JPH01155938A - Binder for granulation - Google Patents

Abstract

PURPOSE:To raise the m.p. of a binder for granulation to >=60 deg.C by preparing the binder with one or more kinds of mono- or dialcoholamides of specified aliphat. straight chain dicarboxylic acid with monoethanolamine, etc. CONSTITUTION:A binder for granulation is prepd. with one or more kinds of mono- or dialcoholamides of 3-10C aliphat. straight chain dicarboxylic acid with monoethanolamine and/or propanolamine. Alcoholamide of dicarboxylic acid adjusted to pH6-8 by the neutralization of the carboxylic acid residue is preferably used and the pref. m.p. of the alcoholamide is 70-100 deg.C. Since the binder can increase granulation temp. to >=70 deg.C, PEG4,000-6,000 may be used as coat wax at a relatively high temp.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to enzymes, vitamins, medicines, amino acids and other physiologically active substances used in detergents, medicines, textiles, leather, feed, fertilizers and other fields, The present invention relates to a water-soluble, high-melting-point binder substance and its granules, which are used when granulating substances that are relatively unstable in water by a heating melting method.

[Conventional technology]

Various methods have been proposed for granulating various enzyme granules, including enzymes for detergents.

For example, in Japanese Patent Publication No. 58-26315, water and a wax-like substance are used as binders used during granulation. As the waxy substance serving as the binder, polyvinylpyrrolidone, dextrin polyvinyl alcohol, and various cellulose derivatives are used.

JP-A-60-262900 proposes starch and its derivatives, sugar, cellulose derivatives, gelatin, polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol, and the like. Also, special public service 59-3010
In No. 9, polyethylene glycol copolymer, polyethylene glycol-polyethylene oxide, etc. are dissolved in water and granulated.

However, when granulating using an aqueous binder, there are various problems such as the enzyme itself being easily deactivated, a lot of adhesion to the granulator, and the shape of the granules being poor.

In order to solve this problem, it is preferable to use a non-aqueous granulation method. ) etc. are used for granulation.

Furthermore, in Japanese Patent Application No. 60-293167, polyethylene glycol 5000.6000. $lioxyethylene, fa
Examples using t-ren copolymers and the like are shown. Among these, only coconut oil ethanolamide has a high melting point of 67°C, but the granulated product using this /J inder has extremely poor solubility in water, and has physical properties with high solubility such as enzymes for detergents. It cannot be used for what is required.

Therefore, considering binders other than coconut oil monoethanolamide, practically usable binders have melting points of 61° C. or lower. Granulating with such a low melting point binder has various problems in terms of manufacturing and physical properties of the resulting product. Therefore, in order to improve these problems, we searched for a binder material with a high melting point, and as a result, we achieved the present invention.

[Problem that the invention seeks to solve]

Polyethylene glycol, polyoxyethylene glycol, and the like are used as binders when granulating easily water-soluble granules by a heat-melting method.

(Japanese Patent Publication No. 58-26315, Japanese Patent Publication No. 60-293167
) For example, in the case of enzyme granules for detergents, the internal particles are granulated with PEG 5000, and then a cosmetic agent and a wax (melting point 45°C or less) of about PEG 1000 to 1540 are granulated to prevent dust generation and improve color tone. I'm wearing an overcoat.

However, in order to prevent dust generation and blocking of the granules, a harder wax having a melting point higher than that of PEG 1540 (45°C or higher), such as about PEG 4000 (m, p, = 53°C), is desirable.

However, as shown above, most polyethylene glycol and polyoxyethylene waxes have a temperature of 61°C.
When coating fi PEG4000 with a material having a melting point below, it is practically impossible because the temperature difference is small.

In other words, in order to overcoat industrially, the coating temperature must be kept above the melting point of the wax, and in order to satisfy the coater temperature of about ±5°C, when overcoating with PEG 4000, the internal granulation The wax needs to be a substance with a melting point of 63°C or higher, preferably 65°C or higher. If the binder wax of the internal particles has a melting point of 60°C or lower and is industrially overcoated with PEG 4000, the internal wax will melt, causing oozing and disintegration, causing problems with the physical properties of the granules. . therefore,
In order to be able to use a binder with a melting point of 45°C or higher as the coat wax, a wax with a melting point of 70°C or higher is required as the binder for granulating the internal particles, and this is being explored. did.

[Failure to solve the problem]

In the present invention, using a stirring granulator having a structure capable of heating the granulated material with a jacket or the like, the granulated material is heated to 6 to 4
0 t, preferably 10 to 30 t16 of binder material (
The enzyme is granulated in a non-aqueous system by adding a wax containing dicarboxylic acid alcohol amide and heating the mixture to 70 to 90°C.

As mentioned above, while satisfying the temperature conditions, for example,
As a result of searching for a variety of good binders that have the same solubility in water as conventional products, such as enzyme granules for detergents, have relatively low hygroscopicity, and also maintain sufficient stability, we found that It has been found that dialcoholamide-based substances satisfy this condition.

We have found that a dialcoholamide of dicarboxylic acid has a relatively high melting point and also has good water solubility.

For example, when the molar ratio of monoethanolamide of adipic acid is 1/2, the melting point of the amide is 115° to 120°C.
, 1/1.6, it is 80-85°C, and has a fairly high melting point.

Also, amide of lauric acid has a temperature of 76 to 80°C,
Since the solubility was poor, a binder with good granulation properties was obtained by mixing both at a constant ratio.

Dicarboxylic acid substances include C3 malonic acid to C1o
C5 geltaric acid and C6 adipic acid are preferable. however,
Which one to choose can be determined depending on the physical properties of the granulated product, but if it exceeds Clo, the water solubility will drop significantly, so as a binder for detergent enzymes, one with a molecular weight of C4° or less is preferable.

Example t C, adipic acid/monoethanolamide = 1/2
The binder, which is a 4/1 mixture of amide and nogrumitic acid amide, has a high melting point of 77 to 86°C,
Granulation properties were also good. In addition, lauric acid ester 4/
Mixture No. 1 had a melting point of 74 to 80°C and good granulation properties. On the other hand, in enzymes that are sensitive to acids, the remaining groups are N
Neutralize with aOH or Ca(OH)2, pH==6.6-8
When granulation was carried out using wax adjusted to the desired degree, stable granules were obtained.

For example, adipic acid amide/lauric acid amide = 8
5/15 was further adjusted to pH=5.7-6.8 using NaOH or Ca(OH)2aq, and the melting points were 74-76°C (NaOH-based) and 76-81°C (
ca(oH)2 system) and became a good binder.

Monocarboxylic acid amides that can be added are not particularly specified, but commonly used ones include tsucurmitic acid,
Lauric acid, stearic acid, etc. can be used.

[Effect]

The melting point of dicarboxylic acid is 97.5 of geltaric acid (C5).
℃ to 151℃ for adipic acid (C6), which is quite a high temperature range. When this is amidated with monoethanolamine, the melting point decreases depending on the amount added.

That is, in the case of adipic acid, when the molar ratio is 1/2, the temperature is 35°C.
In the case of 1/1.6, by about 70°C, the melting points become about 120°C and 80°C, respectively.

Also, the solubility in water is adipic acid 1.4g/100
IIH20, pimelic acid 2.5 g/l 011) f2
0, geltaric acid improves to 63.9 N/100 E H2O. On the other hand, in order to adjust the hygroscopicity, monocarboxylic acid amide is added. For example, lauric acid amide has a melting point of 76 to 80°C, while stearic acid amide has a relatively high melting point of 90 to 95°C. , becomes close to the amide of dicarboxylic acid, and easily dissolves together, forming a good /S inder.

Since a wax having a melting point of 50° C. to 60° C. and hardness can be used as the coat wax, the quality of the product granules is improved.

Furthermore, since the granulated internal particles are also a fairly hard substance, the dicarboxylic acid alcohol amide itself is not easily crushed, and hard particles can be obtained.

A high melting point is preferable from a process standpoint because it facilitates cooling and solidification after granulation, improving the efficiency of cooling assimilation.

Example 1゜A: Granulation API-21 enzyme bulk powder 500.9, crushed sodium sulfate 10ION, titanium oxide 60F, and adipic acid monoethanolamide (mixture of mono and di, melting point 84°C) 430# were mixed in a granulator with stirring. After mixing for 2 minutes at a spindle rotation speed of 25 Orpm and 300 Orpm, the mixture was granulated at a temperature of 9°C. (granulation time 13 minutes). The particle size distribution of the obtained particles was 14ON
8.6 China 14-42 88% 42 PASS 3.4%, granulation was possible with a fairly good yield. Moreover, no adhesion to the wall of the granulator was observed, and all of it could be discharged, making it an excellent granulating binder.

B: Coating Of the granules in A, 150ON particles ranging from 14 to 142 were coated with polyethylene glycol 6000 (m, p-61°C) at a product temperature of 65°C. The addition rate is 7 g of PI) C6000 per particle, cosmetic agent (40% titanium oxide, 5 g of talc)
0%, silica 10%) was 15%.

Example 2゜A: Granulation API-21 enzyme bulk powder 500g, CaSO
4-2H201040,! i', titanium oxide 60.9
, adipic acid amide/lauric acid amide = 85/
15 was neutralized to −=7 with Ca(OH) 2 and granulated at 85° C. The amount of wax added is 4
00g, and other conditions are the same as in Example 1.

The particle size distribution of the obtained particles is 14ON 5.1
% "14-42 78.3%" 42 PASS 16.6, which was good, and there was no adhesion.

Na φ B: Of the granules of coating A, 100 (l) of particles in the range of 14 to 42 were mixed with PEG4000 (m
, p, 53°C). Other conditions were the same as in Example 1. The whiteness of the particles after coating was good, L = 80 cm, and the solubility (10° C., 3 minutes) was 92 cm.

Example 3゜A: Enzyme powder 250#, crushed sodium sulfate 500g
, 30 g of titanium oxide, and 2209, a mixture of adipic acid monoethanolamide and adipic acid monoisopropanol diamide with a melting point of 78 to 85°C, were charged into a stirring type granulator, and the product temperature was brought to 98°C with jacket hot water, and the main shaft was heated to 98°C with jacket hot water. 250rpm.

Granulation was performed using a chopper at 300 rpm for 22 minutes. The particle size distribution of the granules after granulation was 14 on 12.1% 14-42" 83.7% 42 pass 4.2%.

No adhesion to the wall of the granulator was observed, and the granulation yield was good at 83.7 cm.

B: A cosmetic agent was overcoated using PEG 6000 at a product temperature of 65° C. using 500 g of particles 14 to 421 of coating A granules. (The composition and addition rate were the same as in Example 1.) The whiteness of the obtained granules was L=81%, and the solubility (10° C., 3 minutes) was 92%, which was good.

Example 4゜In Example 2, the pH of the binder was 5.5, 6,
7.

Pelletization was performed using the product prepared in 8.9. In the granulation process, almost the same results as in Examples 2 and 3 were obtained.

These granules were stored for two weeks at 40° C. and humidity of 80° C., and the residual activity was measured 1 to determine storage stability.

The correlation between the obtained storage stability and - is as shown below,
A pH range of 6 to 8 was effective.

5.5 69.7chi 6.0 95.3chia, 0 97.4chi 8.0 96.1chi 10.0 75.1chi Comparative example 1゜Enzyme 500g, Na2SO41010Jil,
Granulation was carried out under the same conditions as in Example 1 using Tie□60II and PEG 6000 as a binder. On the other hand, P
55℃ using EG 4000 as coating binder
However, the enzyme color oozed out and the whiteness significantly decreased to 1 inch of beef.

Comparative Example 2゜Enzyme 5009, Na2SO41010,9Tie□
60. ! In Example 9, granulation was carried out in the same manner as in Comparative Example 1 using PEG 6000 as a binder. PEG to the obtained particles
An attempt was made to overcoat 6000 at 59°C, but granulation occurred during coating and the particles became coarse.

〔effect〕

This binder has a melting point of 60°C or higher, and the granulation temperature can be set to 70°C or higher.
000 can be used.

The granules obtained by this method had good whiteness, little hygroscopicity, and sufficient solubility.

On the other hand, like the adipic acid type, the present Tinder is inexpensive and can be used industrially.

Claims (1)

[Scope of Claims] 1. At least one mono- or dialkholamide of an aliphatic linear dicarboxylic acid having 3 to 10 carbon atoms with monoethanolamine and/or propanolamine is used. Binder for granulation. 2. The binder according to claim 1, wherein the carboxylic acid residues of the dicarboxylic acid alcohol amide are neutralized to have a pH of 6 to 8. 3. The melting point of dicarboxylic acid alcohol amide is 70-1
The binder according to claim 1, wherein the temperature is 00°C.