JPH06506719A - Chemical composition of surfactant paste to form highly active surfactant particles - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Chemical composition of surfactant paste to form highly active surfactant particles field of invention The present invention relates to a method for producing a composition containing concentrated detergent particles. It was manufactured by spray drying method. In the spray drying method, surfactants and Detergent compositions such as detergents and builders are mixed with as much as 35-50% water to form a slurry. do. The resulting slurry is heated and spray dried, which is expensive but The agglomeration method would probably be cheaper.

Spray drying must remove 30-40% water. Realize spray drying The equipment used is expensive. The resulting particles have high solubility but low bulk density , the packaging volume is large. Also, the flow of particles obtained by spray drying The properties are hampered by the large surface irregularities and the appearance of the particles is poor.

There are other known problems with the preparation of granular detergents by spray drying.

A variety of non-spray drying methods exist for making detergent particles. These methods are also lacking. Has a point. Many require mixers and separate granulation operations. Also someone else The method requires the use of acid type surfactants. Other methods require high temperatures, This causes the raw material paddy to deteriorate. In these methods, highly active surfactant are avoided due to their sticky nature.

EP-A-0,110,731 forms a solid without evaporative drying and therefore Detergent powder is manufactured by mixing sex agent solution with builder powder and neat face. discloses a method to do so. Methods of grinding solid bars or blocks are described However, the pace for directly forming highly active particles by agglomeresicon is Conditioning is not listed.

EP-A-0,345,090 describes the use of acid detergents together with carriers in the absorption zone. A granular detergent composition is produced by contacting a granular detergent composition with a granular neutralizing agent or a salt-based detergent. Discloses how to do so.

EP-A-0,349,201 describes the combination of a dry detergent builder and a highly active surfactant. Disperse into a uniform powder, freeze this dough, and granulate it using a fine dispersion method to create a uniform powder. Discloses a method for producing concentrated detergent particles by forming free-flowing particles. Ru.

The method for continuous production of granular detergents or compositions described in EP-0,390,251 is The detergent surfactant and the builder fine particle fragments f4 are treated in a high-speed mixer, Second, processing in a medium speed granulator/densifier and third, a drying/cooling device. in the second stage or in the first stage and the second stage. Add powder in the middle of the floor to reduce the amount of oversized particles.

A. David Zinn or B. M. Mild Widoski, 5ynthtlc Detergents % John Viley & 5ons, 6th edition, 1978 discloses a general description of detergents, including the manufacture of finished detergent products. .

Although high shear/cold mixing methods are known per se, these methods require extra grinding steps or or other work is required. For example, in the second and third methods, acidic surfactants are Use a dry neutralization technique to mix with thorium. U.S. Patent No. 4°515.707; See Japanese Patent Application No. 183540/1983 and Nipponbare No. 61-118500. Light. Extra amounts of carbonate are required for adequate conversion of acid-type surfactants (2- 20 moles extra). This extra carbonate will lower the pH of the wash water into the very alkaline range. is particularly undesirable for low phosphate compositions.

When using acidic surfactants, immediate cold storage is generally required. . Highly reactive acids, such as alkyl sulfates, degrade during storage without cooling. This is because it tends to be hydrolyzed to form free sulfuric acid and alcohol. practically , such prior art methods require coupling the production of acid-type surfactants with granulation. Yes, this requires additional capital investment.

A second method, known in the industry and in the patent literature, is to During the step, the acidic anionic surfactant is dissolved in a caustic solution (e.g. 50% NaOH) or Neutralization in situ with a caustic powder (eg Na2C03). in this case , undesirable shadows on residual surfactant matrix during storage or washing Care must be taken to completely neutralize the acid to prevent effects. The particles obtained are very The particles are dense and can be incorporated into granular detergents.

This second method uses lower temperatures and lower degrees of shear than the clutching/spray drying method. However, there are many limitations. On the one hand, chemical reactions during or just before the granulation stage (neutralization reaction), the processing conditions that may be used (temperature, composition etc.) significantly restricting the range of The pH of acidic anionic surfactants is very low. This precludes the use of compounds sensitive to such acidic conditions.

But above all, it is chemically unstable or physically unstable in its acid form. For anionic surfactants such as It is necessary to closely connect the neutralization treatment unit with the neutralization/granulation stage.

As a result, these methods require significant logistics and/or facility design considerations. There are limitations and the overall process control system becomes complex and difficult.

The present invention solves the above-mentioned problems and also improves the treatment of granular detergent compared to conventional methods. The aim is to provide a method that is flexible and versatile. The present invention utilizes sulfate/sulfone Based on an agglomeration/granulation stage completely separated from the acid chlorination process There is. In order to significantly increase the surface activity of the agglomerates, the present invention By increasing the powder ratio, it is possible to form particles that are hard and easy to crush. This is a special chemical structure. Paste chemistry and/or or achieved by physical configuration. The basis of the present invention is the use of anionic surfactants. salt, preferably in the form of a highly concentrated aqueous solution of its sodium salt. be. These highly active (low moisture) surfactants are highly viscous, but their stable temperatures Pumping is still possible at degrees. This allows this compound to be removed from the manufacturing site. suitable storage facilities can be used prior to particle formation.

Intermediate buffering can also be used when the sulfate/sulfonate oxidation process immediately precedes the granulation stage. A tank can be installed to simplify control of the entire unit. highly viscous liquid In the case of certain surfactants or their mixtures that develop crystalline phases, this technology may form a low viscosity phase (e.g. neat face) or undergo some kind of viscosity modification. It is necessary to use additives (eg hydrotropes).

Another book! The following describes how to perform paste conditioning. chemical structure Addition of formulation agents, temperature control and/or removal of water from the paste may affect viscosity, melting point and These physical properties are important for paste mixing/adhesiveness and other physical properties. It has been discovered that granulation determines the properties of detergent particles produced by granulation. this pace A very effective way to achieve this conditioning is to use an extruder. was also discovered.

The main object of the present invention is to provide a densely packed solution by a spray/dry method and a different liagromeresic method. The process involves producing a concentrated detergent particle product. Other objects of the invention will be apparent from the following: Dew.

Summary of the invention The present invention provides a dense, concentrated detergent particle product, particularly a set containing very highly active concentrated detergent particles. Use of a highly active paste agglomerated silane step in an economical process for the production of products and a method for carrying out the chemical treatment of the resulting paste. .

The invention particularly applies to all neutralized AS aqueous pastes. The present invention Applicable to various types of surfactants.

Detailed description of the invention The present invention provides a process for making a flowable granular detergent in which an effective amount of a chemical structuring agent and at least 40% an effective amount of an aqueous surfactant paste having a detergent activity of %; A homogeneous stiff paste is rapidly produced from the mixture at a paste temperature of 20 to 90°C. and granulating the paste when mixed with dry detergent powder. , the surfactant paste comprising at least one anionic surfactant. , and other surfactants, these surfactants can be anionic, nonionic, Selected from bitter ionic, amphoteric and cationic surfactants and mixtures thereof. It concerns how to In a preferred method, the chemical structuring agent is applied in a continuous process. It is added in the process.

The present invention provides an agglomeration process that is completely separate from the sulfate/sulfonate treatment. Condensation/granulation stage and the paste resulting from said stage to further produce highly active particles. and a chemical conditioning step.

Paste conditioning refers to high It means changing the physical properties of the paste so that it forms active agglomerates. . The invention applies in particular to all neutralized AS aqueous pastes. Main departure Light is used in various surfactants (e.g. coconut surfactant, tallow surfactant, etc.) It was discovered that it can be applied. In one embodiment of the invention, anionic surfactant The sex agent is introduced in the form of a highly concentrated aqueous solution of its salt, preferably its sodium salt. . These highly active (preferably low moisture) surfactant pastes have high viscosity but , these surfactants are pumpable at stable temperatures. In addition to the present invention In embodiments of the invention, at least one anionic surfactant in which a highly viscous liquid crystalline phase occurs Anionic surfactant mixtures containing sex agents should form a low viscosity phase and requires the use of some kind of viscosity modifier. In a further preferred embodiment may contain organic or organic compounds that alter the physical structure and/or properties of the surfactant paste. and/or inorganic compounds are added to the paste. Such surfactants Addition to the paste reduces the stickiness of the paste, increases its viscosity, It also increases its softening point. This makes it easier to use during the agglomeration process. It is possible to add a larger amount of paste, i.e. more than 50%, thus making it more active. resulting in agglomerates of. The processing method for such surfactant paste is the batch method. The method can be carried out in a continuous mode or in a continuous mode, but preferably in a continuous mode.

In a preferred embodiment of the invention, the press is used for conditioning the paste. The exit machine is used. The extruder mixes 2F1 or two or more pastes and/or Alternatively, it is a general-purpose device that adds and mixes a chemical structuring agent to a viscous paste. difference In addition, this extruder can remove moisture under vacuum, and the paste temperature can be reduced. Control is possible.

Paste conditioning, as used herein, refers to (a) the apparent increase in viscosity; (b) increase its effective melting point, (C) increase the "hardness" of the paste, and (d) reducing the stickiness of the particles formed; The hardness/softness of the paste is A STM D 217-IP50 by softness needle meter according to Taha ISO2137 It can be measured. The hardness of the paste measured in this way is preferably 2 cm or less. or less than 1 cm.

Conditioning of this paste consists of (i) cooling the structuring agent and (ii) drying it. (ii) Adding a structuring agent (usually an electrolyte) to the highly active detergent paste This is achieved by The paste used in the invention is at least 40% by weight of anionic surfactant salt, which has a small At least 10 Pa.

It has a viscosity of S and a shear rate of 25 s-1.

chemical structuring agent Various chemical structuring agents, when added to a surfactant paste, modify the chemical properties of the paste. altering the properties and/or physical properties to form highly active agglomerates.

These structuring agents can be solid, liquid or solution according to their specific chemical properties. Can be done. Examples of structurants used in the present invention are 50% NaOH (aqueous), 5 0% K OH (aqueous), NaCl, phosphate, silicate, silica, starch, potassium remers, copolymers, nonionic surfactants and urea. the chemical structuring agent mentioned above; can be made independently or in combination with each other according to their compatibility.

paste For use in the present invention, one or more water-soluble salts of anionic surfactants may be used. Pastes, preferably sodium salts, are preferred. In a preferred embodiment, Anionic surfactants are preferred to the extent that they can be pumped at their stable temperature. be as concentrated as possible (i.e., allow this surfactant to flow like a liquid). (condensed to the minimum moisture content obtained). Various pure surfactants or surfactant mixtures Although a granulation method using In order to produce particles with suitable physical properties for incorporation into agents, anionic fields must be The surfactant is 10% or more, preferably 10-95%, more preferably 20-95%. , most preferably at a concentration of 40-95%. No.

The water content in the surfactant aqueous paste must be sufficient to maintain the fluidity of the paste. It is preferable to lower the This is because low moisture means high concentration of surfactant in the finished particles. This is because it causes degree. Preferably the paste has a moisture content of 5 to 40%, more preferably It preferably contains 5 to 30% water, most preferably 5 to 20%. Agrome Reduces the moisture content of the paste before entering the lacquer, eliminating problems associated with very high viscosities. The preferred method to avoid this is at the outlet of an atmospheric or vacuum flash dryer. This is a plant in which a line is connected to an agglomerator.

When using highly active surfactant pastes, the system must be It is preferred to minimize the total moisture level in the fluid. Low moisture levels reduce (1) activity High surfactant:builder ratio, e.g. 1:1, (2) paste or particle (3) increasing the level of other liquids in the formulation without causing sticking; and (3) increasing the granulation temperature tolerance. (4) grain size to meet the final moisture limit; Child dryness decreases.

Two important parameters of surfactant paste that affect the mixing/granulation stage are temperature and viscosity of the yeast.

Viscosity is a function of concentration and temperature, and in this application is approximately 10.0OOcp. s to 10,000,000 cps. Preferably a page entering the system. The viscosity of the yeast is about 20,000 to about 100,000 cps.

More preferably, the range is from about 30,000 cps to about 70,000 cps. Main departure The viscosity of the light paste is determined to be 71111 at a temperature of 70°C.

The paste is placed in a mixer with its softening point (generally within the range of 40-60°C) and its deterioration. (depending on the chemical nature of the paste, e.g. alkyl sulfate pastes have a temperature of 75-8 It can be introduced into the mixer at an initial temperature between 5°C and 5°C. high adoption Temperature reduces viscosity and makes paste easier to pump, but lower activity agglomerates generate a rate. However, using an in-line moisture reduction step (e.g. flash drying) If used, higher temperatures (100° C. or higher) must be used. To the present invention In this case, the activity of agglomerate is kept high due to the removal of water.

To introduce the paste into the mixer, use the pipes before introducing the paste into the mixer. For example, simply injecting the paste into a high-pressure pump through a small hole at the end of the pump. This can be done in a number of ways. All these methods are based on agrochemicals with excellent physical properties. Although effective in the production of romelate, in a preferred embodiment of the present invention, The extrusion process improves the distribution of the paste in the mixer and increases the yield of particles of the desired size. It was discovered that it increases Using high pumping pressure before entering the mixer can increase the activity in the final agglomerate. Both of these effects Connect the paste to the desired flow rate while pumping the system into the system. The paste is introduced through a hole (extrusion hole) small enough to retain maximum This gives very desirable results.

Highly active surfactant paste The activity of the aqueous surfactant should be at least 30% and can increase to about 95%. Wear. Preferred activities are in the range 50-80% and 65-75%. pace The residue is mainly water, but may contain processing aids such as nonionic surfactants. can. At higher active concentrations, the builder is used for cold granulation of the paste. - little or no required. The obtained concentrated surfactant particles are Added to dry builder or powder used in agromelencon operations I can do things. Aqueous surfactant pastes contain anionic, zwitterionic, amphoteric and amphoteric surfactant pastes. selected from the group consisting of surfactants, cationic surfactants, and mixtures thereof. Contains surfactant. Anionic surfactants are preferred. Second surfactant or processing aid A nonionic surfactant is used as the agent, which nonionic surfactant is It is not included in "active" surfactants. The surfactants used in the present invention are disclosed in U.S. Pat. No. 3,664,961 and U.S. Pat. No. 3,919,678. . The cationic surfactant that can be used in the present invention is disclosed in U.S. Patent No. 4,222,905. and U.S. Pat. No. 4,239.659. But cation Surfactants are generally poorly compatible with the aluminosilicate materials used in the present invention. Therefore, it is used at low levels in the compositions of the present invention. The following is a book This is an example of a typical surfactant used in the invention.

In the composition of the present invention, water-soluble esters of higher fatty acids, that is, "soaps" are It is an effective anionic surfactant. This ranges from about 8 to about 24 carbon atoms, preferably Sodium salts, potassium salts, anhydrous salts of higher fatty acids containing about 12 to about 18 carbon atoms Includes alkali metal soaps such as monium salts and alkylammonium salts. this These soaps are produced by direct saponification of fats and ura, or by neutralization of free fatty acids. Manufactured by. Particularly effective are fats derived from coconut oil and tallow. Sodium and potassium salts of fatty acid mixtures, i.e. sodium or potassium tallow and coconut soap.

Further, the anionic surfactant used in the present invention has about 10 to about 20 An organic sulfuric acid reaction product having an alkyl group containing carbon atoms and a sulfonic acid ester group. Water-soluble salts of the products, preferably alkali metal salts, ammonium salts and alkyl salts Contains ammonium salts (the alkyl portion of an acyl group is included in "alkyl") ). Examples of this group of synthetic surfactants include higher alcohols (C8-018 carbon Sodium alkyl sulfate and potassium atom obtained by sulfating products, such as those obtained by reducing the glycerides of tallow or coconut oil, and alkyl groups containing about 9 to about 15 carbon atoms in a straight or branched chain. Sodium and potassium alkylbenzene sulfonates, e.g. U.S. Pat. No. 20°099 and U.S. Pat. No. 2,477.383. Special Straight chain alkyls having an average number of carbon atoms in the alkyl group of from about 11 to about 13 are preferred. Killbenzene sulfonate, which is called C11-C13LAS It is.

The anionic surfactant is sodium alkyl glyceryl ether sulfonate, especially These ethers of higher alcohols derived from tallow and coconut oil, coco Sodium oil fatty acid monoglyceride sulfonate and sodium sulfate, molecule contains about 1 to about 10 units of ethylene oxide and about 8 to about 1 alkyl group. Sodium of alkylphenol ethylene oxide ether sulfate containing 2 carbon atoms or potassium salts, containing from about 1 to about 10 units of ethylene oxide per molecule. an alkyl ethylene oxide ether in which the alkyl group has about 1 to about 20 carbon atoms; Sodium or potassium sulfate.

Other effective anionic surfactants contain about 6 to 20 carbon atoms in the fatty acid. alpha-sulfonated fatty acids containing about 1 to 10 carbon atoms in the stellate group; water-soluble salts of esters, alkane moieties containing about 2 to 9 carbon atoms in the acyl group; 2-acyloxy-alkane-1-sulfur containing about 9 to 23 carbon atoms in water-soluble salts of fonic acid, containing about 10 to about 20 carbon atoms in the alkyl group; Alkyl ether sulfate containing 1 to 30 moles of ethylene oxide, about 12 to 24 Water-soluble salts of olefin sulfonates containing carbon atoms, and in the alkyl group about 1 to 3 carbon atoms, and about 8 to about 20 carbon atoms in the alkane moiety Contains beta-alkyloxyalkane sulfonates. Acidic salts are typically discussed. Although discussed and used, acid neutralization can be performed as part of the fine dispersion mixing step. can.

Preferred anionic surfactant pastes in the present invention have 10 to 16 carbon atoms. a linear or branched alkylbenzene sulfonate containing an alkyl of 10 to It is a mixture with alkyl sulfates containing alkyls of up to 18 carbon atoms. These pages The yeast is usually produced by reacting a liquid organic substance with sulfur trioxide to form a sulfonic acid or sulfuric acid. It is produced by producing an acid and then reducing this acid to produce a salt of the acid. this Salts are surfactant pastes discussed throughout this specification. among others The sodium salt is preferred due to the cost and performance of NaOH for abrasive agents, but K It is not limited to this as other salts such as OH can also be used.

Use of water-soluble nonionic surfactants as secondary surfactants in the compositions of the present invention I can do that. Practically preferred methods use anionic/nonionic mixtures.

Particularly preferred pastes are from about 0.01:1 to about 1=1, preferably about 0.05+ It consists of a mixture of nonionic and anionic surfactants in a ratio of 1:1. Non-i On-surfactants can be used in amounts up to the same amount as the primary organic surfactant. like this Nonionic surfactants are composed of alkylene oxide groups (hydrophobic in nature) and organic hydrophobic compounds. (aliphatic or alkyl aromatic in nature).

The length of the polyoxyalkylene group that is fused with a particular hydrophobic group depends on the hydrophobic element and its affinity. Easily obtain water-soluble compounds with the desired balance with aqueous elements: Can be done.

Suitable nonionic surfactants are oxidized polyethylene condensates of alkylphenols, e.g. For example, a straight or branched alkyl group containing 6 to 16 carbon atoms. alkylphenol and about 4 to 25 moles of oxidation per mole of alkylferrule. Condensation product with ethylene.

Preferred nonionic surfactants have 8 to 22 carbon atoms in a straight or branched chain. aliphatic alcohol containing 4 to 25 moles of ethylene oxide per mole of alcohol. It is a water-soluble condensation product with Particularly preferred nonionic surfactants are about 9 to Alcohols with alkyl groups containing 15 carbon atoms and per mole of alcohol Condensation product with about 4 to 25 moles of ethylene oxide, and propylene gelcol It is a condensation product of ethylene oxide and ethylene oxide.

Semipolar nonionic surfactants have a 1-fulkyl moiety of about 10-18 carbon atoms. a group consisting of alkyl and hydroxyalkyl groups of about 1 to about 3 carbon atoms; a water-soluble amine oxide containing two moieties selected from 1 alkyl moieties and alkyl groups of about 1 to about 3 carbon atoms and hydroxy A water-soluble oxidized protein containing two moieties selected from the group consisting of alkyl groups. sphine, 1 alkyl moieties of about 10-18 carbon atoms and about 1-3 carbon atoms 1 selected from the group consisting of child alkyl groups and hydroxyalkyl groups; a water-soluble oxidized sulfoxide containing a moiety.

Amphoteric surfactants are aliphatic derivatives of heterocyclic box 2 and tertiary amines. Group moieties may be linear or branched and one aliphatic substituent may be about 8- contains 18 carbon atoms and at least one aliphatic substituent contains an anionic water-soluble group Including things.

The Zvitter ion is a derivative of aliphatic quaternary ammonium and one aliphatic substituent. sulfonium compounds containing about 8-18 carbon atoms.

Particularly preferred surfactants are linear surfactants containing about 11-14 carbon atoms in the alkyl group. Alkylbenzene sulfonate, tallow alkyl sulfate, coconut alkyl group Lyceryl ether sulfonate, alkyl moiety is approximately 14-18 carbons an alkyl ether sulfate containing atoms and having an average degree of ethoxylation of about 1-4, about 1 Olefin or paraffin sulfonate containing 4-16 carbon atoms, alkyl an alkyldimethylamine oxide in which the group contains about 11-16 carbon atoms; Alkyldimethylaminopropane sulfonic acid containing about 14-18 carbon atoms salt and alkyldimethylamino hydroxypropane sulfonate, approx. Higher fatty acid soap containing 2-18 carbon atoms; about 3-8 mol with C9'15 alcohol condensation products with ethylene oxide, and mixtures thereof.

An effective cationic surfactant is a water-soluble quaternary ammonium of the R4R5R6R7N+X-form. R4 has 1.0-20, preferably 12-18 carbon atoms. alkyl, R, R and R7 are each C1-C7 alkyl, preferably methyl R, X- includes anions such as chloride. Such trimethyl An example of an ammonium compound is C12-014 alkyl trimethylammonium Chloride and Cocoalkyl Trimethylammonium Mesosulfate.

Particularly preferred surfactants for use in the present invention are: "C11'13 alkyl Benzene sodium sulfonate, α-olefin sulfonate, C11 '13 Alkylbenzene Triethanolammonium sulfonate, alkyl Sulfates (derived from tallow, coconut, palm, synthetic oils, e.g. 045), alkyl Sodium sulfate, MES, coconut alkyl glyceryl ethers Sulfation of sthorium sulfonate, tallow alcohol and about 4 moles of ethylene oxide Sodium salt of condensation product, coconut fatty alcohol and about 6 moles of ethylene oxide a condensation product of tallow alcohol and about 11 moles of ethylene oxide, a fatty alcohol containing about 14 to about 15 carbon atoms and about 7 moles of ethylene oxide. Condensation product, condensation of C12-C13 fatty alcohol with about 3 moles of ethylene oxide Product, 3-(N,N-dimethyl-N-coconut alkyl ammonio)-2- Hydroxypropane-1-sulfonate, 3-(N,N-dimethyl-N-co coconut alkyl ammonio)-propane-1-sulfonate, 6-(N-dode Sylbenzyl-N,N-dimethylammonio)hexanoate, dodecyl oxide Methylamine, coconut alkyldimethylamine oxide, and coconut and animal Contains water-soluble sodium and potassium salts of fatty acids.

(In the specification of the present invention, "surfactant" refers to a non-ionic surface, unless otherwise specified.) means an activator. Surfactant active ingredients (excluding non-ionic ingredients) and dry detergent building The ratio of powder to powder is 0.005 to 19:1, preferably 0.05 to 1. The ratio is within the range of 0:1, more preferably 0.1=1 to 5:1. even more preferable The wall active ingredient: builder ratio is preferably 0.15:1 to 1:1, more preferably is 0.2:1 to 0.5:1) extruder The extruder functions to pump and mix the viscous surfactant paste on a continuous basis. Tasu. The basic extruder consists of a barrel with a smooth inner cylindrical surface. of this barrel An extrusion screw is installed inside. Highly active paste introduction boat is placed When the screw is rotated, the paste is transferred to the longitudinal force of the barrel.

Depending on the detailed design of the extruder, various functions can be implemented. First, in the barrel Add other ingredients, including chemical structurants, directly into the barrel through the addition boat. can be done. Second, a vacuum pump and a seal around the screw shaft ensure that the It can suck in air to lower moisture levels. Third, the barrel for temperature control Means for heating or cooling are provided within the wall. Fourth, the extrusion screw A deliberate design facilitates the mixing of the paste on its own and with other corrections. Can be done.

A preferred extruder is a twin screw extruder. This type of extruder has the same barrel Two screws are mounted in parallel inside the rotation) or in the opposite direction (counter-rotation). Co-rotating twin screw pusher The extractor is the most preferred device for use in the present invention. used in the present invention In extruders, liquid nitrogen or solid carbon dioxide is added to the barrel. By this, the pace] is effectively cooled (this is because ordinary extruders cannot overcome viscous shear forces). As a result of mechanical energy and human power, the contents are heated. (which is surprising) and at the same time extrude an increasingly viscous (cooled) paste. From the machine it is pumped into a mixer/agglomerator for granulation.

A suitable twin screw extruder for use in the present invention is the APV Ba1c er (CP series), W e r n e r and Pf 1 eiderer (Conttnua series), Wenge r (TF series), Lei stritz (ZSE series) and Buss (LR series) be done.

The extruder can condition the paste by reducing moisture and temperature. can. Moisture is removed in vacuum, preferably at OmmHg (gauge) and −55 mml−1 Can be removed within the range of g (gauge) (atmospheric pressure, O-7.3kPa) .

The temperature can be adjusted by adding solid carbon dioxide or liquid nitrogen directly into the extruder barrel. It can be lowered by Preferably liquid nitrogen is present at up to 30% by weight of the paste. In a preferred embodiment of the present invention, the anionic surfactant is applied in the form of a paste as described above. introducing an amount of surfactant as a powder stream, e.g. by blowing. It can be introduced in powder form. In such embodiments, an open tube for the powder flow maintains the properties and moisture at low levels to prevent anionic surfactant “load” increases. , it is necessary to prevent the production of agglomerates with excessively high surfactant concentrations. other For the introduction of surfactants and/or polymers, preferred agglomerates A liquid stream can also be used as a method. This introduces the surfactant into the liquid stream. By premixing or introducing multiple liquid streams into the agglomerator It is carried out depending on the situation. These two methods specifically require interfacial activity prior to particle formation. When a sex agent mixture is formed, the properties of the finished particles (dispensing properties, gelling properties, (solution rate, etc.). Taking advantage of these differences, each preferred process Particles can be used to

The use of such technology provides advantages over other known methods. high levels of compounds (e.g., nonionic surfactants, citric acid) in the final composition. The main properties of the matrix (caking characteristics: fine dispersion mixing and Granulation "Fine dispersion mixing and/or granulation" as used herein means Fine dispersion mixer with a blade tip speed of about 5 m/s to about 50 m/s It means mixing and/or granulating the mixture in a sacer. mixed and The total residence time of the granulation step is preferably 0.1-10 minutes, more preferably 0.1-10 minutes. 5 minutes, most preferably 0.2-4 minutes. A more preferable blade tip speed is About 10-45 m/s, more preferably 15-40 m/s.

The ratio of paste to powder is such that individual particles are visible at all stages of the process. selected. These particles become sticky at high temperatures, but during the mixing/granulation stage can be carried out simultaneously or sequentially without blockage of the mixer/granulator. These particles must be free-flowing so that the

Any equipment, plastics suitable for surfactant treatment may be used to carry out the method according to the invention. suitable equipment may be used, such as a falling film Including sulfonation reactor, digestion tank, esterification reactor, etc. Mixer/ Since it is an agglomeration system, various mixers/agglomerators can be used. Ru. In a preferred embodiment, the method of the invention is carried out continuously. Especially good The preferred device is the Fuk, manufactured by Fukae Barachik Kogyo KK, Japan. This is a mixer of the aeRFS-C series. This device essentially starts from the top boat. It consists of an accessible bowl-shaped container with a substantially vertical axis of stirring at the bottom of the container. It is equipped with a stirrer and also has a cutter located on its side wall. stirrer and cutter They are operated separately from each other and run at separate variable speeds.

The container is equipped with a cooling jacket and, if necessary, a refrigeration unit.

Other similar mixers suitable for use in the method of the invention are Dierlcs & 5ohne, Germany, is commercially available.　Vshi Leeds, and T.K.

Pharma MatrixR commercially available from Fielder Ltd., UK including. Other suitable mixers are commercially available from Fuji Sangyo KK, Japan. FujiRVG-C series, and Zanchetta & Co5rl, RotoR commercially available from Italy It is.

Other preferred suitable devices include Gustau Eirich Hardheim, Eirichl manufactured by Itsu? Nries RV, LodigeMach Batch mixer manufactured by inebau GmbH, Bubble Born, Germany Lodge for service? For series FM and continuous mixers/agglomerates Baud KM series, Drais Werke GmbH, Mannheim, Germany Drais RT160 series manufactured by Itsu, and Winkwor th Machinery Ltd.

W i n k W o r t h manufactured by Barshire, UK It is RRT 25 series.

With internal chopping blade Littleford Mixer SM Model #FM-130-D-12, and Culsinart Fo with 7.75 inch (19,7 cm) blade od%Model #DCX-Plus are two examples of suitable mixers. Has fine dispersion/granulation ability and 0 ．． Any other mixer with a residence time of 1 to 10 minutes can be used. . “Turbine-type” impeller mixers with several blades on a rotating shaft are preferred. stomach. The invention can be practiced in batch or continuous processes.

operating temperature The preferred operating temperature should be as low as possible.

This is because it is possible to increase the surfactant concentration in the finished particles. Ru. Preferably, the temperature in the agglomerates is 100°C or less, more preferably The temperature is preferably within the range of 10-90°C, most preferably 20-80°C. Inventor The relatively low temperatures used in the process can be achieved using various methods known in the art, such as nitrogen cooling. This can be done by cooling the equipment, cooling water jacket, adding solid CO2, etc. The preferred method is solid CO2, most preferably nitrogen cooling.

Preferred options of the present invention to further increase surfactant concentration in the final particles for liquid streams containing anionic surfactants and/or other surfactants. , increase the viscosity and/or melting point of the paste, reduce the stickiness of the paste, etc. This is done by adding the following ingredients. In a preferred embodiment of the invention The addition of these elements is inline as they are pumped into the agglomerator. It can be carried out at Examples of these elements are the various powders detailed below. Ru.

Final agglomerate composition The present invention produces dense particles for use in detergent compositions. granular The preferred composition of finishing liaglomerates incorporated into detergents is high surfactants. It has concentration. By increasing the surfactant concentration, particles/agglomerates according to the invention The rates are appropriate for a variety of detergent formulations. With such a high surfactant concentration The agglomerate has fewer finishing stages until the finish reaches rear agglomerate. used in other processing steps (spraying, drying, dust removal, etc.) throughout the detergent manufacturing process. This eliminates the need to use large amounts of processing aids (such as inorganic powders).

Particles made by the present invention are large, low dust, free-flowing, Preferably about 0.4 to about 1.2 g/cc, more preferably about 0.6 to about 0.8 It has a bulk density of g/cc. The weighted average particle size of the particles of the present invention is about 200 to about 1 ,000 microns. Preferred particles have a particle size of 200 to 2,000 microns. Has a range. A more preferred granulation temperature is about 10°C to about 60°C, most preferably is about 20°C to about 50°C.

drying The desired moisture content of free-flowing particles according to the invention can be achieved by drying conventional powders such as in a fluid bed dryer. By drying in a dryer, the level can be adjusted to suit the desired application. Ru.

If a hot air fluidized bed dryer is used, care must be taken to avoid deterioration of the heat-sensitive components of the particles. must be considered. It is also preferable to carry out a cooling step before large-scale storage. stomach. This step can be carried out in a conventional fluidized bed operated by cold air. Ru. Drying/cooling of agglomerates can be carried out using conventional powder drying equipment such as rotary dryers. It can also be done inside.

For use in detergents, the final moisture content of the agglomerate must be Must be maintained below the level for transport and storage. accurate moisture 1 novel depends on the composition of the agglomerate, but typically 1-8% native mountain water (i.e. water not bound to crystalline spenes in agglomerates), Most typically it is held at 2-4%.

detergent builders and powders In the methods and compositions of the present invention, any compatible detergent builder or builder may be used. Combinations or powders can be used.

The detergent composition according to the present invention contains a crystalline aluminosilicate ion exchange material of the formula: I can do it.

Na [(AIO), (SiO)], xH20z 2z 2y where Z and y are at least about 6, the molar ratio of z and y is from about 1.0 to about 4, and 2 is From about 10 to about 264.

The amorphous hydrated aluminosilicate material used in this case has the following empirical formula:

M (zAIO-yS102) Here M is sodium, potassium, ammonium or substituted ammonium, 2 is from about 0.5 to about 2, where y is 1, and the material is anhydrous aluminosilicate graphite. per gram, at least 50 milligram equivalents of CaCO3 hardness. Has on-exchange capability. Sodium hydrate with a particle size of approximately 1 to 10 microns Zeolite A is preferred.

The aluminosilicate ion exchange builder material used is in hydrated form and is crystalline. If it is amorphous, it contains about 10 to about 28 weight 96 water, and if it is amorphous, it contains an even larger amount of water. contains. A particularly preferred crystalline aluminosilicate ion exchange material is its crystalline substrate. It contains about 18% to 22% water by weight. Further crystalline aluminosilicate The ion exchange material has a particle size of about 0.1 to about 10 microns. amorphous material chopsticks Often smaller, eg, about 0.01 micron or less. preferred ion The exchange material has a particle size of about 0.2 microns to about 4 microns. What is “particle size”? Identified by conventional analytical techniques such as the Ill standard method using a scanning electron microscope It is the weighted average particle size of the ion exchange material. Crystalline aluminosilicate ion exchange material is at least about 200 mg equivalent of water hardness of CaCO3 calculated on a dry basis /aluminosilicate has a calcium ion exchange capacity of 1 gram, and generally this ion Exchange capacity ranges from approximately 300 mg eq, 7 g to approximately 352 mg eq, 7 g. It's within. The ion exchange material contains at least 2 grains Ca/gal/min/g Has an ion exchange rate based on calcium ion hardness of ram/gallon, and The ion exchange rate ranges from 2 grains/gal/min/gram/gal to about 6 grains/gal. In the range of gallons/minute/grams/gallon. The best aluminum used by builders Minosilicate contains at least about 4 grains/gallon/minute/gram/gallon of calcium. ion exchange rate.

The amorphous aluminosilicate ion exchange material generally contains at least about 50 mg eq. , CaCO3/g Mg ion exchange capacity (12mgMg”7g) and at least It has a Mg exchange rate of approximately 1 grain/gal/min/gram/gal. amorphous The quality was observed when examined by Cu radiation (1,54 angstrom units). It shows no discernible diffraction pattern.

The aluminosilicate exchange materials used in practicing this invention are commercially available. . These aluminosilicates can have crystalline or amorphous structures and are naturally occurring It can be an aluminosilicate or a synthetic aluminosilicate. This a A method for producing luminosilicate ion exchange materials is disclosed in U.S. Patent No. 3,985,669. No. 1, and this is cited as an example. A preferred ion exchange material is zeolite A1 zeolite. It is commercially available under the trademarks Olite B and Zeolite X. Particularly preferred embodiments , this crystalline aluminosilicate ion exchange material has the following formula, where: where X is about 20 to about 30, particularly about 27, and generally has a particle size of about 5 microns or less. do.

The granular detergent of the present invention contains a neutral or alkaline salt having a pH of 7 or above. It can be either inorganic or organic. This builder salt is desirable for detergent particles. It helps give density and bulk. A few salts are inert, but many salts are Acts as a detergent builder substance in the rinse solution.

Examples of neutral water-soluble salts are alkali metal, ammonium, or substituted ammonium chlorides. Contains fluoride, fluoride and sulfate. Alkali metals, especially sodium and its salts is preferred. Sodium sulfate is commonly used in detergent particles and is a particularly preferred salt. It is. Citric acid and generally other organic or inorganic acids are agglomerates. may be included in the granular detergents of the present invention as long as they are chemically compatible with the other ingredients of the composition. Can be done.

Other useful water-soluble salts include compounds commonly known as detergent builder materials. building The carrier is generally a variety of alkali metals, ammonium or substituted ammonium phosphates. . Polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, boric acids selected from salts and polyhydroxysilicates. Alkali metals, especially sodium and its salts as mentioned above are preferred.

Examples of inorganic phosphates are sodium and potassium tripolyphosphates, Pyrophosphates, polymeric metaphosphates and orthophosphates having a degree of polymerization of about 6 to 21. It is a triphosphate. An example of a polyphosphonate bilgu is ethylene diphosphonic acid. Sodium and potassium salts, ethane 1-hydroxy-1,1-diphosphone Sodium and potassium salts of acids, and ethane, 1.1.2-triphosphone Sodium and potassium salts of acids.

Other phosphate builder compounds are described in U.S. Patent Nos. 3,159,581; 3,213,0 30; 3,422,021; 3.422,137. 3,400,176 and and 3°400.148, which is incorporated by reference.

Examples of non-phosphate inorganic building blocks are carbonic acid, bicarbonate, bicarbonate, decahydrated sodium tetraborate. um and potassium, and about 0. 5 to about 4.0, preferably about 1.0 to It is a silicate having a SiO:alkali metal oxide molar ratio of about 2.4. present invention The compositions made by the method do not require extra carbonate to be treated and are preferred. or more than 2% fine potassium carbonate as described in U.S. Pat. No. 4,196,093. and preferably potassium carbonate.

As mentioned above, zeolites, carbonates, silicas, silicates, citrates, phosphates Powders commonly used in detergents, such as auxiliaries such as , perborate, and starch can be used in embodiments of the invention.

polymer A variety of organic polymers can also be used, some of which can be used as builders to improve detergents. Acts as a. These polymers include sodium carboxy-low low alkyl cellulose, sodium low alkyl cellulose and sodium hydride Roxy-lower alkyl cellulose, e.g. sodium carboxymethyl cellulose Rose, Sodium Methyl Cellulose and Sodium Hydroxypropylene cellulose, polyvinyl alcohol (often containing a few polyvinyl acetates) ), polyacrylamides, polyacrylates and various copolymers, e.g. Mention may be made of copolymers of maleic acid and acrylic acid. These polymers The molecular weight of - varies widely but is mostly within the range of 2,000 to 100,000. It is in.

Polymeric polycarboxylate builders are described in U.S. Pat. No. 3,308,067. It will be posted. Substances of this type include maleic acid, itaconic acid, mesaconic acid, fumaric acid, of aliphatic carboxylic acids such as aconitic acid, citraconic acid and methylenemalonic acid. Contains water-soluble salts of homopolymers and copolymers.

Optional ingredients Other ingredients commonly used in detergent compositions may be included in the compositions of the present invention. can. These ingredients are flow aids, color spectra, bleaching agents and bleach activators. agents, foam boosters or foam inhibitors, anti-tarnish and corrosion inhibitors, soil suspension agents , soil remover, dye, filler, brightener, fungicide, pH adjuster, non-builder alkaline Contains potash agents, hydrotropes, enzymes, enzyme stabilizers, chelating agents and fragrances. nothing.

Detergent particles according to the invention are particularly useful in bagged through-the-wash products. It will be done. Materials such as tetrahydrate and monohydrate sodium perborate may also be used in the granular detergent composition of the present invention. It can be included as part of a product. Bagged-through-the-wash products are not accepted by the industry. is known and described in commonly assigned U.S. Pat. No. 4,740,326. other An effective bag consists of a polymeric film in which at least one of its walls has micropores. Ru. As used in this specification, rLAsJ and rAsJ are each referred to as "lauryl base". ``sodium benzenesulfonate'' and ``alkyl sulfate''.

rMESJ means sodium methyl ester sulfonate. "C45" All terms mean C14 and C15 alkyl unless otherwise specified. TAS is a beast means fatty alkyl sulfate.

The invention will be further elucidated by the following non-limiting examples. Percentages are not specified. The amount is based on the amount of mold before drying.

The treatment method is disclosed following the table.

Example 1 This example is a pilot plant scale high shear mixer, Eirich Figure 2 shows the batch mode process in RVO2. First, the powder mixture used in the mixer, this , fill with a mixture of 2:1 zeolite A; fine carbonate or fine citrate. Fill it up. The surfactant is C4.0 with 78% detergent activity and 13% water. Al Kill sulfate. In this example, a 50% solution of NaOH (0.6 kg) was used. Add the liquid to the paste (3k g) in the mixer (Ei r i ch RVO2). After the addition, granulation is started.

During mixing, the paste solidifies and is ground by a mixer at 250 Or, p, m. be done. The process is stopped and powder (1,050 kg) is added. Granulation starts Activate the mixer with Ruma. This process is then stopped and the agglomerates are added to the fluid bed. It is dried in a sieve and classified through a mesh sieve. The produced agglomerates are It has a detergent activity of 60% and a density of 600 g/L. These agglomerates are Shows excellent physical properties.

This example is similar to Example 1. The powder mixture is again in a 2:1 ratio of zeolite. Light A: Fine carbonate.

The surfactant is C4S with 78% detergent activity and 13% water content. It is a water-based paste. In this example, powder (1,05 kg) and paste ( After adding 3k g) to the mixer (Ei r i ch RVO2), Start the grain. Add a certain amount of dry ice to the mixer to lower the temperature to -15°C. let The mixer is then started at a speed of 1600 (2500) r, p, m. first At low temperatures, the mixture is in the form of a fine powder. Run the mixer until the temperature rises to 12°C However, granulation occurs there. The process is stopped and the agglomerates are dried in a fluid bed. , classified through a mesh sieve. The agglomerate produced is 60% detergent. activity and a density of 625 g/L. These exhibit excellent physical properties.

Example 3 This example demonstrates batch processing in a laboratory scale high shear mixer (food processor). Indicates the processing performed in the mode. First fill the mixer with the powder mixture used, The powder in this case is a 2:1 ratio of zeolite A: finely divided sodium carbonate. Surface activity The sex agent is a C45 alkyl sulfate with 72% detergent activity and 24% water content. Ru. In this example, silica powder (40g) was turned into paste (400g). After addition, granulation begins. Upon mixing, the paste solidifies. stop processing and add the powder (105 g) to the paste (335 g). Mix until granulation occurs. Activate the sensor. The process is then stopped and the agglomerates are dried in a fluid bed and met Classify through Shushib. The agglomerate produced is 55-60% detergent This example has excellent physical properties, with activity and density of 650 g/L. Pilot plant twin screw extruder with barrel consisting of Yon, We paste conditioner in continuous mode in rner/Pfleiderer C58 The paste from the extruder is then subjected to laboratory scale high shear stress. A treatment method of immediate granulation in a mixer is shown. Surfactant has detergent activity of 7896 and Sodium alkylbenzene sulfonate (NaLAS) with 18% moisture ) is an aqueous paste. This paste was placed in an extruder at a temperature of 70°C and at a temperature of 150°C. Introduce at a flow rate of kg/hr. The paste coming out of the extruder is Zeolite A: differential carbonate powder in a 2:1 wt% ratio in a high-shear Kamixer Granulate with. Until an average particle size agglomerate of 400-800 μm is obtained. , add the paste to the powder bed. The agglomerate is then dried in a fluid bed and LA Analyze for S content (expressed as activity).

The paste is simply pumped through an extruder operating at 100-120r, p, m. sent. The paste coming out of the extruder is still at 70°C, and the resulting agglomerate The activity of this drug is 32%.

Example 5 The agglomerates are made using the same equipment and weight ratios as in Example 4. This implementation In the example, while pumping the paste through the extruder, the first Contain tap water at 15°C in the second section and odor in the last four sections. The paste is then cooled by a cooling coil containing cooling glycol at -20°C. fixed The exit temperature of the paste under normal conditions is 30°C, and the activity of the obtained agglomerate is The gender is 45%.

Example 6 The agglomerates are made using the same equipment and weight ratios as in Example 4. This implementation In the example, a solid powder of a copolymer of maleic acid and acrylic acid enters the extruder. Added to the paste by mouth. Without cooling, the temperature of the paste leaving the extruder The temperature was 68°C, and the activity of the agglomerate obtained was 38%. Similar to Example 5 If the extruder barrel is cooled, the paste exit temperature is 30°C, and the resulting The activity of glomerate is 54%.

Example 7 The agglomerates are made using the same equipment and weight ratios as in Example 4. But this In the example, instead of NaLAS, a carbon chain length of C14-Cl3 A field containing 6ofIn% sodium alkyl sulfate and 25% moisture. Use surfactant paste. The inlet temperature is also 70°C in this case.

The paste is simply pumped through the extruder and exits at a temperature of 70°C. obtained The activity of agglomerate is 36%.

Example 8 Using the same equipment and weight ratios as in Example 7 and using the alkyl sulfate paste of this example. is used to produce agglomerates. However, in this example, one Vacuum capable of supplying 70mbar vacuum through Nokurel vacuum boat Apply vacuum using a device. In all sections of the barrel at the same time, − Cooling is performed via an internal coil using glycol at 20°C.

The paste leaving the extruder has a moisture content of 22% and a temperature of 25°C. This page The agglomerate produced by ST has an alkyl sulfate activity of 60%.

Example 9 Using the same equipment and weight ratios as in Example 7, and using the alkyl sulfate paste of this example. Agglomerates are produced using However, in this embodiment, the cooling Glycol at -20℃ passing through the coil and a further flow rate of 15kg/hr. It was cooled by liquid nitrogen injected into the fourth section of the tube. from extruder The exiting paste has a temperature of 15°C and the agglomerates obtained are 65% alkylated. It had sulfuric acid activity.

Submission of translation of written amendment (Article 184-8 of the Patent Law) October 12, 1993 1. Display of patent application PCT/US 92102879 2. Name of the invention Chemical composition of surfactant paste to form highly active surfactant particles 3. Patent applicant Address: One, Broctor, End, Cincinnati, Ohio, United States Gamble, Plaza (no street address) Name: The, Broctor, End, Gamble , Company 4, Agent (Postal code 100) 2-3 Shiratama-chome, Maruno, Chiyoda-ku, Tokyo (1) One translation of the written amendment The scope of the claims 1, 1! In the method for producing a shrinking detergent composition, (i) in excess alkali, or neutralize multiple anionic surfactant acids to achieve high activity (at least 40% by weight) anionic surfactant) to form a paste, the paste having a constant δ11 at 70°C. has a viscosity of at least 10 Pa, s and a shear rate of 25 s-1 when a step of making the (ii) increasing the apparent viscosity of the paste at the temperature and the shear rate; conditioning the paste by (its) in the presence of an effective amount of detergent powder in a high shear mixer/granulator. forming highly active detergent particles.

2. Pumping the highly active paste and/or reducing its moisture content. and/or cooling and/or pressing when adding chemical structurants to the paste. 2. A method for carrying out step (i) of claim 1, characterized in that a device is used.

36 The paste has a temperature range of 40℃ to 80℃ and 0 to 7.5kPa (large 2. The introduction boat of the extruder is entered under a vacuum of less than or equal to atmospheric pressure. The method described in.

4. Powder and/or add additional paste and mix these powders and paste in an extruder 4. A method according to claim 2 or 3, characterized in that:

5. The barrel of the mixing section of the extruder is cooled by suitable means, and this cooling Up to 30,721% of solid carbon dioxide or liquid nitrogen is directly added to the extruder barrel. 5. The method according to any one of claims 2 to 4, further comprising the step of adding the How to put it on.

6. Claim 2, wherein the extruder is a twin screw extruder. 5. The method according to any one of items 5 to 5.

7. Any one of claims 1 to 6, wherein the chemical structuring agent is in the form of powder. The method described in Section 1.

Continuation of front page (72) Inventor: Vega, Jose Louis, Belgium, Stromby Coupe-Belle, New Verran, 121.5

Claims (7)

[Claims] 1. In a method for producing a concentrated detergent composition, (i) in excess alkali, or multiple anionic surfactants to neutralize acids and create highly active (at least 40% by weight ionic surfactant) to form a paste, and said paste is measured at 70 °C at least 10 Pa. having a viscosity of s and a shear rate of 25 s; (ii) conditioning the paste; (iii) in the presence of an effective amount of detergent powder in a high shear mixer/granulator; forming highly active detergent particles. 2. Pumping and/or reducing the moisture content of the highly active paste /or extruded upon cooling and/or adding chemical structurants to said paste. A method for carrying out step (ii) of claim 1, characterized in that using a device. 3. The paste has a temperature range of 40°C to 80°C and a temperature range of 0 to 7.5kPa (atmospheric pressure). 3. The device enters the port of the extruder with a vacuum of: How to put it on. 4. Powder and/or Adding additional paste and mixing these powders and paste in the extruder The method according to claim 2 or 3, characterized in that: 5. The barrel of the mixing section of the extruder is cooled by suitable means; up to 30% by weight of solid carbon dioxide or liquid nitrogen directly into the extruder barrel. The method according to any one of claims 2 to 4, characterized in that it comprises the step of adding . 6. Claims 2 to 3, wherein the extruder is a twin screw extruder. 5. The method according to any one of 5. 7. Any one of claims 1 to 6, wherein the chemical structuring agent is in the form of a powder. The method described in.