JPS58185406A - Preparation of perboric acid salt - Google Patents

Abstract

PURPOSE:To obtain a perboric acid salt free from agglomerating tendency and having high solubility in water, by adding a phosphoric acid compound and a soluble metallic salt to a powdery perboric acid salt, and granulating and drying the mixture. CONSTITUTION:The powdery perboric acid salt is sodium perborate powder having particle diameter of 40-150mu. The phosphoric acid compound added to the salt is primary sodium phosphate and/or secondary sodium phosphate, etc., and its amount is 0.1-2.0wt% based on the perborate. The soluble metallic salt is one or more compounds selected from magnesium sulfate, magnesium chloride, etc., and its amount is 0.05-0.5wt% based on the borate. The mixture is added with water to the water-content of about 10-15% before granulation. The granules are dried at 35-100 deg.C. The obtained perboric acid salt has excellent stability when compounded with a detergent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a ma7F method for perborate, especially sodium perborate, which has a strong caking property, poor solubility in water, and excellent detergent formulation stability. to.

Perborates are generally said to have better storage stability than percarbonates such as sodium percarbonate. However, when stored under high temperature and high humidity, it is prone to drying out, especially during summer, and the product value is significantly reduced.

In addition, when perborate is added to a detergent, the moisture contained in the detergent not only promotes the solidification of the perborate, but also causes the perborate to split up and become an active oxygen decreases.

Additionally, perborates generally have various disadvantages such as being sensitive to cold water. Conventionally, as a method to improve storage stability, polyethylene glycol monostearate was coated on the surface of sodium perborate. However, attempts have been made to suppress the decrease in active aIIA under high temperature and high humidity conditions, but these are not necessarily sufficient. On the other hand, no reports have been found so far regarding the improvement of am property against cold water.

The present inventors have completed the present invention as a result of various studies to improve the drawbacks of the above points IIf and -1.

The object of the present invention is to maintain caking properties even under hot and humid conditions, and to prevent caking or decomposition when added to detergents.
``It is an object of the present invention to provide a perborate salt, particularly sodium perborate, which has excellent storage stability and excellent solubility in cold water.

The present inventors have discovered that phosphoric acid, phosphates, magnesium sulfate, etc., which have been conventionally used to stabilize percarbonates such as sodium percarbonate, have been converted into powdered filtrate. When added to sodium borate and subjected to wet granulation, a water-repellent coating is formed on the surface of the particles, which gives the particles straightness, improves storage stability, and significantly improves caking. It was found that the improvement was found, and when one set of water glass, Chiya-Kei d14, was added, the salt became gelatinous and the particles of sodium perborate were deposited in the granulation filter. It was found that the size of this gelling quickly affects the 41 + 4 cases of granulating and drying granulated sodium perborate in cold water. It has been found that the perboric acid combination has extremely high stability, anti-caking properties and other properties.

This invention was made based on Chiaki Nyoshin in E.
The powdered per5111 salt was mixed with at least -4 ν of 1v of gold phosphate and at least -1 of the IITsI metal salt, pounded with silkworms, magnetically granulated, and then dried to # value, and A et al. V
Addition of at least one kind of phosphor compound, at least one kind of if-containing metal, and at least one kind of 'r4fi hydro/l salt or silicate, granulation, and then drying. Concerning the removal of perborate with excellent hardness and mildness. .

The phosphoric acid compound used in the present invention, a (@ metal salt and hydrosyl silicate or silicate, may be referred to as "1 addition" hereinafter, and in this case, "phosphoric acid compound" is the first addition). a second group of additives;
and [hydrosyl silicate or silicate salt] are referred to as the third group of additives.The perborate of the present invention will be explained using perborate salt.

The above first group of additives used in this book are primary, secondary and tertiary phosphates, IJium, secondary and tertiary potassium phosphates, sodium tripolyphosphate, hexametaphosphorus. Selected from sodium chloride.

In order to fully achieve the purpose of the present invention, these first additions 7xl#ll are usually 0.1 to 2.
0 weight Il is used, and furthermore, 0.2 to 1.0 weight Il
Excellent is preferred. Moreover, these first group 171Q agents are usually used as an aqueous solution of 5 to 204 degrees centigrade for CV use. Among the additives of the first group, monosodium phosphate and dibasic sodium phosphate are particularly suitable.

In addition, as the recurrent metal salt which is the additive Qom of the second group of t in the present invention, magnesium sulfate, fine magnesium salt of magnesium chloride, calcium salt such as calcium chloride, aluminum salt such as aluminum chloride, aluminum sulfate, etc. , barium chloride, etc. These second group additives are usually 0.05 to 1.0 weight of sodium perborate, and more preferably 0.1 to 1.0 weight of sodium perborate.
0.5 weight t4 is suitable, and these additives belonging to the second group are usually used as an aqueous solution with a resistance of 1 to 1 Ω.

Among the additives in the second group, magnesium sulfate and magnesium chloride are particularly suitable.

These additives are added at the time of granulation, but it is important to mix the two types of additives in advance or to add them simultaneously from separate supply ports. It is not preferable to add the additives of the first group and the additives of the second group individually and sequentially, as this would sufficiently impair the object of the present invention.

Furthermore, in the present invention, -J of the third group described above
It is possible to add silicates or silicates which are II+@, and this third group of additives can be added to
By doing so, the moisture resistance, storage stability, +1II of the particles
I4 characteristics can be improved.

The third group of silicates that are used for stock cutting include r-alkali gold salts of silicic acid, commercially available No. 1 to No. 5 permanent glass, potassium silicate, lithium silicate, @woody sodium silicate. etc. Hydrosil silicate is also called colloidal silica or silica sol, and is known per se as an aqueous dispersion of silicon oxide with a particle size of 10 to 100 mμ. A commercially available product is, for example, "Snowtex." Among the gay 1114, No. 1 to No. 3 missing glass are 1 to 2.
54 concentration was used, and other silicates were used at concentrations of 1 to 2.
0 to 11 degrees are used. These are used in a weight range of 0.01 to 0.5 as 5102 relative to sodium perborate. In addition, hydrosyl silicate is 1
~SO 憾Im & direct is used, and the same f 0.01~0゜5 as 8i02 for sodium perborate.
It is used in the Kaji of Chūkan-ō.

If the usage of these third group additives is outside the above range, the objects of the present invention cannot be fully achieved and the remarkable effects cannot be exhibited.

The powdered sodium perborate used in the present invention is generally obtained by a method in which a permanent solution of sodium metaborate is treated with hydrogen peroxide to form crystals from an aqueous solution. If the grain size of crystallized crystals becomes too large, it becomes difficult to perform granulation, so
It is preferable to keep it within the range of 0 to 150j, and for this purpose, it is desirable that the fla11 time of the crystal in the reactor be within 2 hours, preferably 0.5 to 1.0 hours.

In the method of the present invention, a wet granulation method is used to granulate IJum perboric acid, and the granulator used for granulation may be any type of granulator used for wet granulation. Although it is also possible to use JIC, a type that can sufficiently perform crosstalk and mixing is preferable.

During granulation, the water content of sodium perborate is 10 to 1.
When the temperature reaches 41 degrees, water is added and kneaded for 1 time.

Examples of the granulator include a pelletizer, which is a screw extrusion plate equipped with a screen at the tip, which mixes and kneads raw materials, additives, etc. using a batch-type or continuous-type kneader or mixer 6.

The granules are then dried in flow state, for example by hot air drying, at a temperature of 35 to 100°C. Drying temperature ILI
Therefore, the shape of the obtained sodium perborate, that is, the water content is different, and when it is dried at an ffi degree of S5~50°C over 4, the majority is usually Na Bo 2 H2O-
5) I20, and when dried directly at 50 to 70 degrees Celsius, most of it becomes NaBO2"I20・I20, and when dried at around 100 degrees Celsius, most of it becomes NaBO11120. By granulating, caking property, storage stability and fI
Although the Is property and the like are improved, in order to fully exhibit these effects, it is desirable to dry at a temperature of 50°C or higher, and a temperature of 50 to 70°C is particularly suitable.

Sodium perborate obtained by the method of the present invention has moisture resistance, solidification resistance, excellent storage stability, and improved solubility in cold water.

Although the present invention has been described above using perboric acid (17um), it can be applied to other perborates and exhibits similar effects.

Reference example (perboric acid) IJum construction example) Filled with sodium perborate 20 '111111 as the working fluid.
The sodium metachloride solution 1a and at were simultaneously and continuously fed, and the solution temperature was maintained at 1B to 20°C, and the reaction was carried out with stirring. The crystallization time in the reaction-intermediate process was 30 minutes. 41 of the produced sodium perborate crystals are continuously taken out from the reactor, separated by a centripetal separator, and placed in a jolly
/H/1 Crystals of sodium perborate were obtained.

The grain size of the obtained crystals was an average grain size of [110μ].

50 tons of solidified sample was taken into a wide-mouthed bottle, solidified, and put back into a constant temperature bath at a cycle of 45°C for 12 hours and 251C for 12 hours.
6-1 Fill a hynyl chloride*fat mt'to with a length of 200 cm and a damper at a position 100 cm from the bottom, and measure the time from when the damper is inserted until all the samples can flow out. This indicates that the outflow time is short and the SM is not running.

Stability in detergent formulation Contains 0.3t of sodium perborate and 2.7V of detergent (the detergent used has AB820, 7 polyoxyethylene lauryl ethers, 20 tripolyphosphoric acid, and boronic acid 504 as main components). Then, it was left open for 7 days at 35°C and 80℃ FLH, and the amount of effective oxygen was determined after being left and after being left open for 7 days.
The decomposition rate was determined according to the following formula and the storage stability was kept constant.

Pour 1 ton of pure water at 25℃ into a 1 ton solubility beaker and raise it to a height of 40 cm.
, 25 Orpm stirring bar with stirring blades 25 cm wide
5 tons of sample was introduced, and the time required for the particles to completely disappear was determined at a constant time.

Example: The sodium perborate obtained in the reference example was charged into a double-arm kneader manufactured by Sigma-ya, and the additives of the second group and the third group were added at the same time. ! After mixing, pure water was added so that the water content was 10 to 15, and the middle part was marked with ink for about 30 minutes. Next, the mixture was granulated using an extrusion granulator (pelletizer) having a 0.7-degree screen, and then fluidized and dried with 1 all of hot air at 50°C.

In addition, the porcelain that was granulated and dried without adding any steel was used.

32

Claims (1)

[Claims] (1) Adding and granulating at least one phosphoric acid compound and at least one soluble metal salt to S wood-like perborate,
Then dry it? First thing to do is to prevent the same f! E and method for producing a perborate with excellent pleasantness (21a Adding at least one phosphoric acid compound, at least one soluble metal salt, and at least one hydrosyl silicate or silicate to the final perborate) 11 Retrospective method for perborate with excellent solid 1 m IFJ-stopping properties and disintegrating properties, characterized by adding, granulating, and then drying. (3) Adding phosphoric acid compound to perborate at a ratio of 0.1 to 1 m 2
．． The manufacturing method according to claim A1 or IB2, in which 0% by weight is added. (4) Add 0.05 to 0.0% of soluble metal salt to perborate.
5] Add 1 amount of 4 to 4 I permission request - around I11 or 2
Manufacturing method of LJ Kii. (IIIllll adding 51 hydrosyl silicate or silicate in an amount of 0.01 to 0.51 per 1 part of perboric acid)
Scope of search for lFIa - manufacturing method according to item 2. 16) Phosphoric acid compounds are secondary and tertiary phosphoric acid f
) 17um, primary, secondary and tertiary potassium phosphate,
The manufacturing method according to claim 1111E1 or 2, which is selected from sodium tripolyphosphate and sodium hexametaphosphate. (c. AI of a patent claim in which ``Chocooking Gold Chapter 4'' is one of magnesium sulfate, magnesium chloride, calcium chloride, aluminum chloride, aluminum sulfate, and barium chloride.
The manufacturing method according to sI item 1 or 112. (8) Water glass with silicate No. 1 to No. 3, potassium silicate, lithium silicate, silicate sodium silicate,
Claim 2 selected from magnesium silicate
Manufacturing method described in section. (9) Dry! The manufacturing method according to claim 1 or 1121g, wherein the process is carried out at 35 to 100° C. once. (10) The method for producing perborate according to claim 1 or 2, wherein the flL straightness of the perborate in the form of a sachet is 40 to 150 tones.