JP2000144197A - Granular deforming agent composition, granular detergent composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a granular defoaming agent and a granular detergent composition mixed with the defoaming agent of wax having a defoaming effect of the defoaming agent of wax, hardly lowering in production, or the like, capable of exhibiting an excellent defoaming effect, and to provide a method for producing these compositions. SOLUTION: In producing a granulating defoaming agent composition or a granular detergent composition mixed with a defoaming agent of wax, a heating process for heating the defoaming agent of wax to its melting point or higher than it into a liquid state and a cooling treatment process for making the defoaming agent of wax in a liquid state into a solid state at <=450 deg.C/minute cooling rate are carried out to produce the granular defoaming agent composition or the granular detergent composition containing the defoaming agent of wax having 5-150 μm average particle diameter and >=1.0 μm average roughness.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a particulate antifoaming composition containing a wax antifoaming agent, a granular detergent composition and a method for producing the same, and more particularly to an improvement in the defoaming effect of the wax defoaming agent. You can do it.

[0002]

2. Description of the Related Art Recently, with the spread of fully automatic washing machines, there has been a demand for a detergent having a low foaming property and a good rinsing property so that rinsing can be surely completed within a program time.
Also, fully-automatic washing and drying machines that are automated from washing to drying are gradually spreading due to the sophistication and diversification of consumers' lives. This type includes a drum type washing machine, which is currently mainly used in European countries. Since drum-type washing machines perform washing by tapping and washing, foaming at the time of washing lowers the washing efficiency and lowers washing performance. Further, when the foaming becomes severe, bubbles may overflow from the washing machine. Also, because the bubble removal during rinsing is very bad,
There is a need for a detergent with reduced foam. Against this background, detergents containing an antifoaming agent have been proposed.

[0003] As antifoaming agents incorporated in detergents, wax antifoaming agents and the like are known. For example, Table 9-501
No. 703 discloses a method of mixing a paraffin wax and a carrier substance and subjecting the mixture to extrusion granulation. It has also been proposed to incorporate a wax defoamer in a granular detergent composition together with a surfactant and other detergent ingredients. For example, Japanese Patent Publication No. Hei 8-512072 discloses a method in which paraffin wax is dissolved in a nonionic surfactant, and this is sprayed onto an activator powder for granulation. However, conventionally, when a wax-type antifoaming agent is blended into a granular antifoaming composition or a granular detergent composition, there is a tendency that an antifoaming effect as expected cannot be obtained depending on a production method. Therefore, it is necessary to increase the compounding amount of the wax antifoaming agent, and there has been an inconvenience such as an increase in cost.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a granular antifoaming composition and a granular detergent composition containing a wax antifoaming agent capable of exhibiting a good antifoaming effect, and a method for producing these compositions. The task is to provide.

[0005]

According to the present invention, there is provided a granular material comprising a wax defoamer having an average particle size of 5 to 150 μm and an average roughness of 1.0 μm or more. An antifoam composition is proposed. Further, the present invention proposes a granular detergent composition comprising a wax defoamer having an average particle diameter of 5 to 150 μm and an average roughness of 1.0 μm or more. Such a particulate antifoaming composition or granular detergent composition comprises a heating step of heating the wax defoaming agent to a temperature equal to or higher than its melting point to a liquid state, It can be manufactured by a manufacturing method characterized by having a cooling treatment step of solidifying at a cooling rate of not more than ° C / min. More specifically, preferably, a step of mixing a wax defoamer, a carrier substance, and an organic binder substance at a temperature equal to or higher than the melting point of the wax defoamer to prepare a mixture, and granulating the mixture. In the method for producing a granular antifoaming composition having a step of forming a granulated product, the mixture and / or the granulated product are heated at least at a temperature not lower than the conversion temperature of the wax defoaming agent from liquid to solid. The liquid wax defoaming agent in the mixture and / or the granulated product is solidified by performing a cooling treatment step of solidifying the mixture at a cooling rate of 450 ° C./min or less in a temperature range of the conversion temperature or less. And In addition, the method includes a step of preparing a mixture by mixing the wax defoamer and the detergent raw material at a temperature equal to or higher than the melting point of the wax defoamer, and a step of granulating the mixture to form a granulated product. In the method for producing a high-density granular detergent composition, the mixture and / or the granulated product may be heated at a temperature ranging from a temperature equal to or higher than the conversion temperature of the wax defoamer from a liquid to a solid to at least 450 ° C. By performing a cooling treatment step of solidifying at a cooling rate of not more than minutes, the liquid wax defoamer in the mixture and / or the granulated material is solidified.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The average particle diameter of the wax defoamer contained in the granular defoamer composition or the particulate detergent composition of the present invention is 5 to 150 μm. If the amount exceeds 150 μm, the number of particles of the wax defoaming agent decreases, and the defoaming effect decreases. The average particle diameter can be determined by, for example, taking an electron micrograph of the sample powder using a scanning electron microscope. In the study of the present invention, a scanning electron microscope JSM-6300 manufactured by JEOL Ltd. was used.

The average roughness is an index indicating the height irregularities of the surface of the sample powder of the wax defoamer in the height direction.
It is a value obtained by measuring and calculating according to the method of determining the ten-point average roughness of SBO601-1994. In the study of the present invention, JIS BO601-1994 was used using a scanning laser microscope 2LM31 manufactured by Lasertec.
After taking in an image according to the method specified in, a straight line was drawn, and the unevenness of a 1.5 μm long portion on the straight line was measured. In addition, about one sample, 25 places were measured and the average value was calculated. The measurement range is 1.5 μm ×
Similar results are obtained for a 1.5 μm plane, and the measurement range may be set in this way due to calculation software.
Thus, the surface of the wax defoamer has an average roughness of 1.0 μm.
By having an uneven structure of m or more, the convex portion (projection) exhibits an inducing effect of breaking the foam film, and as a result, a good defoaming effect can be obtained. If the average roughness is less than 1.0 μm, a satisfactory effect cannot be obtained. Further, the upper limit of the average roughness differs depending on the thickness of the foam film, and therefore cannot be unconditionally set.

When a wax defoamer is blended into a granular defoamer composition or a granular detergent composition, generally, an operation of heating a solid wax defoamer to a liquid state is performed. There are many. In this case, after blending into the granular antifoam composition or the granular detergent composition, the wax antifoam is inevitably cooled to be changed from a liquid state to a solid state again.

The particulate antifoaming composition or the detergent composition of the present invention is prepared by heating a solid wax defoaming agent into a liquid in order to mix it with other components in the production process. This liquid wax defoamer is heated at 450 ° C /
The cooling rate is controlled by controlling the cooling rate within a specific range of 400 ° C./minute or less, preferably 400 ° C./minute or less. Therefore, it is necessary to control the cooling rate in the temperature range from the transition start temperature at which the wax defoamer starts to change from a liquid state to a solid state until the wax becomes a solid state. The transition start temperature can be measured by a differential scanning calorimeter.

Specifically, for example, a wax-type defoamer is
A mixture (kneaded material) is prepared by kneading with the other components at a temperature equal to or higher than the melting point of the wax defoamer, and the mixture is granulated. The specific method from preparation of the mixture to granulation is not particularly limited, and the mixture is prepared by kneading and kneading and granulated by a crushing granulation method, an extrusion granulation method, or a combination of these granulation methods. Or an agitation granulation method in which a mixing operation and a granulation operation of a wax antifoaming agent and other compounding components are simultaneously performed. In addition,
Known methods such as a tumbling granulation method and a fluidized bed granulation method can be employed.

When the mixture is granulated and cooled, or cooled after granulation, the cooling is performed while controlling the cooling rate at least in a temperature range equal to or lower than the conversion temperature. For example, in the crushing granulation method, a granulation operation is performed while flowing cool air, but the temperature of the cold air, the temperature of the material to be crushed into the crushing granulator, the residence time in the crushing granulator, the material to be crushed, The cooling rate can be adjusted by controlling the weight or the like. In the case of the extrusion granulation method, the cooling rate of the obtained extruded product is usually adjusted in order to extrude at a temperature equal to or higher than the melting point of the wax defoamer. In addition, the temperature at the time of granulation in the stirring granulation method is equal to or higher than the melting point temperature of the wax defoamer. Therefore, the cooling rate of the obtained granules is adjusted.

Further, even after the granulated material is once cooled and the wax defoaming agent in the granulated material becomes solid, it is heated again to make the wax defoaming agent liquid. ,
The cooling treatment can be performed at a cooling rate of 450 ° C./min or less. In addition, a liquid wax defoaming agent can be sprayed and blended with a powder or granulated product composed of other blending components. In this case, the cooling process is performed by controlling the cooling rate after spraying. Furthermore, after mixing and dispersing the powdered or granulated material composed of other components and the powdered wax defoamer, the mixture is heated to a temperature equal to or higher than the melting point of the wax defoamer and cooled. The cooling treatment can be performed at a rate of 450 ° C./min or less.

[0013] That is, in the present invention, the wax defoamer which is finally converted from a liquid state to a solid state by the cooling treatment is blended into the granular defoamer composition or the granular detergent composition. If so, the above-described effects can be obtained, so that various manufacturing methods can be adopted. That is, it is considered that the reason why the defoaming effect of the wax defoaming agent has been reduced conventionally is that the particle diameter and the uneven shape of the surface are changed due to the wax defoaming agent changing from a liquid state to a solid state. In the present invention, by controlling the cooling rate, the wax antifoaming agent having the above-described average particle size and average roughness can be blended into the granular antifoaming composition or the granular detergent composition. Therefore, a good defoaming effect can be obtained.

In the above-mentioned production method, the wax antifoaming agent can be uniformly compounded in the composition. Therefore, a mixture with other components is prepared, and this mixture is subjected to a crushing granulation method. A kneading / kneading granulation method in which granulation is performed by an extrusion granulation method or a combination of these granulation methods; a stirring granulation method in which mixing and granulation of a wax antifoaming agent and other compounding components are performed simultaneously are preferable. . In addition, according to these methods, a granular detergent composition having a high bulk density suitable for a recent mainstream compact detergent can be obtained.

Hereinafter, examples of the methods of producing the granular antifoaming composition and the granular detergent composition (high bulk density granular detergent composition) of the present invention will be described with respect to kneading, kneading and granulating methods, and stirring granulating method, respectively. This will be specifically described. (I) Method for producing granular antifoam composition (i) Ingredients (a) Wax antifoam The wax antifoam is insoluble in water and has a melting point of 25 to 135 ° C.
There is no particular limitation as long as it has a defoaming function, but one having a melting point higher than the washing temperature of a detergent containing a wax antifoaming agent is preferred. This is because the unevenness of the surface of the wax antifoaming agent is maintained during washing, thereby improving the defoaming effect. Examples thereof include those mainly containing hydrocarbons; those mainly containing esters of fatty acids and higher alcohols or fatty acid amides.

[0016] Examples of those mainly containing hydrocarbons include paraffin waxes extracted from petroleum lubricating oil fractions (in general, the distribution of carbon numbers is C16 to C40, and linear hydrocarbons of C20 to C40 are mainly used). ), Petroleum waxes such as microcrystalline waxes (generally containing C30 to C60 non-linear hydrocarbons as main components) extracted from heavy oil fractions of petroleum; and Fischer-Tropsch wax (generally C17). And a synthetic wax such as polyethylene wax (mainly composed of low-polymerization degree polyethylene); and a mineral wax such as ozokerite and ceresin.

The ester or fatty acid amide of a higher fatty acid and a higher alcohol may be any of animal waxes, plant waxes, mineral waxes, synthetic waxes and the like.
The main component is 32. As the main component containing fatty acid amide, a mixture of fatty acid amide and silica can also be used. In the present invention, petroleum wax is preferred because of its high effect and availability, and paraffin wax, particularly normal paraffin wax, is preferred because of its excellent effect. The compounding amount of the wax antifoam in the granular antifoam composition is 0.5 to 40% by weight, preferably 1 to 35% by weight. If it is less than 0.5% by weight, a sufficient defoaming effect cannot be obtained, and if it exceeds 40% by weight, fluidity (powder characteristics) may be reduced.

(B) Carrier substance As the carrier substance, inorganic or organic particles having oil absorbing properties and capable of carrying a wax antifoaming agent are selected. Further, those which improve the cleaning effect of other detergent raw materials mixed with the particulate antifoaming composition are preferred. Specifically, natural starch or modified starch insoluble in cold water; amino acid salts; metal sulfates such as sodium sulfate, potassium sulfate, calcium sulfate, and magnesium sulfate; metal carbonates such as sodium carbonate, potassium carbonate, calcium carbonate, and magnesium carbonate Salt; metal soap; zeolite; silica; clay mineral; silicon oxide and the like.

The compounding amount of the carrier substance in the granular antifoam composition is 2 to 90% by weight, preferably 5 to 80% by weight.
The amount of the carrier material is determined by the numerical range of the amount and the weight ratio of the carrier material to the wax defoamer. That is, the weight ratio of the carrier substance / (wax defoamer) is 2 to 10, preferably 4 to 8. If it is less than 2, the wax antifoam may not be sufficiently carried.
If it exceeds 10, the defoaming performance may decrease.

(C) Organic binder substance The organic binder substance is preferably solid at room temperature,
A water-soluble substance that melts when heated is preferred. Preferably, its melting point is 25-100 ° C, more preferably 40-80 ° C. If the melting point of the organic binder substance exceeds 100 ° C., it may take a long time to uniformly mix with other materials, or the operating temperature may be high, resulting in a decrease in productivity. Further, under a washing condition at a relatively low temperature such as that of tap water, the wax defoaming agent is less likely to be released from the particulate antifoaming composition, and the defoaming effect may be reduced.

The following can be exemplified as the organic binder substance. For example, polyethylene glycol; polyethylene oxide; polyethylene glycol alkyl ester; polyvinyl alcohol; glycerin; a fatty acid having 8 to 20 carbon atoms; a higher alcohol; an alcohol having 8 to 20 carbon atoms and ethylene oxide (EO)
A nonionic surfactant having an average of 4 to 50 moles added thereto; an alcohol having 8 to 20 carbon atoms and ethylene oxide (E)
O) in an average of 4 to 25 mol, propylene oxide (P
Nonionic surfactants to which 3 to 15 moles of O) have been added.

Among them, the average molecular weight is particularly preferably 400 to 3
0000 of polyethylene glycol is preferred, more preferably 1000 to 20000, most preferably 400
0 to 20,000 polyethylene glycol. Further, a polyethylene glycol addition type nonionic surfactant is also suitable, and specifically, EO is 3 to 80 per mole of alcohol having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms.
It is preferable to add one, preferably 10 to 50 moles. The organic binder material is present in the particulate antifoam composition at 10%.
-80% by weight, preferably 15-70% by weight. If the amount is less than 10% by weight, the effect of addition cannot be obtained, and if it exceeds 80% by weight, the powder properties and the storage stability of the particulate antifoaming composition may decrease.

(D) Others In the present invention, various inorganic particles (inorganic builder) or organic particles (inorganic builder) which do not inhibit the defoaming function of the wax defoamer, in addition to those shown in (a) to (c) above. Organic builder) and the like. In addition to the essential wax defoaming agent, a silicone defoaming agent having a defoaming function can be added. When a silicone antifoaming agent is compounded, the silicone contained in the silicone antifoaming agent is not particularly limited, but a typical example is a polyorganosiloxane.

(Ii) Production method (a) Kneading and kneading granulation method First, an apparatus capable of kneading and extruding materials is set in advance at a melting point of the wax defoamer or higher and the melting point of the organic binder substance. The above-mentioned temperature is set, and the above-mentioned wax defoamer, carrier substance, organic binder substance and, if necessary, other components are added, preferably as a mixed powder, and kneaded (consolidation kneading). ) And extrude into noodles. The apparatus is preferably an extruder-type kneader. For example, Hosokawa Micron Corporation
Extruded omics or the like can be used. Further, a twin-screw kneading extruder is also preferable, and a twin-screw extruder KEX type manufactured by Kurimoto Iron Works, Ltd. or the like can be used.

The kneading and extrusion operations can be performed by separate devices. As the mixer, for example, a screw type kneader is exemplified, and specifically, a KRC kneader manufactured by Kurimoto Iron Works, Ltd. or the like can be used. The extruder is
A pelleter double manufactured by Fuji Paudal Co., Ltd. can be used. At this time, the wax defoaming agent can be charged into the kneading machine, or can be blended when the kneaded product is charged into the extruder.

The diameter of the noodle-like extruded product is as follows:
It is 0.5 to 30 mm, preferably 0.7 to 20 mm. Its shape is cylindrical, prismatic, triangular prism, etc.,
There is no particular limitation as long as the kneaded material can be adjusted to an appropriate size to improve the operability of the subsequent crushing step.

The temperature of the extruded product immediately after being obtained in this way is usually higher than the transition start temperature of the wax defoamer. Next, this extruded product is put into a crushing granulator,
A cooling rate of at least 450 ° C.
Crushing while controlling to not more than / min to obtain a particulate antifoaming composition by adjusting to a predetermined particle size. As the crushing granulator, a crusher that applies a shock and a shearing force to a crushed object by a high-speed rotating knife cutter having a rotation speed of 30 to 100 m / s is preferable, and specifically, manufactured by Fuji Paudal Co., Ltd. And a Fitzmill manufactured by Hosokawa Micron Corp. can be used. The cooling rate is the temperature of the extruded product (crushed material) charged into the crushing granulator, the temperature of cold air applied to the crushed material during the crushing operation, the residence time in the crushing granulator,
It is prepared according to the weight of the material to be crushed. When kneading and extrusion are performed in separate steps, the kneaded product obtained in the kneading step can be crushed without going through the extrusion step to obtain a particulate antifoaming composition.

It is preferable, but not essential, that the crushing be performed in the presence of a grinding aid. Average particle size 2 as grinding aid
Powders of 0 μm or less are preferred. For example, average particle size 1 to 15
μm aluminosilicate is preferred because it acts as a calcium ion scavenger during washing. Other examples include silicon dioxide, bentonite, talc, clay, titanium oxide, calcium carbonate, sodium carbonate, and the like. When a grinding aid is used, the operability is improved, and the surface of the particles is coated with these grinding aids, thereby improving the fluidity. The amount of the crushing aid is 20% by weight or less, preferably 3 to 10% by weight, based on the total amount of the particulate antifoaming composition. If the amount is less than 3% by weight, no effect is obtained, and if it exceeds 20% by weight, the effect is saturated.

(B) Stirring granulation method First, a mixed powder containing preferably a wax defoamer, a carrier substance, an organic binder substance and, if necessary, other compounding ingredients is placed in a stirring mixer (high-speed mixer). The mixture is charged and agitated and granulated at a temperature not lower than the melting point of the wax defoamer and not lower than the melting point of the organic binder substance. As the stirring granulator, a horizontal stirring mixer such as a Ladyge mixer, a vertical stirring mixer such as a high-speed mixer, or the like is used. Next, the granulated product is gradually cooled while controlling the cooling rate at a temperature lower than the transition temperature of the wax-based antifoaming agent to 450 ° C./min or less to obtain a granular antifoaming composition.

The average particle size of the thus obtained granular antifoaming composition of the present invention is 100 to 2000 μm, preferably 150 to 1500 μm. If it is less than 100 μm, the fluidity may decrease, and if it exceeds 2000 μm, the solubility may decrease. The granular antifoam composition is usually used by mixing a powder with a high bulk density granular detergent composition containing a surfactant or the like. When the granular antifoaming composition is noodle-shaped particles, the diameter is 2000 μm or less (if the hole provided in the extrusion die is not circular, the circumscribed circle is the diameter), and the length is smaller than the diameter. At least 1 to 10 times occupies at least 50% by weight. By satisfying this condition, the solubility does not decrease, and the classification does not easily occur when it is blended in the detergent raw material.

(II) Method for Producing High Bulk Density Granular Detergent Composition (i) Ingredients (a) Wax Defoaming Agent The same ones as illustrated can be used. The compounding amount of the wax defoaming agent is 0.05 to 10% by weight, preferably 0.0 to 10% by weight in the high bulk density granular detergent composition.
It is 5 to 5% by weight. If it is less than 0.05% by weight, the defoaming effect cannot be obtained, and if it exceeds 10% by weight, the solubility of the high bulk density granular detergent composition may decrease.

(B) Surfactant (main detergent material) Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant,
Alternatively, a mixture thereof can be exemplified. Examples of the anionic surfactant include an alkyl sulfate, a polyoxyethylene alkyl sulfate, an alkylaryl sulfonate, an α-olefin sulfonate, and an α-sulfofatty acid ester salt. As the amphoteric surfactant,
Examples thereof include alkyl betaine. Examples of the nonionic surfactant include polyoxyethylene alkyl ether and polyoxyethylene alkyl aryl ether. Among these, it is preferable to use an anionic surfactant or a nonionic surfactant since the defoaming action of the wax antifoaming agent is effectively exerted. The amount of the surfactant is 5 to 40% by weight, preferably 10 to 30% by weight in the high bulk density granular detergent composition.

As the surfactant, for example, a granular material containing the surfactant is supplied to the production method of the present invention. Examples of the granular material containing the surfactant include those obtained as spray-dried particles together with other detergent raw materials. Spray-dried particles containing a surfactant, for example, of the surfactants exemplified above, those having heat resistance and other detergent raw materials are made into an aqueous slurry, which is obtained by spraying this from a spray-drying tower or the like by a conventional method. Particles having a bulk specific gravity of about 0.2 to 0.5 g / ml. Also, it is not limited to spray-dried particles,
Granules containing a surfactant formed by another method may be used. In addition, not limited to the granular form, for example, an anionic surfactant involves a neutralization step in the production process, and an aqueous slurry obtained after the neutralization step can be used.

(C) Other detergent raw materials Other detergent raw materials include builders (organic builders and inorganic builders); nonionic surfactants added in addition to main surfactants; carrier substances; pigments; enzymes; Agents; bleaching agents; bleaching activators; fragrances and the like.

Examples of the builder include alkali builders such as tripolyphosphate, pyrophosphate and carbonate;
Examples thereof include inorganic builders such as a type, X-type or amorphous synthetic zeolite; organic chelate builders such as EDTA; organic builders such as a maleic acid-acrylic acid copolymer; and neutral builders such as sodium sulfate. A carrier material is added as needed. The carrier substance can be selected from those exemplified as the builder described above, and other inorganic particles, organic particles, and the like that do not hinder the cleaning effect of the surfactant and the defoaming effect of the wax defoamer are selected. Can also. For example, starch, modified starch, soap, metal soap, clay, carboxymethyl cellulose salt and the like can be mentioned, and these can be used alone or as a mixture of two or more. The method of compounding these other detergent raw materials is arbitrary, and is adjusted according to the properties and characteristics. For example,
When preparing spray-dried particles of surfactant,
It can be blended when mixing with a wax defoamer. Enzymes, fragrances and the like can be mixed after molding the high bulk density granular detergent composition or sprayed on the surface thereof.

In the high bulk density granular detergent composition produced here, the wax defoamer plays a role of a binder, and if necessary, such as polyethylene glycol or the like to be added to the granular defoamer composition. Organic binder substances can also be included.

(B) Production Method As a method for producing the high bulk density granular detergent composition, the same method as that for the granular antifoaming composition described in the above (I) can be employed. For example, in the case of the kneading / mixing granulation method, a wax defoamer, a spray-dried particle containing a surfactant, and other compounding components are kneaded and extruded into a noodle shape. Next, crushing is preferably performed in the presence of a crushing aid while controlling the cooling rate to 450 ° C./min or less. In the case of the stirring granulation method, for example, a wax defoamer, spray-dried particles containing a surfactant, and other compounding components are charged into a stirring granulator and granulated, and then the cooling rate is set to 450 ° C./min. Cool while controlling as follows. Further, in the above-mentioned granulation step, when the cooling is performed at a cooling rate exceeding 450 ° C./min, or when the heating temperature is lower than the melting point of the wax defoaming agent, the wax defoaming agent is not melted. Even when blended in the high bulk density granular detergent composition, after granulation, the high bulk density granular detergent composition is reheated to the melting point of the wax defoamer or higher, and the cooling temperature is controlled to 450 ° C./min or less. If the cooling is performed, the effect of the present invention can be obtained.

The particle size of the high bulk density granular detergent composition is usually 3
00-3000 μm, preferably 350-2000 μm
It is said. If it is less than 300 μm, the fluidity may decrease, and if it exceeds 3000 μm, the solubility may decrease. The bulk density of the high bulk density granular detergent composition is preferably 0.5 g / ml or more, more preferably 0.7 to 1.
It is 5 g / ml. If it is less than 0.5 g / ml, it is not suitable for a compact detergent, and if it exceeds 1.5 g / ml, the solubility may be reduced.

The embodiments of the present invention are summarized as follows. (1) In the present invention, in cooling a liquid wax defoamer to a solid state, the wax is cooled at a cooling rate of 450 ° C./min or less, preferably 400 ° C./min. Therefore, the cooling rate in the temperature range from the transition start temperature at which the wax defoamer starts to change from the liquid state to the solid state to the solid state is controlled. (2) In the present invention, a wax antifoaming agent which is finally changed from a liquid state to a solid state by the cooling treatment may be blended into the granular antifoaming composition or the granular detergent composition. (3) As a method for producing the granular defoamer composition or the granular detergent composition, a kneading / kneading granulation method and a stirring granulation method are preferable.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. (I) Measurement of transition onset temperature of wax defoamer Paraffin wax (manufactured by Nippon Seiro Co., Ltd.) was heated and melted using a differential scanning calorimeter (DSC) (DSC220 manufactured by Seiko Instruments Inc.). The change in calorific value when the temperature was lowered at 2 ° C./min was measured, and the exothermic onset temperature was defined as the transition onset temperature. Figures 1 and 2 show that the melting point provided by the manufacturer is 43 ° C.
DSC charts of the paraffin wax and the wax defoamer of paraffin wax at 58 ° C. are shown respectively.
The respective conversion starting temperatures were 44.3 ° C and 56.2 ° C.

(II) Production of granular antifoam composition and performance evaluation (i) Production of granular antifoam composition (Examples 1 to 4, Comparative Examples 1 and 2) Using the measured paraffin wax, granular antifoam compositions were produced at the mixing ratios shown in Table 1, respectively. The sodium sulfate shown in Table 1 is the carrier material, PEG # 6000 and PEG # 20,000.
Is an organic binder substance (melting point 62 ° C, 64 ° C, respectively)
It is.

That is, the materials shown in Table 1 were converted to Extruded Omics EM-6 (Hosokawa Micron Corporation)
Manufactured). Then, the mixture is kneaded at a jacket temperature of 75 ° C. and extruded from a die having a plurality of holes having a diameter of 1.0 mm, and has an average diameter of 1.0 mm and an average length of 20 to 10 mm.
A noodle-like extruded product having a diameter of 0 mm and an average temperature of 60 ° C. was obtained.

This extruded product was put into a crushing granulator (DKA-3 type Fitzmill, manufactured by Hosokawa Micron Corp.) together with cold air and crushed to obtain a bulk density of 0.7 g / cc.
A crushed granulated product (granular antifoaming composition) in the form of a cylindrical pellet having an average particle diameter of 700 µm and a length of 3 to 5 mm was obtained. At this time, the crushing was performed by adjusting the temperature of the cold air under the conditions shown in Table 2 and adjusting the temperature of the outlet of the crushing granulator to change the temperature of the crushed granules discharged from the outlet. The inside cooling rate was controlled. The cooling rates shown in Table 2 are:
The difference between the temperature (60 ° C.) of the extruded product charged into the crushing granulator and the temperature of the crushed granulated material discharged from the crushing granulator is divided by the residence time (about 4 seconds) in the crushing granulator. Value. The crushed and granulated material is left to cool to room temperature if necessary, and then put into a gyro shifter (manufactured by Tokuju Kosakusho Co., Ltd.) which is a sieve with a tapping ball.
The fine powder was classified using a 5 μm mesh. A part of the crushed and granulated product was reheated in a fluidized bed at an air temperature of 70 ° C., and then left naturally until the temperature reached room temperature. The cooling rate at this time was 10 ° C./min or less.

[0044]

[Table 1]

[0045]

[Table 2]

(Ii) Production of high bulk density detergent particles High bulk density detergent particles having the composition shown in Table 3 were produced by kneading, kneading, crushing and granulating methods. First, a slurry of about 50% by weight of water containing anionic surfactant such as sodium α-sulfofatty acid methyl ester, soap, zeolite, alkali builder, fluorescent agent, etc. is adjusted at about 70 ° C., and is subjected to countercurrent spraying. Spray-drying was performed at 250 ° C. using a drying tower. The resulting dry powder has a bulk density of 0.3 g / cc,
The average particle size was 350 μm.

A nonionic surfactant (polyoxyethylene dodecyl ether) and water are added to this dry powder to form S-
The mixture was charged into a 4KRC kneader (manufactured by Kurimoto Iron Works, Ltd.), and a consolidation kneaded product was obtained by adjusting the temperature by flowing arbitrary warm water through the jacket. Then, the consolidation kneaded material was extruded using a pelletizer double (manufactured by Fuji Paudal Co., Ltd.) and pellets (extruded product) having a diameter of 10 mm and an average length of 20 mm were obtained.
I got The pellets and 6% by weight of sodium carbonate (crushing aid) were put into a DKA-3 type Fitzmill (manufactured by Hosokawa Micron Corp.) together with cold air to be crushed, and crushed and granulated (bulk density: 0.85 g / cc, The average particle size was 550 μm).

[0048]

[Table 3]

(Iii) Performance evaluation The granular antifoaming composition produced in the above (i) was subjected to the above (i)
3.7 parts each in the high bulk density detergent particles produced in i).
5% by weight (0.75% by weight as a wax defoamer) was added. Then, the detergent composition was subjected to a foaming test during washing under the following conditions to evaluate the defoaming effect.

(Washing height test during washing) 25 g of the detergent composition was
Drum type washing machine containing 1 kg of cloth (ES-E made by Sharp
60), and a washing operation was performed using water at 20 ° C. Then, the foam height 35 minutes after the start of washing was measured from the lower edge of the round window and evaluated according to the following criteria. The results are shown in Table 2. Cleaning foam height evaluation criteria A: 50 mm or less B: 50 to 120 mm C: 120 to 170 mm D: 170 mm or more Since the diameter of the round window was 200 mm, 35
When the height reached 200 mm within minutes, the measured value of the foam height was described as 200 mm up in Table 2.

Further, 5 g of the obtained particulate antifoaming composition was
It was dissolved in 100 g of purified water at 15 ° C. (a temperature lower than the melting point of the wax defoamer), filtered through a glass filter (No. 4), and washed with purified water. Then, the filtration residue was re-dispersed in 200 g of purified water, allowed to stand at room temperature (20 ° C.) for 2 days, and the wax defoamer particles floating on the water surface were collected with a slide glass, and further subjected to a humidity of 60%. % Was dried in a room for one day, and these measured values were determined as a sample for measuring the average particle diameter and the average roughness. The average particle diameter was obtained by subjecting an image obtained by a scanning electron microscope to image processing by a computer, approximating a circle by the projected area of the particle, and defining the diameter as the particle diameter. The number of particles measured at this time was 1000 or more. The results are shown in Table 2.

From the results shown in Table 2, the examples show that the defoaming effect of the wax defoamer is better than that of the comparative example. In addition, from the results of Examples 3 and 4, it was confirmed that good results could be obtained even after reheating and cooling after the production of the particulate antifoaming composition.

(II) Production and Performance Evaluation of High Bulk Density Granular Detergent Composition (i) Kneading, Kneading and Crushing Granulation (Examples 5 to 11, Comparative Examples 3 and 6) S-4 KRC Kneader (Kurimoto Iron Works) (Manufactured by Toshosho Co., Ltd.), except that a compacted kneaded product containing the wax antifoaming agent was produced, and (ii) of (II) above.
Two kinds of crushed granules (bulk density: 0.85 g / cc, average particle diameter: 550 μm) having the compositions shown in Table 4 were produced in the same manner as in the production of the high bulk detergent particles.

[0054]

[Table 4]

The crushing and granulating operation was carried out in the same manner as in (I) the method for producing a granular antifoaming composition of the above (I), the cooling rate under the conditions shown in Table 5. Was controlled. Further, in Examples 8 and 11, the crushed granules were reheated in a fluidized bed at an air temperature of 70 ° C., and then left naturally until the temperature reached room temperature. The cooling rate at this time was 10 ° C./min or less. The average particle diameter and average roughness of the wax defoaming agent in the obtained crushed and granulated product were measured in the same manner as in the above-described granular antifoaming composition.
μm and 2.0 μm.

(Ii) Stirring granulation method (Examples 12 and 13) A dry powder containing the same surfactant as that used in the method (I) for producing a granular antifoaming composition was used to remove waxes. The resulting mixture was charged into a Lodige mixer together with the foaming agent, and water and polyoxyethylene dodecyl ether were added while rotating the main shaft and the chopper to produce agitation granules of the type shown in Table 4. The temperature of the stirred granulation was adjusted to 65 ° C. by flowing arbitrary warm water through the jacket of the Lodige mixer.
The resulting product had a bulk density of 0.78 g / cc and an average particle size of 60.
It was 0 μm. Then, it was left to cool to room temperature and cooled at a cooling rate of 10 / min or less. In addition, the average particle diameter and average roughness of the wax antifoaming agent in the obtained agglomerated granulated product were measured in the same manner as in the above-mentioned granular antifoaming composition, and were 6.5 μm and 2.0 μm, respectively. Met.

A fragrance, an enzyme, and a layered silicate were respectively added to the crushed granules and the stirred granules prepared by the methods (i) and (ii) to obtain a high bulk density granular detergent composition. Then, the same test as the above-described foam height during washing test was performed, and the same defoaming effect was evaluated. Further, for the wax antifoaming agent in the obtained high bulk density granular detergent composition, the average particle diameter and average roughness were measured in the same manner as in the above-described granular antifoaming composition, and the above-described antifoaming effect was measured. The results are shown in Table 5 together with the evaluation results.

[0058]

[Table 5]

From Table 5, it is clear that the examples have better defoaming effects than the comparative examples. In addition, it was confirmed that a good defoaming effect could be obtained even when the granular antifoaming composition was reheated and cooled after production.

[0060]

As described above, in the granular defoamer composition or the granular detergent composition of the present invention, a good defoaming effect can be obtained by setting the average particle diameter and the average roughness of the wax defoamer. can get. As a result, a sufficient defoaming effect can be obtained with a small amount of the wax defoaming agent, and the cost can be reduced. Further, the granular antifoam composition or the granular detergent composition of the present invention can be obtained by controlling the cooling rate when the wax antifoam is changed from a liquid state to a solid state in a manufacturing process. Therefore, a new compounding component is not required, and various production methods can be adopted.

[Brief description of the drawings]

FIG. 1 is a DSC chart of a paraffin wax having a melting point provided by a manufacturer of 43 ° C.

FIG. 2 is a DSC chart of a paraffin wax having a melting point provided by a manufacturer of 58 ° C.

Continuation of the front page (72) Inventor Takashi Kishino 1-chome, 3-7, Honjo, Sumida-ku, Tokyo F-term in Lion Corporation (reference) 4D011 CB01 CB03 CB04 CB07 CB08 CB11 CC01 CC07 4H003 AB03 AB15 AB19 AB21 AB44 AC08 BA10 CA20 DA01 EA12 EA16 EA28 EB02 EB22 EB29 EB32 EB36 EC01 EC02 FA19

Claims (4)

[Claims] 1. A granular antifoaming composition comprising a wax antifoaming agent having an average particle diameter of 5 to 150 μm and an average roughness of 1.0 μm or more. 2. A granular detergent composition comprising a wax defoamer having an average particle diameter of 5 to 150 μm and an average roughness of 1.0 μm or more. 3. A method for producing a granular antifoaming composition containing a wax antifoaming agent, comprising: heating the wax defoaming agent to a liquid state by heating it to a temperature equal to or higher than its melting point; 4 wax defoamers
A method for producing a particulate antifoaming composition, comprising a cooling treatment step of solidifying at a cooling rate of 50 ° C./min or less. 4. A method for producing a granular detergent composition containing a wax defoamer, comprising: a step of heating the wax defoamer to a liquid state by heating it to a temperature equal to or higher than its melting point; Defoamer 4
A method for producing a granular detergent composition, comprising a cooling treatment step of solidifying at a cooling rate of 50 ° C./min or less.