodium, potassium and ammonium salt forms (also known as mono-, di- or I-liethanolamine) They may also exist as soluble salts of organic bases such as Anio in the detergent of the present invention The anionic surfactant or anionic surfactant mixture content is preferably between 5 and 40 wt. %, more preferably 8 to 35% by weight. In one particularly advantageous embodiment, the washing The agent contains 10 to 35% by weight of sulfonate and/or sulfate, especially 15-30% by weight and up to 8% by weight of soap, especially 0.5-5% by weight do.

Anionic surfactants are in solid form (e.g. spray-dried or granular); Alternatively, it can be used in a liquid or paste state. Therefore, the manufacturing method During the process, anionic surfactants used as plasticizers and/or lubricants are added to the aqueous world. It can be added in the form of a surfactant paste.

The ethoxylated alcohol used in the present invention as a nonionic surfactant in detergents. The amount is preferably 1 to 15% by weight, more preferably 2 to 10% by weight.

The destructuring agent content used in the present invention automatically follows this nonionic surfactant content. cormorant. The detergent is a polyethylene glycol with a relative molecular weight of 200-1.500 preferably up to 5% by weight, especially 1 to 3% by weight.

The weight ratio of anionic surfactant to nonionic surfactant is preferably at least 1 :1, more preferably 1:1 to 6:1, for example 2:1 to 6:1. .

In addition, as a nonionic surfactant, general formula R-0-CG) x [wherein R is 8 to 22 straight-chain or 2-methyl branched, preferably containing 12 to 18 carbon atoms. The aliphatic group, G, is a glycose unit containing 5 or 6 carbon atoms; - degree X is 1 to 10, preferably 1 and 2, more preferably 1.4 or less. It is possible to use 1 to 10% by weight of an alkyl glycoside represented by the following.

Suitable organic and inorganic builders precipitate calcium ions or A mildly reactive acidic, neutral, and alkaline compound capable of forming complexes. Soluble and/or insoluble components. 100~200+g CaO/g (do NaA has a calcium binding ability of suitable, especially ecological, materials such as microcrystalline synthetic aqueous zeolites of It is preferable to use a safe builder. Their average particle size is generally 1 to 101 (measured with Coulter Counter) , volume distribution). The zeolite content of detergents is typically , up to 50% by weight, preferably at least 10% by weight, especially 20-40% by weight %. During production as an aqueous slurry (masterbatch), zeolite Na A accumulates, which is commonly utilized in the production of modern laundry detergents. It must be dried by some method, especially by spray drying. zeolite, or at least a portion of the zeolite, an undried masterbatch, Alternatively, it can be used in the form of a partially dried masterbatch.

In particular, other builder components that can be used with zeolites include polyacrylic Polycarboxylate (co)polymers such as rylates and polymethacrylates copolymers, especially copolymers of acrylic acid and maleic acid (preferably maleic acid 50-10% copolymer). Relative content of homopolymer to free acid The molecular weight is typically within the range of 1.000 to 100,000, while the molecular weight of the copolymer is The relative molecular weight is typically between 2.000 and 200,000, preferably between 50,000 and It is within the range of 12o, ooo. Particularly preferred acrylic acid/maleic acid copolymers - has a relative molecular weight of 50,000 to 100,000. Of these things Among these, suitable but less preferred compounds are acrylic acid or methacrylic acid. Copolymers of lylic acid and vinyl ethers such as vinyl methyl ether and the percentage content of this acid is at least 50%. any other suitable For example, U.S. Pat. No. 4,144.226 and U.S. Pat. No. 4.1 Carboxylic acid polyacetals of the type described in No. 46.495, as well as Acid polymers obtained by polymerizing chlorein and then causing a disproportionation reaction with an alkali. This acid polymer contains acrylic acid units and vinyl alcohol unit or acrolein unit. During the manufacturing process, polycarboxylate (co ) Polymer in a solid or liquid state, i.e., an aqueous solution, preferably 30 to It is added in the form of a 55% by weight aqueous solution. Polycarboxylate (co)polymers in detergents The reamer content is preferably up to 10% by weight, more preferably from 2 to 8% by weight. Ru.

If there are no ecological problems with the use of builders, suitable organic builders and For example, citric acid and nitrilotriacetate (NTA). Examples include polycarboxylic acids which are preferably used in the form of their sodium salts.

Other suitable detergent formulations include bicarbonates, carbonates or silicates. It is a water-soluble inorganic alkalizing agent. In particular, alkali metal carbonate and alkali metal silicates, especially sodium oxide (NazO) and oxidized Sodium silicate in which the molar ratio of silicon (Si01) is 1=1 to 1:4.0 is used as an alkalizing agent. During the manufacturing process, the alkalizing agent is added in solid form. It is preferable to However, the alkalizing agent may also be used in a small (and partially aqueous) form. state, for example, the state of an aqueous alkali metal silicate solution, or the state of a solid alkali metal silicate. Can be used in the form of a mixture of carbonate and alkali metal silicate solutions Wear.

The sodium carbonate content in the detergent is preferably up to 20% by weight, advantageously between 5 and 15%. Weight%. The sodium silicate content of detergents is typically up to 10% by weight, preferably The content is usually 2 to 8% by weight.

Other detergent formulations include anti-redeposition agents (stain-settling agents), foam suppressants, bleaching agents and Contains bleach activators, optical brighteners, enzymes, fabric softeners, dyes, fragrances and neutral salts. Ru.

Among compounds that are used as bleaching agents and produce hydrogen peroxide (H, O) in water, Of particular interest are sodium borate tetrahydrate and sodium perborate-hydrate. .

Other useful bleaching agents include, for example, bebenzoate, peroxyphthalate , diverazelaic acid or diverdodecanedioic acid. Carbonates, peroxypyrophosphates, citrate perhydrates and peroxides Mention may be made of persalts or peracids that produce hydrogen. The bleach content in the detergent is preferably preferably 5 to 25% by weight, more preferably 10 to 20% by weight, and sodium perborate Preference is given to using lithium hydrate.

Improved bleaching effect when washing at 60°C or lower Bleach activators can be combined with detergents to obtain bleaching agents. suitable bleach activator Examples include hydrogen peroxide, preferably N, N, N', N'-tetraa N,N'-tetraacylated diamines such as cetyl ethylene diamine, Also, carboxylic acid anhydrides and polyesters such as glucose pentaacetate N-acyl compounds or O-acyl compounds that form organic peracids with esters of Examples include compounds. The content of bleach activators in bleach-containing detergents is normally within the range of Preferably it is 1 to 10% by weight, more preferably 3 to 8% by weight.

Anti-redeposition agents can keep dirt removed from fibers soaked in the washing solution. Therefore, re-adhesion can be prevented. Suitable soil settling agents are typically For example, water-soluble salts of carboxylic acid polymers, glue, gelatin, starch or carboxylic acid ether salt or sulfonic acid ether salt of lulose, or water-soluble organic compounds, such as salts of acidic sulfate esters of cellulose or starch; It is a colloid. Also suitable for this purpose are water-soluble polyamides containing acidic groups. .

Also soluble starch preparations, also e.g. degraded starches, aldehyde starches It is also possible to use other starch products other than those mentioned above, such as It is. Polyvinylpyrrolidone can also be used. carboxymethyl Cellulose (sodium (Na) salt), methyl cellulose, methyl hydroxyethyl Chillcellulose and mixtures thereof and polyvinylpyrrolidone in detergents However, it is particularly preferred to use it in an amount of 0.5 to 5% by weight.

By combining appropriate surfactants, the foaming power of surfactants was enhanced. or attenuate it. i.e. adding non-surfactant organic substances It can also be attenuated by Often when detergents are used in washing machines The reduced foaming power that is desirable for For example, sulfate and/or sulfonate can be added to a nonionic surfactant by Obtained by combining with sex agents and/or soaps. Regarding soap, foam The suppression increases with the degree of saturation of the fatty acid ester and the length of the carbon (C) chain.

Therefore, suitable foam inhibitors have a high percentage content of C1M-24 fatty acids. Soaps made from natural and synthetic ingredients. Suitable non-surfactant foam suppressants include organopolymer Siloxane and organopolysiloxane with trace amounts of optionally silanized mixture with silica, paraffin, wax, microcrystalline wax, and mixtures of organopolysiloxanes and silanized silicas. Also CI ! -Bis-acyl derived from 1°alkylamine and Cm-6 dicarboxylic acid Mido can also be used. Also mixtures of various foam suppressants (e.g. silicone and paraffin or wax) can also advantageously be used. Foam control The agent is fixed on a granular carrier that is dissolved or dispersed in water, and the plasticizer and/or Preferably, it is combined with a lubricant.

Detergents contain diaminostilbendisulfonic acid derivatives and their like as optical brighteners. may contain an alkali metal salt of. Suitable optical brighteners include, for example, 4°4 °-Bis-(2-anilino-4-morpholino-1,3,5-triazinyl-6- salt of amino)-stilbene-2,2'-disulfonic acid or its morpholino group is a jetanolamino group, methylamino group, anilino group or 2-methoxy- Compounds with the same structure substituted with an ethylamino group may be mentioned. Also replaced 4, Brighteners of the 4'-distyryldiphenyl type, for example the compound 4,4'-bis- (4-chloro-3-sulfostyryl)-diphenyl may also be present. In addition, the above increase Mixtures of whitening agents can also be used.

In other preferred embodiments of the invention, conventional doses (e.g. 0.1-0.5% by weight) In addition to the usual optical brighteners, preferably in the range of 1 to 0.3% by weight, detergents also contain , a small amount (e.g. 10-6 to 10-3% by weight, preferably about 101% by weight) of blue If a color dye is also included, uniform white granules are obtained. Particularly preferred dyes are tea Tinolux: Trademark, Ciba-Gei gy) products].

Suitable enzymes are proteases, lipases and amylases or mixtures thereof. An enzyme selected from the group consisting of: Bacillus subtilis, Bacillus licheniformis (Ba cillus 1ichenifor■is) and Streptomyces grise bacterium such as S treptomyces griseus Particularly suitable are enzymes obtained from strains of Ria or from fungi. subtilisin type proteases, especially Bacillus 1 entus Preferably, a protease obtained from To protect against premature decomposition Additionally, the enzyme can be adsorbed onto a carrier and/or encapsulated in an encrusting material. .

Particularly suitable stabilizers for compounds and enzymes are salts of polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP).

Detergents can be produced entirely from extrudates with the above formulations. However, It can also be obtained from a mixture of several different granules, in which the extrudate of the invention forms the main component. Ru. For example, bleach activators, enzymes and dyes, and fragrances may be later incorporated into the extrudate. You can let it happen. Both bleach activators and enzymes can be used in separately manufactured extrudates, e.g. It is preferable to use it in compressed granule form as a is obtained using a pellet press.

First of all, the solid compound Cm-l8 alkylbenzene sulfonate sodium 2,000 g of um salt powder (90% by weight of active substance), C++-+s fatty alcohol Rusulfate powder 2,250g (91% by weight of active substance), Ct*-+s fat Sodium acid soap 200g 1 Wessalith P [trademark, Zeolite NaA, product of Degussa AG, Federal Republic of Germany 1 3,700g, anhydrous sodium carbonate 650g.

Sokalan CF2 [trademark, a combination of acrylic acid and maleic acid] Polymer, 95% by weight of active substance, product of BASF, Federal Republic of Germany] Powder 88 0 g, 8% by weight of silicone oil and 5% of sodium sulfate as inorganic carriers. 1,650 g of concentrated foam suppressant containing 8% by weight and 20% by weight of water glass; Add 2,100 g of sodium perborate hydrate to the cutter head. Place it in a batch mixer (20 liters) equipped with a After adding H, C12-1 @ fatty alcohol 5 ethylene oxide 330 g, 200 g of beef tallow fatty alcohol, 5-functional tyrene oxide, and a relative molecular weight of 400. A mixture of 250 g of polyethylene glycol was added. Then, 35% by weight Sodium icate aqueous solution (sodium oxide silicon dioxide 1:3.0) 780 g and 30% by weight of tetrasodium 1-hydroxyethane-1,1-diphosphonic acid 165 g of an aqueous solution of aluminum salt was added. After homogenizing the mixture for 2 minutes, the housin (including the granulation head of the extruder) into a twin screw extruder maintained at 45°C. Sent out. Directly after plasticizing the compound under the shearing effect of the extruder screw Pressed under a pressure of 120 bar to form a good strand with a diameter of 1.2 ■I. After being extruded through the perforated plate of the extruder head and exiting from the perforated plate, the granules are substantially spherical. (length-to-diameter ratio approximately 1, hot cut) using a blade. storage Place the warm granules in a Marumerizer type dish. After treatment for 1 minute in a commercially available spheronizer, the inlet air temperature was 120°C in a fluidized bed dryer. Dry at ℃. The coarse product was sieved through a 1.6-inch mesh sieve.

Less than 3% of the particles were larger than 1.6 fins in size. The bulk density of the obtained granules is It was 820g/i'.

The dissolution rate of the granules was determined by conductivity measurement.

Pour 500 g of deionized water (20°C) into a 1 liter glass container and add it to the propeller. Turn on the stirrer (speed 900r, p, m,) and insert the conductivity measurement cell. Submerged in water. Thereafter, 5 g of detergent granules were added. Instrument that records changes in conductivity recorded. Continue measurements until no further increase in measurable conductivity occurs did.

The time required for the conductivity to reach a certain value is the dissolution time of the granules (100%). Ru. The dissolution time for 90% dissolution was calculated.

The dissolution time of the granules of the invention was 2.20 minutes at 20°C/90% dissolution.

Comparative example 1 Ethoxylated alcohol and polyethylene glycol, not in the form of a mixture, but each Compounds having the same composition as the examples of the invention, except that each compound is added separately. was prepared in a similar manner.

The compound was extruded, cut, shaped into spheres and dried in a similar manner to the examples of the invention. It was dried and passed through a sieve. The bulk density of the granules C1 was 820 g/f.

The dissolution time of granules C1 was 3.77 minutes at 20°C/90% dissolution.

Comparative example 2 A method similar to the example of the present invention, except that polyethylene glycol is not added. A compound containing the same components and amounts in the same amounts as in the examples of the present invention was prepared. present invention The compound was extruded, cut, shaped into spheres and dried in a manner similar to the example in , sieved. The bulk density of granules C2 is 820g/j! Met.

The dissolution time of granules C2 was 3.85 minutes at 20°C/90% dissolution.

Continuation of front page (72) Inventor: Jacobus, Jochen Federal Republic of Germany Day-5600 Wuppertal 12, Tässienzutbel No. 50 (72) Inventor: Vogt, Günther, Federal Republic of Germany 4154 Zinisforst 2, Bruckner Strasse No. 13

Claims (19)

[Claims] 1. Anionic surfactants using solid and liquid detergent raw materials as solid components; Nonionic surfactants for use as builders and alkalizing agents and as liquid components or by granulating and combining after drying if desired. A method for producing high bulk density solid detergents with improved dissolution behavior and easy combination. A homogeneous mixture with a destructuring agent (liquid nonionic surfactant and deconstructive agent) Liquid nonionic surfactant is used in a dissolving agent weight ratio of 10:1 to 1:2. A method for producing a high bulk density solid detergent. 2. Polyethylene glycol or polypropylene glycol as structural decomposition agents polyethylene glycol or polypropylene glycol sulfate or and/or disulfate, polyethylene glycol or polypropylene Recall sulfosuccinate and/or disulfosuccinate, or A method according to claim 1, characterized in that a mixture thereof is used. 3. As a structural decomposition agent, C6-18 ethoxylated fatty alcohol 20-45 ethylene oxide, preferably beef tallow fatty alcohol 30 and 40 ethylene oxide The method according to claim 1, characterized in that Cid is used. 4. As a liquid nonionic surfactant, 8 to 20 carbon atoms and alcohol 1 Ethoxylated fat containing an average of 1 to 15 mol of ethylene oxide per mol The manufacturing method according to any one of claims 1 to 3, characterized in that a fatty alcohol is used. . 5. The weight ratio of liquid nonionic surfactant and structure decomposition agent is 8:1 to 1:1.5. The manufacturing method according to any one of claims 1 to 4, characterized in that: 6. The weight ratio of ethoxylated alcohol to destructuring agent is 10:2 to 1:1, preferably Preferably from 10:3 to 10:8, with a homogeneous mixture of ethoxylated alcohols. The manufacturing method according to claim 5, characterized in that a decomposition agent is used. 7. Anionic surfactants in solid, liquid or paste-like form The manufacturing method according to any one of claims 1 to 6, characterized in that it is used in. 8. The surfactant is used in an amount of 20 to 45% by weight based on the detergent. The manufacturing method according to any one of claims 1 to 7. 9. The weight ratio of anionic surfactant to nonionic surfactant is preferably at least 1:1, more preferably 1:1 to 6:1, 5 to 40% by weight of detergent , preferably 8-35% by weight of anionic surfactant and 1-15% by weight, preferably Alternatively, 2 to 10% by weight of a nonionic surfactant is used. 8. The manufacturing method described in 8. 10. The soap is used in an amount of 0.5 to 5% by weight based on the detergent. The manufacturing method according to claim 8 or 9. 11. Characterized by the use of optical brighteners and blue dyes as further components The manufacturing method according to any one of claims 1 to 10. 12. As further solid component, a bleaching agent, preferably sodium perborate hydrate is used in an amount of 5 to 25% by weight based on the detergent. 1. The manufacturing method according to any one of 1. 13. As a further component, polycarboxylate (co)polymers can be used in solid or 13. The method according to claim 1, wherein the method is used in liquid form. 14. A homogeneous solid compound to which plasticizers and/or lubricants have been added is heated at high pressure (2 5-200 bar), extrusion die with pore size corresponding to the intended granule size. Immediately after exiting the extrusion die, the strand is cut using a cutting device. Combining detergent raw materials by cutting them into granules of the desired size The manufacturing method according to any one of claims 1 to 13, characterized in that the molding is carried out by molding. 15. Bleach activators, enzymes and dyes, and fragrances are later combined into the extrudate The manufacturing method according to claim 14, characterized in that: 16. Separately produced extrudates obtained using a kneader or pellet press A claim characterized in that the bleach activator and the enzyme are used in compressed form. 15. The manufacturing method described in 15. 17. Detergent formulations or spray-dried detergent formulations or spray-dried detergent formulations Either the mix or the non-spray-dried detergent mix is pressurized in a high-speed mixer. At the same time, the liquid nonionic surfactant and destructuring agent are homogeneously mixed in the mixer. or with a homogeneous mixture of a liquid nonionic surfactant and a destructuring agent. After processing, detergent raw materials are combined by processing in other equipment. The manufacturing method according to any one of claims 1 to 13, characterized in that they are molded together. 18. Spray-dried and/or non-spray-dried detergent formulations , liquid nonionic surfactants and structures with the addition of carriers, especially zeolite-containing carriers. Detergent raw materials are made into granules together with a solution or dispersion of a decomposer. The manufacturing method according to any one of claims 1 to 13, characterized in that molding is performed in combination. . 19. A bulk density of 600 to 1.000 g/l is fixed in the detergent. The manufacturing method according to any one of claims 1 to 18.