DE2136978A1 - Method for preventing caking of particles of a core material with a coating - Google Patents

Description

TELEPHONE, 55547 «8000 MONKS Ϊ5, TEtEGRAMME: KARPATENT NUSSBAUMSTRASSE 10

July 23, 1971 W 40 622/71 - Ko / DE

Ueno Pine Chemical Industries Ltd., Osaka / Japan

Method of preventing particles of a core material from caking together with a coating

The invention relates to a method for preventing the caking or caking of particles consisting of a Kernmäteria.l with a coating of a There are coating agents, the main component of which is a hardened oil.

Hardened oils have heretofore been used for such purposes as preventing moisture absorption, retention the effectiveness or prevention of a reaction of drugs and chemicals in drugs for humans and animals, for agricultural chemicals, food additives and the like, being used as a surface coating for such drugs and chemistries

ORiGtNAL INSPECTED 209808/1893

micalia served as core materials. In particular _; When the core material consists of a food additive, the application of a hardened oil coating has often been carried out with excellent results, that is, prevention of elution of the additive at room temperature, but elution of the same during the step of heating the food product, thereby causing decomposition of the core material in the food material and any harmful effect of the nuclear material on the food material has been prevented.

Hardened oils for use for the purpose indicated above are those with a melting point in the range from 45 to 85 ^° C. B. occur in summer. Particularly favorable hardened oils, for example, hardened beef Talk (melting point 59 to 61 ° C), hardened whale oil (55 to 6O ⁰ C), hardened rapeseed oil (melting point 59 to 62 ⁰ C), hydrogenated soybean oil (melting point 60 to 69 ⁰ C), hydrogenated Cottonseed oil (melting point 55 to 61 ^° C.) and hydrogenated castor oil (melting point 82 to 85 ^° C.).

As a method of coating core materials such as Medicines for humans and animals, agricultural chemicals and hydrogenated oil additives, numerous methods are known, for example, the following;

1. The spray method consists in that the hardened Oil is melted in the heat, the core material is dispersed in it and then this dispersion in a gas with a temperature below that of the melting point of the hardened oil, for example air, nitrogen or carbon dioxide.

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is sprayed so that the core material is coated and at the same time the particles are cooled and solidified will.

2. The pan coating process in which the coating of the particles is carried out by repeating an operation in which the core material is converted into a Plating pan placed the hardened oil dissolved in a solvent on the core material under Shake the pan and then spray the solvent by blowing it off, for example with Hot air, is evaporated and removed from the coated particles.

3. The coating process by suspension in air, wherein the core material floats in an air stream and the floating core material by spraying a Solution of a hardened oil is coated against the material.

4. The vacuum evaporation process, with the hardened oil is heated in a vacuum and it is evaporated against the core material, so that a vapor deposition of the hardened oil is effected on the surface of the core material.

5. The electrostatic coating process, with the Particles of the core material and the particles of the hardened oil solution have opposite electric charges are applied so that these particles are combined.

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6. The melt dispersion method, in which the hardened oil is melted in a liquid by heat, which does not dissolve it, the core material is dispersed in the melt, the dispersed core material formed into small particles and then cooled and solidified.

The particle size of these coated particles, which consist of a core material with the coating of a hardened Oils consist varies depending on the intended use of the core material and they are commonly used made to have a suitable particle diameter in the range of 500 to 2000 microns. It is most favorable when these coated particles are independent of one another and have flowability. Palis bake the coated particles together and in one are in a lumpy state, this is not only unfavorable in use, but sometimes for certain purposes totally unsuitable. In particular, if the core material is to serve as a food additive, is it necessary? agile that these particles are uniformly mixed in the food material. A nutritional supplement where the Particle present in a caked state serves its purpose and does the opposite Effect of the deterioration in the quality of the food as it is in the food product in the non-uniform State is incorporated.

In view of the foregoing reasons, in order to prevent this caking which causes excessive deterioration in the commercial value of the product, the addition was made in the order of 0.3 to ⁵ % based on that coated with hardened oil

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Particles of a finely divided inorganic substance such as silica, magnesium aluminum silicate, magnesium carbonate or tertiary calcium phosphate or alkaline earth salts of higher fatty acids, such as calcium stearate or Magnesium stearate executed “Despite the addition of these caking inhibitors, it happens frequently on that the product cakes together as the product is shipped from the manufacturing plant to the consumer.

It is therefore an object of the invention to provide hardened oil coated particles which can cause this caking does not occur.

It has been found that the above caking of the hardened oil coated particles is due to a change in the crystal structure of the hardened oil used as the coating agent, so that the desired object of the invention can be achieved by the following procedure: The particles, i.e.: each consist of a core material with a coating of a coating agent, the main component of which is a hardened oil with a melting point of 45 to 85 ^° C., are left to stand for at least 20 hours at a temperature higher than 25 ^° C., but lower than the softening point of the hardened oil , whereby the crystal structure of the hardened oil is stabilized, whereupon these particles are decomposed with a caking inhibitor in an amount of 0.3 to 5% by weight based on the particles.

The changes in the crystal structure of a hardened Oils are made depending on their thermal treatment. That left the solidified mass of the hardened Oil consists of a plurality of crystals, that is, a congregation of small crystals, and consequently

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this results in changes in the crystal structure the thermal treatment of these small crystals instead. Either through cooling and solidification or Precipitation from a solvent for a hardened oil, which is in the molten state as a result of heating is, precipitated solidified hardened oil lies in a structure in which a plurality of small crystals in unstable form together in relatively loose Arrangement are united. If these crystals are left to stand for long periods of time in a state where heat is supplied from outside, the unstable crystal structure becomes a stable crystal structure transferred and continue the small crystals, which are present in a relatively loose arrangement, are properly and attached compactly, so that they are very much stabilized. The crystal structure stabilized in this way no longer undergoes any changes at temperatures below the softening point.

The changes indicated were within the scope of the invention the crystal structure of the hardened oil due to the temperature treatment in detail by means of thermal Differential analysis or X-ray diffraction or infrared absorption analysis examined. With regard to the prevention of caking of hardened oil coated Particles have so far remained the crystal structure of the hardened oil out of consideration and it has been investigated completely neglects the crystal structure of the hardened oil in terms of caking prevention and rather, these investigations were exclusively on classes and amounts of the inhibitors to be used limited for caking. As an explanation of the cause of the caking, it was only assumed that part of the hardened oil at a temperature in the

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Near the softening point melts, so that a melting takes place between the particles, resulting in a caked state. In the context of the present Investigations into the relationship between the changes in the crystal structure of the hardened Oil and caking has now been found to be the caking of the hardened oil coated particles is affected not only by the temperature at which the particles are allowed to stand, but that the Temporal temperature treatment course of the coated particles (temperature © history) also has a great influence on this caking phenomenon.

The relationship of the changes in crystal structure and caking will be explained with reference to the accompanying FIG Drawings explained, with hardened beef talc as an example is used, in the drawings Pig. 1 a graphical representation of results of the thermal Differential Analysis of Hardened Beef Talk and Pig. 2 is a graphical representation of the results of a Infrared absorption analysis of hardened beef tallow are.

When a differential thermal analysis is carried out with hardened beef talc (melting point 69 to 61 ^° C.) after it has been heat-melted and then cooled and solidified, three classes of curves are obtained which are described in Pig. 1, which depend on the method used for the cooling treatment. The crystal forms of the hardened oil that give these three classes of different thermal curves are referred to as Forms A, B and C. The crystal form A is the crystal form obtained when the heat-melted hardened oil is rapidly cooled and solidified in cold water and which, although stable at low temperatures, gradually turns into the crystal

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Form B converts when the temperature rises and is finally converted into crystal form C. The crystal form B is the crystal form obtained when the hardened oil is cooled and solidified under relatively mild conditions, that is, when it is allowed to stand at room temperature. Under these conditions, the crystal form B is obtained without the step of the crystal form A being passed. The crystal form B is unstable like the crystal form A and therefore gradually changes to the crystal form C. The crystal form C is the crystal form which is obtained when the crystal forms A and B are either 15 days or longer at 25 ^° C. or 3 days or longer be left to stand ^{at 30 ° C.} This crystal form C is extremely stable and no longer shows any further changes at temperatures below the softening point. Furthermore, at the same time as this conversion, there is a change in the attachment of the small crystals from a loose arrangement to an orderly arrangement. This not only stabilizes the crystal shape but also increases the stability of the overall structure. According to the graphical representation in JIPig. 1, the maximum peak temperature of the crystal form A 68 ⁰ C, the crystal form B that of 64 ⁰ C and that of the crystal form C 7O ⁰ C, so that the crystal Form C has the highest value, while the crystal form B has the lowest value. This means that in the pail of hardened beef talc, the conversion takes place first from crystal form A to crystal form B with a lower maximum peak temperature and then to crystal form C, which is the most stable. This kind of

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Conversion is a phenomenon that is commonly shown in the case of higher fatty acids and higher alcohols. In the I ¹ Ig. 2, the curve I shows the infrared analysis values of the crystal form C and the curve II shows that of the crystal form A. The shape of the curve I is more complicated than that of the curve II, and the difference is clearly seen.

In general, however, the hardened oils precipitated from a solvent are of the G crystal form the crystal form C is still unstable in this pail. Furthermore, the crystal structure is not yet built up properly, but lies in loose arrangement. If this hardened oil is left to stand above a certain temperature, change it the crystals turn to crystal form C, which has stability and whose crystal structure is proper Arrangement shows.

Curve III of the Pig. 2 shows the results of an infrared analysis of hardened beef tallow, which was crystallized by evaporation of chloroform from a chloroform solution at '2O ⁰ C, with clearly shows the difference in appearance compared with the curves I and II. When these hardened oil crystals are left to stand above a certain temperature, they change to stable crystals corresponding to those of curve I.

The speed at which the crystal structure changes from shape A or B to shape C is determined by the The temperature at which the crystals are left to stand is influenced, the speed becoming higher when the temperature gets higher. At low temperatures, where the conversion does not proceed, being general

When the speed becomes very slow, when the temperature drops below 15 ^° C., the particles coated with a hardened oil of crystals of form A or form B do not stick together, even if the particles are left to stand for a long period of time.

The caking of those coated with hardened oil Particles that take place when the crystal structure changes from Form A or B to Form C can be explain as a phenomenon, whereby the particles are mutually absorbed into the crystals of the other particles on the surface of the same during the period when the transformation of the crystals of Form A and Form B into the stable form C takes place, unite or where there is a change in the loose arrangement of the small crystals into one proper arrangement takes place.

In order to carry out the stabilization of the crystal structure of the hardened oil according to the invention, i.e. the transition from the form A and the form B to the crystal form C as well as the change of the loose arrangement of the small crystals into a proper arrangement, the cords coated with hardened oil are favorable left to stand at a temperature above 25 ^° C. and preferably above 30 ^° C. At temperatures below 25 ^° C. either the rate of conversion is extremely slow or no conversion takes place. For example, a change to the completely stable form of the crystal takes place in 15 days at 25 ^° C., 3 days at 30 ^° C., 24 hours at 40 ^° C. and 20 hours at 45 ^° C. Thus the period of time during which the particles must be allowed to stand to complete their stability becomes shorter as the temperature increases. The parts coated with hardened oil, which have been stabilized in this way,

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are passed through a sieve and lose the slight caking that took place during the transformation Has. The particles, which in this way became independent of one another, are then added with 0.3 to 5% by weight, preferably 0.5 to 3 wt .- ^, based on the particles, an inhibitor against caking, whereby the product according to the invention of improved flowability is obtained that does not cake at temperatures lower than the softening point of the hardened oil and consequently has a high commercial value. All of the above inhibitors for the Caking can be used as long as they do not affect or inhibit the function of the core material and usually silica, magnesium aluminum silicate, Magnesium carbonate, calcium tertiary phosphate, calcium stearate or magnesium stearate are favorably used.

The procedure for carrying out the stabilizing treatment is simple. For example, the coated particles "just need to ^{stand in a room with a temperature higher than 25 0} C, but lower than the softening point of the hardened oil" immediately after their production until the transformation of the crystal structure to form C. This is done with Particles spread thinly in a vessel such as a pan in such a way that minimal stress is placed on the particles, the reason for avoiding excessive stress on the particles is to be as great as possible Since it is impossible to prevent caking during the conversion, it is necessary to avoid pressure at this stage which increases the contact area between the particles, in order to reduce the possibility of caking.

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"baking is reduced to a minimum at this stage.

The procedure for incorporating the caking inhibitor is also simple. A procedure, wherein the prescribed amount of the caking inhibitor with the coated particles is mixed using a conventional mixer is sufficient. The slight caking that occurred during the stabilization treatment is completely lost during this mixing, while at the same time, the caking inhibitor is uniformly mixed with the coated particles. Through this Coated particles are obtained with flowability, in which no caking takes place.

The following examples serve to further illustrate the invention without limiting it. The percentages in the examples are based on weight.

example 1

4 kg of hardened beef tallow was melted in the heat and kept at a temperature of 70 ^° C. 1 kg of powdered sorbic acid was added to the melted hardened beef tallow and the mixture was mixed with thorough stirring using a homomixer and a homogeneous dispersion was obtained. This dispersion was sprayed into air at 20 ^° C. and, on cooling and solidification, sorbic acid particles coated with hardened oil were obtained which were suitable as food preservatives. The following caking test was carried out on the obtained coated particles.

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The individual classes of the in Tables I-I "through I-Y indicated caking inhibitors were added separately to the coated particles, followed by the coated particles among the various conditions given in Tables I-I to I-Y were allowed to stand. Then the the coated particles are packed in a cylindrical tube 40 mm in diameter and 60 mm in height, and the particles subjected to pressure by placing a weight of 500 g on the packed particles. the Particles in this state for 7 days at the test temperatures given in Tables I-I to I-V ditched. Then, the coated particles contained in the pipe were taken out therefrom and placed thereon made sure that the caked state of the particles was not disturbed, whereupon the removed Particles with a 10 mesh sieve. were sifted. The amount of coated particles left on the sieve the total amount was then calculated and given as a percentage. This value, which as a total of * degree of baking ($) is indicated in the tables I-I to I-Y indicated. The larger this value, the greater the caking of the particles. In the tables I-I to I-Y also show the crystal forms of the hardened beef tallow before and after the experiment.

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Table I-I

Conditions "when the particles are left to stand

Type and amount of added inhibitor against caking

Test temperature ()

Assembly granular form
extent

Yor dem

attempt

After the
attempt

examined immediately after manufacture

10

15-20

to ο <o

likewise likewise

likewise likewise likewise

- 30th 90-95 A. σ tertiary
Calcium phosphate
phosphate 3 # 10 below 1 A. A. as well 30th 80-90 A. σ Silica 3 # 30th 70-80 A. C. Ma gne s iuma Ium iraa-
silicate $ 3 30th 70-80 A. C.

CD CD -J OO

Table I-II

Conditions for allowing the particles to stand

Type and amount of added inhibitor against caking "experimental caking temperature
( ⁰ C) (#)

Crystal shape

Before the
attempt

Oh that
attempt

O (O OO O

OO CO CO

after 3 days of standing at 25 ⁰ C after the production

likewise likewise

likewise likewise

10-20

tertiary CaI

calcium phosphate 3%

Silica $ 3

Ma gne s iumalum inlxm silicate 3%

30th 90-95 B. C. S. 30th 80-90 B. C. VJt I. 30th 70-80 B. C. 30th 70-80 B. C.

CT) CO

Table I-III

CO 00 O CD

Conditions at Type and amount Attempt Caking Crystal shape After this
attempt Let the
Particle of the added
Inhibitor
against the ver
to bake temperature
( ⁰ C) extent
(*) Before the
attempt C. after standing
for 15 days
at 25 ⁰ C after
the production - 10 15-20 C. , C as well - 30th 15-20 C. σ as well tertiary
Ca1ciumpho sphat
2 i> 10 below 1 C. C. as well as well 30th as well C. σ as well Silica $ 1 30th as well C. σ as well Magnesium-
aluminum silicate
1 * 30th as well C.

!Tabel I-IV Assembly
extent Crystal shape
“Before the after
»Please try C.
C.
C. Conditions at
Let the Type and amount
of the added
to bake Try
temperature
( ⁰ C) 5-10
1-5
1-5 C.
σ
0 for 3-day a
Leave
at 30 ⁰ C after the
Manufacturing
as well
as well tertiary calcium
phosphate $ 0.5>
Silicic acid $ 0.5>
Ma & nesium aluminum 30th
30th
. 30th

as well

silicate 0.5 9 ^

tertiary calcium phosphate 2 #

below 1

rs)

co

CX)

Conditions at
Let the
Particle Table I-V Experimental
temperature
Cc) Caking
extent
W. Crystal shape
Before after
Try try σ after 20 hours
Let stand by
45 ⁰ C Type and amount
of the added
Inhibitor
against the ver
to bake 10 15-20 C. C. as well - 35 15-20 C. σ
C. as well
as well - tertiary calcium 35
phosphate 2 %
Silicic acid i2 96 35 below 1
as well C.
C. σ. O
(O
CO
O
OO as well Magnesium aluminum 35
silicate $ 2> as well σ ^ 1 893

Example 2

Hydrogenated castor oil 3 kg (melting point 80 to 85 ⁰ C) were heat-melted. After adding 4 g of soy lecithin as a surface-active agent, 1 kg of finely divided fumaric acid was added, whereupon the mixture was agitated thoroughly with stirring and the dispersion was obtained. This dispersion was kept at 90 ^° C. and sprayed into air at 30 ^° C., whereupon it cooled and solidified. Fumaric acid particles coated with hardened castor oil were prepared.

The resulting coated particles were separated with the various inhibitors shown in Table II decomposed against caking and attempted caking Carried out in the same manner as in Example 1 under the various conditions given in Table II. The results are given in Table II.

The fumaric acid coated with hydrogenated castor oil was added to a food base, thereby reducing the elution range of fumaric acid at room temperature prevents, however, the elution of the acid during the heating stage effected, this being used for the purpose of lowering the pH of the food product. There how Table II shows the degree of caking according to the invention Coated particles are low, they are particularly suitable for this purpose.

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Table II

Conditions "when the particles are left to stand

Type and amount of inhibitor added against the caking

Attempt directly n8_, ch of the production as well

CO Q CD

Ma gne s iuma aluminum silicate 2 $>,

Test ^{temperature (0} C)

Degree of assembly

as well tertiary oalcium
phosphate 2 # 35 as well Silica $ 2 35 after 2 days
Let stand by
45 ⁰ C after the
Manufacturing 10 as well - 35 as well
as well Magnesium aluminum
silicate 2 #
tertiary calcium
phosphate 2 % 35
35 as well Silicic acid $ 2> 35

55-10

80-85 70-80

as well

also 5-10

5-10 below

likewise likewise

N)

GO

CD CD

OO

Example 3

A Glutaminsäurepulver having a fineness corresponding to 40 mesh was placed in a tJberzugspfanne and shaking a solution of 30 #ige hardened beef tallow was sprayed (melting point 59 to 61 ⁰ C) in chloroform. Shaking of the powder particles was continued for a while, and after uniform wetting of the surface of the glutamic acid particles was achieved, the chloroform was evaporated by hot air. The above operation was repeated until the hardened beef tallow content in the particles became 40 % . Thereby, coated glutamic acid particles were obtained which could be used as a seasoning agent as well as a pH lowering agent for food products.

The obtained coated glutamic acid particles became allowed to stand under the conditions given in Table III, whereupon the various caking inhibitors were added and the caking experiment was carried out. The results are given in table III. . .

Table III

Conditions "beία Let the particles stand

Type and amount of inhibitor added against caking

Try temperature ( ⁰ C)

Degree of supplementation
(*)

examined immediately after manufacture

10-15

as well . - as well Calclurastearate 3 # as well Magnesia stearate 3 ' as well Magnesium carbonate 3 after 3 days
Let stand by
37 ⁰ C ί as well as well Calcius stearate 3 ^ as well Magnesium stearate 3 as well Magnesium carbonate 3

35 60-70 35 40-50 35 as well 35 as well 10 10-15 35 10-15 35 below 1 35 as well 35 as well

GO CD CO

OO

It can be seen from the values in the tables above that the caking of the hardened oil-coated particles is pronounced at the point in time when the crystal structure changes occur, so that if the crystal structure of the hardened oil has not been stabilized, the caking inhibitor, with which the coated parts are offset, is practically ineffective and shows no effectiveness. On the other hand, it can be seen that, if the present invention incorporates the caking inhibitor in hardened oil coated particles after stabilizing the crystal structure of the hardened oil by allowing the coated particles to stand at temperatures higher than 25 ^° C. but lower than the softening point of the hardened oil , the effectiveness of the anti-caking inhibitor is fully exhibited, and stable hardened oil-coated particles which have fluidity and which do not caking at normal temperatures are obtained.

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Claims (4)

Claims 1. A method for preventing caking of coated with hardened oil particles, characterized in that the particles are composed of a core material with a coating of a coating agent which is tiber predominantly of a hardened oil having a melting point of 45 his 85 ⁰ C , for at least 20 hours at temperatures higher than 25 ⁶ C, but lower than the softening point of the hardened oil to stabilize the crystal structure of the hardened oil and then to these particles an inhibitor against caking in an amount of 0.3 to 5 wt .- ^, based on the weight of the particles, is added. 2. The method according to claim 1, characterized in that that as the core material, medicines for humans or animals, agricultural chemicals or food additives are used will" 3 · The method according to claim 1 or 2, characterized in that as an inhibitor against caking finely divided inorganic substance is used. 4. The method according to claim 1 or 2, characterized in that that an alkaline earth salt of a higher fatty acid is used as an inhibitor against caking. 5. The method according to claim 1 or 2, characterized in that as an inhibitor against caking silica, Magnesium aluminum silicate, magnesium carbonate, tertiary Calcium phosphate, calcium stearate or magnesium stearate are used will. 209808/1893 Z5 Blank page