JPH09279200A - Granular nonionic detergent composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject detergent composition consisting mainly of a nonionic surfactant good in fluidity even after its moisture absorption, and to provide a method for producing the composition. SOLUTION: This detergent composition comprises a nonionic surfactant and a water-soluble high molecular compound which has a low-shear viscosity of 10-150 poise, high-shear viscosity of 0.1-2 poise and thixotropic index of 20-300. This detergent is obtained by compaction and granulation of a detergent component composed of a nonionic surfactant and the above water-soluble high molecular compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a granular nonionic detergent composition containing a nonionic surfactant as a main component, which has good fluidity even when absorbing moisture, and a method for producing the same.

[0002]

2. Description of the Related Art Nonionic surfactants generally have a low foaming property, their detergency is hardly affected by the hardness of water, and they are particularly excellent in dirt dispersibility and stain dispersibility at low temperatures. Furthermore, it is an excellent surfactant because it has good biodegradability, low environmental load, low toxicity and no safety problem. However,
Since nonionic surfactants are generally liquid at room temperature, the exudation of nonionic surfactants from nonionic granular detergent products into detergent containers has been a problem. When the nonionic surfactant seeps into the detergent container, not only the product appearance is deteriorated, but also the detergency is reduced due to the decrease in the nonionic surfactant at the container contact portion, and further, the fluidity of the detergent particles, Caking resistance is adversely affected. Further, since the nonionic surfactant has a property of being weak against heat, the nonionic surfactant is thermally decomposed by the conventional manufacturing method of spray drying a mixed slurry of the surfactant and the washing builder. Is emitted to the atmosphere as exhaust gas, which may cause environmental damage such as air pollution, which is not preferable. Furthermore, since the detergent composition contains a component having a high hygroscopicity as exemplified by a surfactant and an alkali builder, the detergent particles absorb moisture in a high humidity environment, and the fluidity and the resistance of the detergent particles are high. The caking property was adversely affected.

By the way, in Japanese Unexamined Patent Publication No. 4-339898, by blending an amorphous oil-absorbing carrier in an amount of 5 to 20%, the nonionic surfactant is prevented from seeping out. Since the agent itself remains liquid at room temperature, there has been a problem that the nonionic surfactant oozes out and deteriorates the fluidity of the detergent particles, especially in the summer when the temperature exceeds 30 ° C. Also, Japanese Unexamined Patent Publication No.
In Japanese Patent No. 125400, the nonionic surfactant is not spray-dried, but is put into a dry granulation apparatus together with an oil-absorbing carrier to perform a granulation process without giving excessive heat, and further, the detergent particles are made of amorphous silica. A method of coating the surface to suppress deterioration of fluidity due to moisture absorption is disclosed. However, even if the surface of the detergent particles is protected with amorphous silica, if the detergent particles are placed in a high-humidity environment for a long time, the detergent particles will gradually absorb moisture, and the problem of deterioration in fluidity and anti-caking properties still remains. Remains. Further, in JP-A-5-209200, components other than the nonionic surfactant, for example, a washing builder is spray-dried, and the obtained dry particles and the nonionic surfactant are charged into a dry granulation apparatus to produce a granulation product. A method of performing grain treatment and coating the surface of detergent particles with aluminosilicate is disclosed. This is considered to have a merit in terms of effective utilization of manufacturing equipment for a manufacturer who manufactures a conventional low bulk density detergent by a spray drying method. However,
When a slurry containing a cleaning builder is spray-dried without blending a binder component such as a surfactant, a large amount of fine particles are generated, which cannot be removed by a dust collector.
Most of it was released to the atmosphere and could cause air pollution. In addition, the spray-dried particles have a hollow porous structure, which makes them suitable for containing large amounts of oily substances such as surfactants, but their weak particle strength causes the particles to break during production and become porous. Is lost, which is not preferable,
Particles are broken in the transportation line and fine powder is generated, which deteriorates the working environment.

In Japanese Patent Laid-Open No. 62-54799, the surface of the granular nonionic detergent particles is coated with PEG to suppress the exudation of the nonionic surfactant. PEG has a high affinity with water. Therefore, when the detergent particles are placed in a high-humidity environment, the surface of the detergent particles is melted, resulting in deterioration of the fluidity of the detergent particles.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a granular nonionic detergent composition containing a nonionic surfactant as a main component, which has good fluidity even when it absorbs moisture. Another object of the present invention is to provide a method for producing the granular nonionic detergent composition which can produce the above-mentioned granular nonionic detergent composition and has a small environmental load.

[0006]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that nonionic surfactants and water in the atmosphere do not become sticky and have a smooth property. By using in combination with a specific water-soluble polymer compound having, even when the detergent particles placed in a high humidity environment absorb moisture, it was found that the fluidity does not decrease, and the present invention has been completed. It is a thing. That is, the present invention provides the following inventions: (1) A granular nonionic detergent composition characterized by containing a nonionic surfactant and a water-soluble polymer compound having the following properties: Properties: low shear viscosity 10 ~ 150 Poise High shear viscosity 0.1 ~ 2 Poise Thixotropic index 20 ~ 300 and (2) Granular nonionic detergent for consolidating / granulating a detergent component containing a nonionic surfactant and a water-soluble polymer compound. A method for producing a composition, wherein the water-soluble polymer compound has the following characteristics: low shear viscosity 10 to 150 poises high shear viscosity 0.1 to 2 poises thixotropic index 20 to 300. Method.

In particular, the conventional technique is based on the idea of suppressing moisture absorption into the detergent particles as much as possible, whereas the present invention does not impair the physical properties of the detergent particles even when moisture is absorbed. There is a big difference in using.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the present invention, various nonionic surfactants can be used as the nonionic surfactant. Examples of preferable nonionic surfactants include:
The following can be mentioned. (1) C3-C22, preferably C8-C18 aliphatic alcohol with C2-C4 alkylene oxide on average 3
Polyoxyalkylene alkyl (or alkenyl) ether added to ３０30 mol, preferably 7-20 mol. Among these, polyoxyethylene alkyl (or alkenyl) ether and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ether are preferable. (2) polyoxyethylene alkyl (or alkenyl)
Phenyl ether. (3) A fatty acid alkyl ester alkoxylate represented by the following formula in which an alkylene oxide is added between ester bonds of a long-chain fatty acid alkyl ester. R ¹ CO (OA) _n OR ² (R ¹ CO represents a fatty acid residue having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. OA represents 2 to 4 carbon atoms such as ethylene oxide and propylene oxide, preferably 2 to 3 represents an addition unit of alkylene oxide, n represents the average number of moles of alkylene oxide added, and generally 3 to 3
It is a number of 0, preferably 7 to 20. R ² has 1 carbon atom
Represents a lower alkyl group optionally having 3 to 3 substituents. (4) Polyoxyethylene sorbitan fatty acid ester. (5) Polyoxyethylene sorbite fatty acid ester. (6) Polyoxyethylene fatty acid esters. (7) Polyoxyethylene hydrogenated castor oil. (8) Glycerin fatty acid ester.

Among the above nonionic surfactants, polyoxyethylene alkyl (or alkenyl) ethers having a melting point of 40 ° C. or less and an HLB of 9 to 16 and fatty acid methyl ester ethoxylates obtained by adding ethylene oxide to fatty acid methyl ester are particularly preferable. Used for. Further, these nonionic surfactants may be used as a mixture. In the present invention, the nonionic surfactant is preferably 10 to 10 based on the weight of the granular nonionic detergent composition.
50% by weight, more preferably 12 to 40% by weight, particularly preferably 15 to 35% by weight. This amount is 10
If it is less than 10% by weight, not only the concentration of the nonionic surfactant in the resulting detergent particles is low but also the bulk density is low, so a good detergent effect cannot be obtained unless the amount of detergent used is increased, and the compactness of recent years It is not preferable because it causes conflicting results. It is also not preferable in terms of resource saving. On the other hand, if it exceeds 50% by weight, it is difficult to suppress the exudation, which is not preferable. As the water-soluble polymer compound used in the present invention,
Those having the following characteristics are used. Low shear viscosity 10-150 poise High shear viscosity 0.1-2 poise Thixotropic index 20-300 Here, low shear viscosity is Brookfield Synchro at 50 ° C. for a slurry having the following model composition. -Lectric) type viscometer. It is a value measured after 30 seconds in a 4-type rotor at a rotation speed of 20 rpm. The model composition slurry is 21 parts by weight of zeolite, 2 parts by weight of sodium sulfite, 21 parts by weight of sodium carbonate, 1 water-soluble polymer compound.
It consists of 55 parts by weight of water and 55 parts by weight of water.

The high shear viscosity is measured as follows. That is, a slurry having the same model composition was used at 50 ° C. using a Haake Rotovisko type viscometer MK500 type and a shear rate D (Sec. ⁻¹ ) of 0 to 0.
The shear stress τ (dyne / cm ³ ) is measured while continuously changing to 1000. The relationship between D and τ is approximated to the following generalized Bingham equation to obtain constants A, B and C. τ = A × D ^B + C Using the formula thus obtained, D = 10000
The viscosity at (Sec. ^-1 ) is calculated from the following formula, and this viscosity value η is defined as the high shear viscosity. η = τ / D = (A × D ^B + C) / D It should be noted that any of the Herkel-Rotovisco viscometer SV-1 type rotor and the like can be used, but in the present invention, the clearance between the rotor and the stator is mainly used. 1.45 mm was used. The high shear viscosity can be measured by the Weissenberg Rheogoniomete in addition to the Herke-Rotovisco viscometer.
r) type cone-flat plate type viscometer, Bingham (B
ingham) type viscometer, and the like, but a Herkelot-Visco type viscometer is preferable in terms of measurement accuracy.

Further, the thixotropic index is calculated by the following formula. Thixotropic Index = Low Shear Viscosity / High Shear Viscosity The water-soluble polymer compound needs to be present inside the detergent particles from the viewpoint of improving the fluidity of the detergent particles when absorbing moisture. Therefore, it is preferable that the water-soluble polymer is swelled or dissolved in water to be blended. For example, a method of adding a water-soluble polymer compound in the state of being swollen in water or in the form of an aqueous solution thereof during the consolidation / granulation treatment of a nonionic surfactant and a washing builder, or a water-soluble solution. Aqueous polymer and an aqueous solution containing a detergent builder are prepared, and then mixed particles with a washing builder are prepared by a method such as a spray drying method, and the resulting detergent builder particles are mixed with a nonionic surfactant and other detergent components. In addition, a method of consolidating and granulating may be used. Here, the compaction / granulation treatment means a granulation operation for densifying the detergent particles.
There is a law. (1) A kneader or other kneading machine (kneading machine) is put into the kneader to knead the mixture to form a high-density detergent solid, which is then crushed to a predetermined particle size to produce a high-bulk density granular detergent. Japanese crushing granulation method. (2) A stirring granulation method in which a detergent component is placed in a stirring granulator and the particles are densified and granulated in the presence of a liquid binder to produce a high bulk density granular detergent.

Among these methods, a slurry of a water-soluble polymer and a detergent builder is prepared in advance by a method such as a spray drying method to prepare detergent builder particles, and then the obtained detergent builder particles are compacted together with a nonionic surfactant. The method of granulating and granulating is preferable. In this case, it is more preferable because the non-ionic surfactant can be absorbed / retained in the mixed particles, the particle strength of the cleaning builder powder can be improved, and the fine particles can be suppressed. Among the compaction / granulation treatments, the kneading / crushing granulation method is particularly preferable because it is easy to achieve high density and uniform components. The low shear viscosity is 10 to 150 poise, preferably 20 to 120 poise, and more preferably 30 to 100 poise. When this value is less than 10 poise, when the particles containing the water-soluble polymer and the washing builder are produced by spray drying, the strength of the dried particles becomes insufficient, which is not preferable. On the other hand, when this value exceeds 150 poise, the obtained detergent particles tend to be lumped in water, and further, the porosity of the particles containing the water-soluble polymer compound and the washing builder is lowered, and It is not preferable in terms of transportation because the absorbability of an oily substance such as an activator is easily lost and the viscosity of a slurry containing a water-soluble polymer compound and a washing builder becomes high.

The value of high shear viscosity is 0.1 to 2 poise, preferably 0.2 to 1.5 poise, more preferably 0.3.
It is preferably ˜1.0 poise. If this value is less than 0.1 poise, when the slurry containing the water-soluble polymer and the washing builder is spray-dried, the atomization of the slurry becomes too good, and the dried powder contains a large amount of fine powder, which causes agglomeration. Not preferable in terms of dust. On the other hand, if this value exceeds 2 poise, the solubility of the detergent in water may decrease. Further, in the case of spray drying, the atomization of the slurry becomes too bad, the drying efficiency decreases, and even if it can be dried, tadpole-shaped particles are generated, and the fluidity of the dried particles is deteriorated, which is preferable. Absent. Slurry containing water-soluble polymer and washing builder shows plastic flow similar to Bingham fluid, apparent viscosity lowers for stress above yield point, flows, and viscosity recovers with time when left standing. Exhibits a reversible phenomenon called so-called thixotropic property. The degree of this is indicated by the thixotropic index, which is defined by the above equation. The thixotropic index is 20 to 300, preferably 40 to 25.
A value of 0, more preferably 80 to 200, is suitable. When the thixotropic index is less than 20, it is not preferable because the effect of improving the fluidity of the moisture-absorbed detergent particles is small. On the other hand, when the thixotropic index exceeds 300, the solubility of the obtained detergent particles is deteriorated and the oil absorption of the spray-dried particles containing the washing builder is deteriorated, which is not preferable.

As the water-soluble polymer compound, various water-soluble polymer compounds can be used as long as they have the above characteristics. Of these, particularly preferable water-soluble polymer compounds include, for example, carboxymethyl cellulose sodium salt having an etherification degree of 1.0 or more (hereinafter, simply,
"CMC-Na"), sodium alginate, crosslinked polyacrylic acid having a crosslink in the molecular structure or an alkali metal salt thereof, xanthan gum, locust bean obtained by a polymerization reaction from an acrylic acid monomer and a polyfunctional monomer. Examples thereof include gum. CMC-
In the pyranose ring of cellulose that constitutes Na,
The maximum number of etherified hydroxyl groups is three. Therefore, the degree of etherification is 3 at the maximum. CMC-Na
The degree of etherification of is preferably 1.1 to 1.8, and particularly preferably 1.2 to 1.5. Also,
The weight average molecular weight of CMC-Na is usually 50,000 to 50.
10,000, preferably 100,000 to 400,000 is suitable. CMC-N
Specific examples of a include, for example, CMC-Na having an etherification degree of 1.2 and a weight average molecular weight of 120,000, or an etherification degree of 1.
3, CMC-Na having a weight average molecular weight of 250,000, further CMC-Na having an etherification degree of 1.5 and a weight average molecular weight of 300,000
And the like.

The weight average molecular weight of sodium alginate is usually 100,000 to 400,000, preferably 150,000 to 300,000. Specific examples of sodium alginate include Duck Algin NSPM (weight average molecular weight 200,000) manufactured by Kibun Food Chemifa Co., Ltd., and Duck Algin NSPH (weight average molecular weight 300,000) manufactured by Kibun Food Chemifa Co., Ltd. It can be preferably mentioned. The crosslinked polyacrylic acid is obtained by copolymerizing an acrylic acid monomer and a polyfunctional monomer. Examples of the polyfunctional monomer include the following functional monomers. (1) Bifunctional monomer Examples of this include vinyl monomers such as divinylbenzene, divinylsulfone, divinylsulfite and divinylether, glycidyl acrylate, 1,3-butanediol diacrylate, ethylene diacrylate. Glycol, tetrahydrofurfuryl acrylate,
Acrylic compounds such as N, N'-methylenebisacrylamide, glycidyl methacrylate, methacrylic compounds such as ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate, ethylene glycol diglycidyl ether, and Propylene glycol diglycidyl ether, allyl glycidyl ether, epoxy compounds such as ethylene glycol diglycidyl ether acrylate, isopropyl tristearoyl titanate, organometallic compounds such as γ-methacryloxypropyltrimethoxysilane, and further diallyl phthalate. . (2) Trifunctional monomer As this example, for example, an acrylic compound such as pentaerythritol triacrylate, trimethylolpropane triacrylate, 2-ethyl-2-hydroxymethyl-1,3-propanediol triacrylate, or the like, Trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, trimethacrylic acid 2
Examples thereof include methacrylic compounds such as -ethyl-2-hydroxymethyl-1,3-propanediol, triallyl isocyanurate, and triallyl trimellitate. (3) Tetrafunctional Monomer As this example, for example, tetramethylolmethane tetraacrylate and the like can be mentioned.

The crosslinked polyacrylic acid constitutes a crosslinked structure by a functional group derived from a polyfunctional monomer. This cross-linked polyacrylic acid comprises an acrylic acid monomer and a polyfunctional monomer in a polyfunctional monomer / acrylic acid monomer (weight ratio) ratio of usually 10 ^{−5 to} 0.05, preferably 5 × 10 ^−4. It was obtained by radical polymerization reaction at about 0.01. The carboxylic acid group of the crosslinked polyacrylic acid may form a salt with an alkali metal such as sodium, potassium or lithium. The weight average molecular weight of the crosslinked polyacrylic acid is usually 100,000 to 10,000,000, and preferably 1,000,000 to 7,000,000. Specific examples of the crosslinked polyacrylic acid include, for example, Nippon Pure Chemical Co., Ltd.
Manufactured by Rheozic 252L (weight average molecular weight, 2,000,000)
, Nippon Pure Chemical Co., Ltd., Rheozic 250H (weight average molecular weight 4 million), Nippon Pure Chemical Co., Ltd., Junron PW
111 (weight average molecular weight 4,000,000) and the like can be preferably cited. Specific examples of the crosslinked polyacrylic acid or alkali metal salt include crosslinked sodium polyacrylate (manufactured by Nippon Pure Chemical Co., Ltd., Rheojic 252L, average molecular weight, 2,000,000), crosslinked sodium polyacrylate (Nippon Pure Chemical). Rheojic 250H, average molecular weight 40
Crosslinked polyacrylic acid (manufactured by Nippon Pure Chemical Co., Ltd., Junron PW111, average molecular weight 4,000,000) and the like.

Specific examples of xanthan gum and locust bean gum include xanthan gum (Dainippon Pharmaceutical Co., Ltd.).
Manufactured by Sansei Co., Ltd.) and Locust Bean Gum (manufactured by Sansho Co., Ltd.). Preferable examples of the water-soluble polymer compound have an etherification degree of 1.0 or more and an average molecular weight of 12 or more.
Over 10,000 carboxymethylcellulose sodium salts (C
MC-Na), sodium alginate having an average molecular weight of 200,000 or more, and crosslinked polyacrylic acid having an average molecular weight of 500,000 or more or an alkali metal salt thereof. Furthermore, from the viewpoint of heat resistance during spray drying, the weight average molecular weight is 5
Particularly preferably, cross-linked polyacrylic acid having an amount of 0,000 or more or its alkali metal salt is used. These water-soluble polymer compounds may be used alone or in combination. By the way, carboxymethylcellulose sodium salt (CMC-Na) having an etherification degree of 0.4 to 0.6, which is said to have a higher anti-redeposition effect than before, and which has been used in detergent compositions, is
Since it has poor alkali resistance, a part or all of it reacts with the alkali metal salt to be transformed into a water-insoluble fibrous substance, which is not suitable for the present invention. In addition, it is said that the chelating effect is high, and the linear type (without cross-linking in the molecular structure) sodium polyacrylate used in the detergent composition rather deteriorates the fluidity of the detergent particles under the moisture absorption condition. Not suitable for the present invention.

In the present invention, the water-soluble polymer compound is
Based on the weight of the granular nonionic detergent composition, preferably
The content is 0.05 to 5% by weight, more preferably 0.1 to 4% by weight, and particularly preferably 0.2 to 3% by weight. This amount is 0.
If the amount is less than 05% by weight, it is insufficient to improve the fluidity of the obtained detergent particles when they absorb moisture, which is not preferable. On the other hand, if it exceeds 5% by weight, the resulting detergent particles are not preferable because they tend to be lumped in water. As the cleaning builder, an inorganic builder or an organic builder can be used without particular limitation. As the inorganic builder, sodium carbonate, sodium hydrogen carbonate, carbonates such as potassium carbonate, sodium sulfite, sulfite salts such as sodium hydrogen sulfite,
Silicates such as sodium silicate, sodium aluminosilicate, crystalline layered silicate, and sodium tripolyphosphate,
A condensed phosphate such as sodium pyrophosphate is mainly used. Organic builders are used as necessary, for example, citrate, organic acid salts such as succinate, acrylic acid-maleic acid copolymers, polymer chelate builder such as acrylic acid-methacrylic acid copolymers, Acetates such as EDTA and nitriloacetic acid can be used.

In the present invention, the wash builder is preferably 10 to 10 based on the weight of the granular nonionic detergent composition.
The content is 80% by weight, more preferably 15 to 70% by weight, and particularly preferably 20 to 60% by weight. This amount is 10
If it is less than 10% by weight, the builder effect on the resulting detergent is insufficient and it is difficult to obtain a sufficient cleaning effect. On the other hand, 80% by weight
Even if it exceeds the above, the builder effect will reach a ceiling, and even if it exceeds it, the effect accompanying it will not particularly increase. The granular nonionic detergent composition of the present invention is not particularly limited as long as it is an optional component usually blended with a detergent raw material, and various types can be used. As such components, for example, the following components can be blended in addition to the above-described detergent builder. (1) As a fluorescent agent, bis (triazinylamino) stilbenedisulfonic acid derivative, bis (sulfostyryl) biphenyl salt [Tinopearl CBS], and the like. (2) As the enzyme, lipase, protease, cellulase, amylase and the like. (3) As a bleaching agent, percarbonate, perborate and the like. (4) As an antistatic agent, a cationic surfactant such as a dialkyl type quaternary ammonium salt. (5) As surface modifiers, finely divided calcium carbonate, finely divided zeolite, bentonite, polyethylene glycol and the like. (6) As anionic surfactant, α-sulfo fatty acid methyl ester salt, linear alkylbenzene sulfonate,
α-olefin sulfonate, alkyl sulfate, fatty acid soap and the like. (7) Polyethylene glycol or the like as a recontamination preventive agent. (8) As a bulking agent, sodium sulfate, potassium sulfate,
Sodium chloride etc. (9) As a reducing agent, sodium sulfite, potassium sulfite and the like.

These optional components can be blended in the granular nonionic detergent composition of the present invention by various blending methods. For example, these components may be blended in the granulation step, or may be mixed with the detergent particles obtained by the granulation treatment. Next, a preferred method for producing the granular nonionic detergent composition of the present invention comprises the following steps. Step A A nonionic surfactant, a water-soluble polymer compound, a washing builder, and other optional components to be added as necessary are consolidated. This compaction treatment is introduced into a kneading extruder such as a kneader or an extruder, preferably a kneader,
Mixing in a kneader while applying shearing force to form granules (solid detergent), or a high speed mixer,
It is introduced into a stirring type granulator such as Sugi mixer, Loedige mixer, Henschel mixer and the like to be stirred and granulated to increase the density of the detergent. Step B The solid detergent obtained in Step A is crushed and granulated, preferably,
Crush with a cutter mill. This step can be omitted when the compaction process is performed by stirring granulation and the target particle size is reached. Step C The detergent particles obtained in Step A or B are mixed with an optional component such as an enzyme or a fragrance.

Each of these steps will be further described below. <Step A> The addition form of the water-soluble polymer compound is not particularly limited in terms of improving the fluidity of the detergent particles when absorbing moisture, as long as it can be present inside the detergent particles.
For example, when performing a consolidation treatment of a nonionic surfactant and a cleaning builder, a method of adding a water-soluble polymer by dissolving or dispersing in water or a nonionic surfactant, a method of adding in the form of powder, spraying Examples thereof include a method of adding a mixture of a water-soluble polymer prepared by a drying method and a washing builder. Among these, a method of consolidating a mixture of a water-soluble polymer prepared by a spray drying method and a washing builder, together with a nonionic surfactant and other detergent components, improves the particle strength of the washing builder powder and generates fine powder. It is more preferably used because an additional effect such as suppression can be obtained.
When preparing a mixture of a water-soluble polymer and a washing builder by the spray drying method, the following steps are added. (1) A step of preparing a slurry containing a water-soluble polymer compound and a washing builder. (2) A step of spray-drying the slurry to prepare particles containing a water-soluble polymer compound and a washing builder.

As a method for producing the slurry, specifically, it is preferable to dissolve the water-soluble polymer compound in a predetermined amount of water, then add a washing builder, and uniformly mix. If the water-soluble polymer compound is added after first adding the washing builder to the water, the water-soluble polymer compound will be lumped and it will take a long time to dissolve, which is not preferable. The water-soluble polymer compound in the slurry is usually 0.1 to 2% by weight, preferably 0.2 to 2% by weight, more preferably 0.3 to
It is compounded in an amount of 2% by weight. When the content of the water-soluble polymer compound is less than 0.1%, the effect of suppressing generation of fine powder when the slurry is spray-dried and the effect of improving the strength of dry particles are small, which is not preferable. On the other hand, if it exceeds 2% by weight, the porosity of the dry particles is lowered, and the slurry tends to be gelled, which makes transportation difficult, which is not preferable. The content of the cleaning builder in the slurry is usually 18 to 59% by weight, preferably 2
It is preferably 3 to 54% by weight, more preferably 28 to 49% by weight. The content of cleaning builder is 18% by weight
If it is less than 1, the amount of water vaporized by drying increases, which is not preferable in terms of energy saving and resource saving, and is inefficient in terms of production capacity, which is not preferable. On the other hand, if the content of the cleaning builder exceeds 59% by weight, the amount of the unclean residue of the cleaning builder in the slurry increases, which may cause precipitation and condensation in the transportation pipe to cause blockage or wear of the pipe. It is not preferable because

The water content in the slurry is usually 40-80% by weight, preferably 45-75% by weight, more preferably 5%.
It is preferably from 0 to 70% by weight. When the water content of the slurry exceeds 80% by weight, more water is evaporated by drying, which is not preferable in terms of energy saving and resource saving.
On the other hand, if the content is less than 40% by weight, the amount of undissolved residual washing builder in the slurry increases, which may cause precipitation and condensation in the transportation pipe, causing blockage, or abrasion of the pipe, which is not preferable. The temperature of the slurry is usually 30-
80 ° C, preferably 40 to 70 ° C, more preferably 45
Controlled at ~ 65 ° C. If this temperature is lower than 30 ° C, it takes a long time to dissolve the water-soluble polymer and the washing builder, which is not economical. On the other hand, when the temperature exceeds 80 ° C,
The water-soluble polymer depolymerizes, and the atomization of the slurry becomes too good, and the dried powder contains a large amount of fine powder, which is not preferable in terms of dust collection and improves the fluidity of the detergent particles when they absorb moisture. This is not preferable because the effect is diminished. In addition, a fluorescent agent, a filler, and the like may be added to the slurry, if necessary. A general spray dryer or a fluidized bed dryer is preferable from the viewpoint of production capacity, and a spray dryer is particularly used. The spray drying device is roughly classified into a pressure nozzle type spray drying device and a disk type spray drying device, but the pressure nozzle type spray drying device is preferable in terms of porosity of dried particles, suppression of fine powder, and production capacity. . The droplet size of the slurry sprayed in the spray dryer is usually 100 to 500 μm.
, Preferably 150 to 450 μm, more preferably 2
The nozzle type or pressure and the disk rotation speed are controlled so as to be from 00 to 400 μm. The hot air temperature in the spray dryer is usually 220 to 400 ° C., preferably 24.
The temperature is set to 0 to 350 ° C, more preferably 260 to 300 ° C.

The detergent builder particles produced in this manner are mixed, for example, in a kneading extruder, preferably a closed-type compaction treatment device, more preferably a horizontal continuous kneader, and a nonionic surfactant, It is introduced together with optional components and mixed in a kneader while applying a shearing force to form a granulated product (solid detergent). In addition to the kneader, a single-screw or twin-screw extruder can be used. Specific examples of the kneading extruder include a KRC kneader manufactured by Kurimoto Iron Works Co., Ltd. The kneading extruder is generally 30 to 60 ° C., preferably 35 to 55 ° C.
More preferably, it is 40 to 50 ° C. If the temperature is lower than 30 ° C., the load on the kneading extruder tends to be excessive, which is not preferable. On the other hand, when the temperature is higher than 60 ° C., on the contrary, the kneaded product tends to adhere to the crusher, which is not preferable. The treatment time is usually 0.2 to 2 minutes, preferably
It is 0.5 to 1 minute. In the stirring granulation method, as a stirring granulator, there is a stirring blade inside the granulator such as a high speed mixer, a Shugi mixer, and a Loedige mixer, and between the stirring blade and the inner wall surface of the granulator. To produce the granular nonionic detergent composition of the present invention by introducing the above-mentioned detergent builder particles, nonionic surfactant and other components into an internal stirring type granulator having a clearance of 30 mm or less and treating the granules. You can The temperature of the stirring granulation is generally 20 to 60 ° C, preferably 30 to 50 ° C, more preferably 35 to 50 ° C. If the temperature is lower than 20 ° C, granulation is difficult to proceed, which is not preferable. On the other hand, when the temperature is higher than 60 ° C., on the contrary, adhesion to the granulator occurs and the load tends to become excessive, which is not preferable. The processing time in the stirring granulation process is usually 1 to 10
Minutes, preferably 2-8 minutes. <Step B> As the crushing granulator, for example, Fitzmill (DKASO6 type manufactured by Hosokawa Micron) can be used. After crushing and granulating with a crushing granulator, preferably a cutter mill, a consolidation treatment is performed. In this case, for example, finely divided aluminosilicate may be added as a grinding aid during crushing and granulation.

The crushing treatment is generally 5 to 30 ° C., preferably 10 to 25 ° C., more preferably 10 to 20 ° C. When the temperature is lower than 5 ° C, dew condensation is likely to occur, which is not preferable. On the other hand, when the temperature is higher than 30 ° C., on the contrary, the adhesion to the crusher is likely to occur, which is not preferable.
The treatment time is usually 1 to 30 seconds, preferably 3 to 30 seconds.
Seconds. The detergent particles thus produced may be subjected to a coating treatment by adding a coating agent in a rolling drum, for example. This can improve the flow properties. As a coating agent, JI
An inorganic fine powder having a content of 50% or more passed through a S200 mesh sieve is suitable, and examples of the material include carbonates such as sodium carbonate and calcium carbonate, and silica such as amorphous silica, calcium silicate and magnesium silicate. Aluminosilicates such as acid salts and zeolites can be used. The coating agent is generally contained in the granular nonionic detergent composition of the present invention in an amount of 0.5 to 15% by weight, preferably 1 to 10%.
Used in amounts by weight. <Step C> The detergent particles produced in this manner include an enzyme,
A fragrance or the like can be added later.

The obtained granular nonionic detergent composition of the present invention has an average particle size of 300 to 3000 μm, preferably 3
50 to 2000 μm, particularly preferably 400 to 1000
μm, and the bulk density is 0.5 to 1.2 g / ml, preferably 0.1.
6 to 1.1 g / ml, particularly preferably 0.65 to 1.0 g / ml.

[0027]

The present invention will be described below in more detail with reference to examples and comparative examples. However, in Examples and Comparative Examples, each sample was evaluated by the following test methods. [Dry Particle Strength Test] Among the dry particles, JIS 24 mesh pass 42 mesh on particles were collected and passed through SUS304 piping (direct system 10 cm × length 20 m) in which air at a wind speed of 30 m / sec is flowing. The particle size and bulk density before and after passing were measured. The weaker the particle strength, the higher the bulk density after passing through, and the smaller the particle diameter. ⊚: Change in bulk density ≦ 0.03 g / ml, Change in particle size ≦
30 μm ○: 0.03 g / ml <change amount of bulk density ≤ 0.05 g / ml, 3
0 μm <change amount of particle size ≦ 80 μm Δ: 0.05 g / ml <change amount of bulk density ≦ 0.12 g / ml, 8
0 μm <change amount of particle size ≦ 150 μm x: change amount of bulk density> 0.12 g / ml, change amount of particle size>
150 μm [fluidity test] 500 g of detergent particles were put on the entire surface of a stainless steel container (length 30 cm × width 20 cm × depth 10 cm) so as to have the same thickness, and this was placed in a constant temperature and humidity chamber at 30 ° C and 85% RH. After the solution was put in and the detergent was allowed to absorb moisture so that the water content was 10 to 15%, the fluidity before and after moisture absorption was measured by the discharge method based on JIS Z2502. [Solubility test] Tap water at 10 ° C was put into a 500 ml beaker, 5 g of the detergent composition was put therein, and the mixture was stirred for 3 minutes. Next, remove the undissolved detergent particles onto a nylon cloth, and
After drying at 05 ° C. for 2 hours, the dissolution residue represented by the following formula was calculated and evaluated according to the following criteria.

Dissolution residue (%) = {(dissolved residue at 105 ° C. for 2 hours dried product g) / 5 g} × 100 ⊚: 0% ≦ dissolved residue <1% ◯: 1% ≦ dissolved residue <5% Δ : 5% ≦ dissolved residue <10% ×: 10% ≦ dissolved residue% [Damaging test] 5 g of the sample was gently placed in a beaker containing 1 liter of tap water at 15 ° C. and shaken gently after 1 minute to prepare a sample. The dispersed state of was observed. ◎: Not lumped ○: Slightly lumped △: Slightly lumped ×: A lot of lumped [bleeding test] Coated cardboard from the outside (basis weight: 35
0 g / m ² ), wax sand paper (basis weight: 30 g / m ² ) and kraft pulp paper (70 g / m ² )
A box measuring 15 cm in length × 9.3 cm in width × 18.5 cm in height was prepared.
Put 2.0 kg of sample in this box, store it in a thermo-hygrostat at 30 ° C and 85% RH for 30 days, take out all the detergent, and visually check the degree of seeping out of the contact area with the detergent inside the box. The following criteria evaluated.

⊚: No bleeding was observed ◯: Slight bleeding was observed Δ: Slight bleeding was observed ×: Many bleeding was observed [moisture of the detergent] 10 g of detergent was placed in a glass petri dish and 1
The weight loss at 05 ° C for 2 hours was measured and calculated by the following formula. Water content (%) = {weight reduction (g) -0.1 × 10 × nonionic surfactant content (%) / 100} / 10 [bulk density] The bulk density was measured according to JIS Z2504. [Oil absorption amount] Based on JIS K6220. [Heat resistance] The sample was placed in a constant temperature bath and heated at a temperature rising rate of 2 ° C / min, and the temperature at which the sample discolored was measured. Examples 1 and 5 and Comparative Examples 1, 2, 4, and 6 As shown in Table 1 below, after the fluorescent agent and the water-soluble polymer were dissolved in water at 50 ° C, a washing builder was added to form a slurry. Prepared (water content 55% by weight). Next, this slurry was sprayed into a spray dryer using a spray nozzle and dried at a hot air temperature of 260 to 300 ° C to obtain dry particles. Next, the dried particles, a nonionic surfactant and other components (excluding enzymes and fragrances) were put into a continuous kneader (KRC-2 type manufactured by Kurimoto Iron Works Co., Ltd.) and kneaded at 40 ° C. for 1 minute. , Manufactured a solid detergent. This solid detergent, together with A-type zeolite as a grinding aid, was put into a Fitzmill (Hosokawa Micron Co., Ltd., DKASO6 type),
Grinding treatment was carried out at 15 ° C. for 5 seconds until the average particle diameter became 500 μm. Finally, type A zeolite is added in a rolling drum to coat the obtained detergent particles, and other optional components such as enzymes and fragrances are further added to obtain a granular nonionic detergent composition (average particle size 500 μm). It was Examples 2 to 4 and Comparative Example 3 A Ledige mixer (M-20 type, manufactured by Matsubo Co., Ltd.) was used as a granulating device, and a nonionic surfactant and a drying agent were used in the same manner as in Example 1. Particles and other ingredients are added, and the mixture is stirred and granulated at 40 ° C. for 3 minutes, and finally, A-type zeolite is added in a rolling drum to coat the obtained detergent particles, and further, other enzymes, fragrances, etc. Add optional ingredients,
A granular nonionic detergent composition having an average particle size of 500 μm was produced. Example 6 5% by weight aqueous solution of water-soluble polymer, nonionic surfactant, cleaning builder and other ingredients (excluding enzyme and fragrance)
Were put into a continuous kneader (KRC-2 type manufactured by Kurimoto Iron Works Co., Ltd.) and kneaded at 40 ° C. for 1 minute to produce a solid detergent.
This solid detergent, along with A-type zeolite as a grinding aid, was fitted with Fitzmill (Hosokawa Micron DK, DK
ASO6 type) and pulverized at 15 ° C. for 5 seconds until the average particle diameter became 500 μm. Finally, type A zeolite was added in a rolling drum to coat the obtained detergent particles, and other optional components such as enzymes and fragrances were further added to give a granular nonionic detergent composition (average particle size 500 μm).
I got Comparative Example 5 The procedure of Example 2 was repeated except that the water-soluble polymer was powder-blended with the granular nonionic detergent composition (average particle size 500 μm) obtained by the granulation treatment. [Raw Materials] The nonionic surfactant, water-soluble polymer compound and cleaning builder used in Examples and Comparative Examples are as follows. Nonionic Surfactant (1) Nonionic Surfactant-1 C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₇ H (Nippon Science Co., Ltd.)
Ltd. Konoru polyoxyethylene alkyl ether obtained by averaging 7 moles addition of ethylene oxide to 20P) (2) nonionic surfactant _{-2 C 13 H 27 O (CH} 2 CH 2 O) 15 (CH 3 CHCH
₂ O) ₃ H (Diadol contains ethylene oxide on average 1
5 mol, polyoxyethylene polyoxypropylene alkyl ether added with 3 mol of propylene oxide on average) (3) Nonionic surfactant -3 C ₁₁ H ₂₃ CO (OCH ₂ CH ₂ ) ₉ OCH ₃ water-soluble polymer compound (1 ) Water-soluble polymer compound-1 (reference) Polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Gohsenol GM-14L) Low shear viscosity = 0.6, high shear viscosity = 0.1, thixotropic index = 6 ( 2) Water-soluble polymer compound-2 (reference) Linear sodium polyacrylate (manufactured by Nippon Pure Chemical Co., Ltd.,
JULIMER AC-10S, average molecular weight 5,000) Low shear viscosity = 0.1, high shear viscosity = 0.01, thixotropic index = 10 (3) Water-soluble polymer compound-3 carboxymethylcellulose sodium salt (Daicel Chemical Industries ( Co., Ltd., CMC Daicel 1330, average molecular weight 120,000, degree of etherification 1.2) low shear viscosity = 10, high shear viscosity = 0.33, thixotropic index = 30 (4) water-soluble polymer compound-4 alginic acid Sodium (Kibun Food Chemifa Co., Ltd.,
Duck Algin NSPH, average molecular weight 200,000) Low shear viscosity = 110, high shear viscosity = 1.8, thixotropic index = 61 (5) Water-soluble polymer compound-5 Crosslinked sodium polyacrylate (Nippon Pure Chemical Co., Ltd. ) Made by
Rheojic 252L, average molecular weight 2,000,000) Low shear viscosity = 35, high shear viscosity = 0.35, thixotropic index = 100 (6) Water-soluble polymer compound-6 Crosslinked sodium polyacrylate (Nippon Pure Chemical Co., Ltd.) Made by
Rheozic 250H, average molecular weight 4,000,000) Low shear viscosity = 48, high shear viscosity = 0.3, thixotropic index = 160 (7) Water-soluble polymer compound-7 (reference) Carboxymethyl cellulose sodium salt (Daicell Chemical Industries Ltd. ) Manufactured by CMC Daicel 1190, average molecular weight 180,000, etherification degree 0.6) low shear viscosity = 5, high shear viscosity = 0.03, thixotropic index = 167 (8) water-soluble polymer-8 cross-linking type Polyacrylic acid (Nippon Pure Chemical Industries, Ltd., Junron PW111, average molecular weight 6,000,000) Low shear viscosity = 70, high shear viscosity = 0.36, thixotropic index = 194 (9) Water-soluble polymer compound-11 ( Reference) Linear sodium polyacrylate (manufactured by Nippon Pure Chemical Co., Ltd.,
Dulimer AC-10SH, average molecular weight million) Low shear viscosity = 41, high shear viscosity = 0.04, thixotropic index = 1025 Cleaning builder (1) Cleaning builder-1 Sodium carbonate: Granular ash (manufactured by Asahi Glass Co., Ltd.) (2) Cleaning builder-2 Crystalline aluminosilicate: A-type zeolite slurry (solid content 53%, manufactured by Mizusawa Chemical Industry Co., Ltd.) (blended in terms of solid content) (3) Cleaning builder-3 amorphous aluminosilicate Salt: Amorphous zeolite (4) Washing builder-4 Sodium sulfite: Sodium sulfite (manufactured by Shinshu Chemical Co., Ltd.) (5) Washing builder-5 Potassium carbonate: Granular product (manufactured by Asahi Glass Co., Ltd.) (6) Washing builder -6 Acrylic acid and maleic acid 7/3 copolymer, average molecular weight 50,000 (BASF Corporation, Sokaran CP5) 40% aqueous solution (blended in terms of solid content) Used in Table 1 The contents of the optional components are as follows: (1) Amorphous silica (Tokuyama Co., Ltd., Tokusil N) (2) Montmorillonite: Natural Ca-type montmorillonite (Kunimine Industries Co., Ltd., KM-1) (3) Hectorite: Synthetic Na-type hectorite (Nissan Gardler Catalyst Co., Ltd., OPTIGEL-SH) (4) 12HSA: 12-hydroxystearic acid (Kawaken Fine Chemicals Co., Ltd.) (5) Grinding aid : Crystalline sodium aluminosilicate (manufactured by Mizusawa Chemical Co., Ltd., Shilton B) (6) Surface coating agent: crystalline sodium aluminosilicate (manufactured by Mizusawa Chemical Co., Ltd., Shilton B) (7) Layered polysilicate: SKS- 6 (Hoechst Japan) (8) Silicone: dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.) (9) Fluorescent agent: 2: 4,4'-bis (2-sulfur) Fostyryl) biphenyl disodium (manufactured by Ciba Geigy Co., Ltd.,
(Tinopearl CBS-X) (10) Enzyme: lipase / protease / cellulase =
1/1/1 mixture

[0030]

[Table 1] Table 1 Examples (% by weight) 1 2 3 4 5 6 Water-soluble polymer compound 3 2 4 2 5 2 6 1.7 0.15 8 0.3 Washing builder 1 23 14 24 21 17 13 2 13 22 20 12 15 10 3 10 20 4 10 2 4 2 1 3 1 1 1 5 2 3.5 1 1 1 6 6 3.5 4 6 5 3 Nonionic surfactant 1 6 6 8 20 25 25 2 5 2 10 2 5 3 6 Amorphous silica 1 2 3 4 4 Montmorillonite 2 6 4 Hectorite 3 4 12HSA 21 Grinding aid 10 5 10 10 Surface coating 2 4 2 7 3 4 Layered polysilicate 5 4 3 5 5 5 Silicone 0.1 0.01 0.05 0.2 0.3 0.1 Fluorescent agent 0.3 0.2 0.4 0.5 0.4 0.3 Enzyme 2 1.5 3 2 2 2 Other minor components Bla * Bla Bla Bla Bla Bla Dry particles Properties Release to the atmosphere None None None None None None Strength △ ◎ ◎ ◎ ◎ ◎ ◎ Heat resistance (℃) 250 220 400 400 400 400 Oil absorption 150 135 130 120 115 123 Detergent particle properties Moisture before storage 5 6 5 5 5 5 (%) After storage 10 10 12 13 15 10 Solubility ◎ ◎ ◎ ◎ ◎ ◎ ◎ Dumminess ◎ ◎ ◎ ◎ ◎ ◎ ◎ Seepage ◎ ◎ ◎ ◎ ◎ ◎ ◎ Fluidity Before storage 45 45 40 35 35 35 (°) After storage 55 50 40 35 35 40 Bulk density (g / ml) 0.88 0.84 0.86 0.88 0.90 0.92 Note) Bla is the remaining amount Indicates.

[0031]

[Table 2] Table 1 (continued) Comparative Example (% by weight) 1 2 3 4 5 6 Water-soluble polymer compound 1 2.3 2 1.4 6 1.7 7 1.5 9 1 Washing builder 1 30 17 18 15 21 17 2 29 10 8 12 15 3 7 10 15 10 4 1 1 1 0.7 1 1 5 1.5 1 1 0.7 1 6 8 5 5 4 6 5 Nonionic surfactant 1 4 15 20 10 20 25 2 4 10 5 10 2 3 1 10 Amorphous silica 4 4 6 3 4 Montmorillonite 3 3 2 6 Hectorite 3 5 12 HSA 4 Grinding aid 5 10 10 10 Surface coating 2.5 2.5 7 3 7 3 Layered polysilicate 3 3 5 2 5 5 Silicone 0.1 0.05 0.2 0.01 0.2 0.3 Fluorescence Agent 0.2 0.4 0.3 0.1 0.5 0.4 Enzyme 1 1.5 2 0.5 2 2 Others Minor components Bla * Bla Bla Bla Bla Bla Dry particles Properties Released to the atmosphere Large amount Very large Very large Extremely large Large large Extremely strong × × × ○ × × Heat resistance Property (℃) 180 400 250 400 400 400 Oil absorption 180 160 100 50 180 180 Detergent particle properties Water before storage 4 4 5 4 5 5 (%) After storage 10 10 12 8 10 8 Solubility △ ◎ × × △ ◎ Dama Conversion Properties × ◎ × ○ △ ◎ ◎ Seepage ◎ ◎ ◎ ◎ ◎ ◎ ◎ Fluidity Before storage 45 45 45 45 40 40 (°) After storage 90 90 90 85 80 90 Bulk density (g / ml) 0.75 0.89 0.92 0.90 0.87 0.89

[0032]

INDUSTRIAL APPLICABILITY According to the present invention, by blending a nonionic surfactant and a specific water-soluble polymer compound, a granular nonionic detergent containing a nonionic surfactant as a main component, which has good fluidity even when absorbing moisture. A composition is obtained.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Seiji Abe 1-3-7 Honjo, Sumida-ku, Tokyo Inside Lion Corporation

Claims (2)

[Claims] 1. A granular nonionic detergent composition comprising a nonionic surfactant and a water-soluble polymer compound having the following characteristics. Properties: Low shear viscosity 10-150 poise High shear viscosity 0.1-2 poise Thixotropic index 20-300 2. A method for producing a granular nonionic detergent composition, which comprises compacting and granulating a detergent component containing a nonionic surfactant and a water-soluble polymer compound, wherein the water-soluble polymer compound comprises: The following properties: Low shear viscosity 10-150 poise High shear viscosity 0.1-2 poise Thixotropic index 20-300.