JP2671099B2 - Method for producing antimony oxide aqueous sol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an antimony oxide aqueous sol, more specifically, an antimony oxide aqueous sol capable of inexpensively producing a high-concentration antimony oxide aqueous sol in which antimony oxide is dispersed in fine particles. It relates to a method for producing a sol.

[0002]

_2. Description of the Related Art Antimony oxide [compositional formula: Sb ₂ O _{3 + x}
(0 <X ≦ 2)] is mainly added to a halogen-containing resin emulsion or a halogen-based flame retardant-added resin emulsion and applied to an object to be processed to make the resin emulsion to be flame-retarded or to be processed. It is widely used as a flame retardant aid for imparting flame retardancy to objects.

Further, the aqueous sol of antimony oxide is
Since the particle size of antimony oxide is very small, it has excellent transparency, and when applied to an object to be processed, it does not impede the hue of the object to be processed as a base.

The method for producing the aqueous sol of antimony oxide is roughly classified into antimony trioxide (Sb ₂ O).
There are known a method of oxidizing ₃ ) with hydrogen peroxide (H ₂ O ₂ ) in water and a method of decomposing an antimonate by acid decomposition.

The above-mentioned method of oxidizing antimony trioxide with hydrogen peroxide includes a method of oxidizing antimony trioxide with hydrogen peroxide without adding an additive, and
There is a method of adding an inorganic or organic additive and oxidizing antimony trioxide with hydrogen peroxide.

In the method of oxidizing antimony trioxide with hydrogen peroxide without adding the above-mentioned additives, in order to obtain an aqueous sol of antimony oxide with a high concentration, antimony trioxide is added with hydrogen peroxide at a high concentration. Oxidation increases the particle size of the generated sol, and when added as a flame retardant aid to a resin emulsion for processing, the transparency of the object to be processed is impaired. Therefore, if it is attempted to keep the particle size of antimony oxide small so as to ensure good transparency, an aqueous sol having a concentration of about 25% (% is% by weight unless otherwise noted) is obtained. It is the limit.

However, in a low concentration antimony oxide aqueous sol having a concentration of 25% or less, the emulsion concentration is lowered when it is added to a resin emulsion as a flame retardant aid, so that the processing characteristics such as coating are remarkably reduced. This causes a problem that it is necessary to add a thickener or the amount of the additive for imparting other properties must be limited.

Therefore, when a low-concentration aqueous sol is concentrated to a high-concentration aqueous sol having a concentration of 50% or more, the viscosity is excessively increased to deteriorate the processing characteristics, and an additional concentration step causes an increase in cost. There is a problem.

Therefore, by simply oxidizing antimony trioxide with hydrogen peroxide, it is not possible to inexpensively produce a high-concentration aqueous sol in which antimony oxide is dispersed in fine particles.

Therefore, as described above, attempts have been made to obtain a high concentration aqueous sol by adding an inorganic or organic additive in the oxidation step with hydrogen peroxide.

Among the methods of adding the additives in the oxidation step with hydrogen peroxide as described above, the methods of adding the inorganic materials are described in JP-B-57-11848 and JP-B-3-3.
There are methods disclosed in JP-A-5248, JP-B-4-29610, JP-A-60-108466, JP-A-2-174929, and the like.

The inorganic substances to be added include hydroxides of alkali metals or alkaline earth metals, inorganic salts,
Inorganic silicic acid compounds are used.

For example, in Japanese Patent Publication No. 57-11848, the antimony trioxide, potassium hydroxide and hydrogen peroxide are reacted at a molar ratio of about 1: 2.1: 2 to produce potassium antimonate. Then, a method for producing a colloidal sol of antimony oxide is disclosed, in which deionization is performed and then deionization is performed.

However, even with the above method, a high-concentration aqueous sol cannot be obtained, and if the concentration is increased to a high concentration, the sol becomes thick and handling becomes difficult, and the cost of concentration increases, which also increases the cost. There was the problem of becoming expensive.

Further, in Japanese Patent Publication No. 4-29610,
In the reaction between antimony trioxide and hydrogen peroxide, the molar ratio of hydrogen peroxide to antimony trioxide is 1: 1.2.
5 to 1.8, and an alkali metal hydroxide or the like in the reaction system is 1.5 to 30 mol% with respect to antimony trioxide.
A method for producing colloidal antimony oxide is disclosed, in which an oxidation reaction is performed by adding the colloidal antimony oxide.

However, this method has a problem that an alkali metal compound is mixed in the antimony oxide colloid, and the alkali metal compound reduces the flame retardant aid effect of the antimony oxide.

As a method of adding an organic substance in the oxidation step with hydrogen peroxide, there is a method disclosed in Japanese Patent Publication No. 61-24330.

In this Japanese Patent Publication No. 61-24330,
The granular antimony component is oxidized with hydrogen peroxide in the presence of a water-soluble stabilizer such as an alkanolamine, an alkanolamine salt, an aliphatic α-hydroxycarboxylic acid, and an aliphatic polyhydric alcohol, or at least a part of the component is oxidized. A method for producing an aqueous sol of antimony oxide is disclosed in which the above water-soluble stabilizer is added after conversion into hydrated antimony oxide colloidal particles.

However, even with the above method, in order to obtain good sol characteristics, only a low-concentration sol can be produced. Therefore, if the concentration is increased to a high concentration, the viscosity increases and the cost increases due to the addition of concentration cost. There was a problem.

Although not a method for producing an aqueous sol, as a prior art relating to the production of antimony oxide, Japanese Patent Laid-Open No.
Japanese Unexamined Patent Publication No. 3-310726 discloses a method for producing an antimony oxide powder composition containing 8 to 13% of water and having good redispersibility by spray drying an antimony aqueous sol containing a stabilizer.

From the antimony oxide powder composition obtained by the above method, it is possible to produce a high-concentration antimony oxide aqueous sol having an antimony oxide concentration of 50% or more, but controlling the water content by spray drying. However, there is a problem in that it is difficult to perform stable production, and that the cost is increased due to the additional cost associated with spray drying.

Further, a composition obtained by subjecting antimony trioxide to an alkali treatment after the oxidation treatment is disclosed in JP-A-60-108466. In this case as well, the alkali metal or alkaline earth metal compound used for the treatment is disclosed. Was mixed in the composition, and the effect of the flame retardant aid of antimony oxide was lowered.

Further, as a method of acid-decomposing the antimonate to peptize it, Japanese Patent Publication No. 4-4980,
JP-A-61-227918 and JP-A-62-182.
There is a method disclosed in Japanese Patent No. 116, etc.

For example, in the above Japanese Patent Publication No. 4-4980, alkali antimonate is added in a stoichiometric ratio of 0.7 to 0.7.
After reacting with a 5-fold amount of a monovalent or divalent inorganic salt to form an antimony oxide gel, the gel is separated and washed with water,
A method for producing an antimony oxide sol, in which the organic base is used for peptization, is disclosed.

However, in any of the above methods of decomposing an antimonate by acid decomposition, since alkali antimonate is used as a raw material in each case, the gel is separated and acid washed after acid decomposition. However, since the alkali metal cannot be completely removed and the alkali metal remains in the produced aqueous sol, there is a problem that the flame retardant aid effect of antimony oxide is reduced.

[0026]

As described above, the conventional method for producing an aqueous sol of antimony oxide has various problems.

For example, in the method of oxidizing antimony trioxide with hydrogen peroxide without adding an additive, the particle size of the sol produced becomes large when high-concentration oxidation is carried out, so that the resin emulsion is used as a flame retardant aid. When added and processed, the transparency of the object to be processed is impaired. Therefore, if an aqueous sol is to be obtained with the particle size kept small so as to ensure good transparency, only a low concentration aqueous sol of about 25% can be obtained.

However, in the case of a low-concentration aqueous sol, the emulsion concentration is lowered when added to the resin emulsion, so that the processing characteristics such as coating are remarkably deteriorated. Therefore, it is necessary to add a thickener which does not need to be added. Needed or
Alternatively, there arises a problem that it is necessary to limit the addition amount of the additive for imparting other characteristics.

When the low-concentration aqueous sol is concentrated to a high-concentration aqueous sol having a concentration of 50% or more, the viscosity is increased and the concentration cost is increased, which leads to an increase in cost.

Therefore, by simply oxidizing antimony trioxide with hydrogen peroxide, it is not possible to inexpensively produce a high-concentration aqueous sol in which antimony oxide is dispersed in the form of fine particles.

Therefore, a method of adding an alkali metal compound or the like in the oxidation step with hydrogen peroxide has been adopted, but the above alkali metal compound remains in the produced aqueous sol, and the flame retardant auxiliary effect of antimony oxide is obtained. Therefore, it is necessary to remove metal ions by ion exchange or ultrafiltration, etc., and the cost is increased due to the addition of costs associated with the adoption of these steps.

Although a high-concentration aqueous sol can be produced by the method in which alkali antimonate is treated with an inorganic acid to deflocculate, even if the gel is separated and washed with acid after acid decomposition, the starting material Part of the alkali metal content in the alkali antimonate is incorporated into the structure of antimony oxide, and as a result, a few% of the alkali metal with respect to antimony oxide remains in the aqueous sol. This will reduce the flame retardant aid effect.

Therefore, a high-concentration oxidation that does not deteriorate the processing characteristics of the resin emulsion, does not impair the hue of the object to be processed, and can sufficiently exhibit the flame retardant aid effect of antimony oxide. The emergence of antimony aqueous sols is desired.

[0034]

Means for Solving the Problems As a result of intensive studies to meet the above-mentioned demand, the inventors of the present invention oxidize antimony trioxide with hydrogen peroxide to form an aqueous sol of low concentration antimony oxide, It was found that when an inorganic acid or an ammonium salt is added to the above aqueous sol to gelate the sol, the obtained antimony oxide gel can be easily filtered.

Furthermore, the present inventors have surprisingly found that
The filter cake obtained by the above-mentioned filtration is agglomerated with a weak cohesive force, and the peptizing power of a dispersant such as triethanolamine easily disperses and peptizes to obtain a high-concentration antimony oxide aqueous sol. I found that.

Therefore, by combining the above two findings, the present inventors can inexpensively produce a high-concentration antimony oxide aqueous sol containing no metal compound other than antimony oxide and having antimony oxide dispersed in fine particles. It succeeded in manufacturing it, and reached the present invention.

In the present invention, since the oxidation of antimony trioxide with hydrogen peroxide can be carried out at a low concentration, the particle size of antimony oxide does not become large. Therefore, when added to the resin emulsion and processed, the hue of the object to be processed is not impaired.

Then, instead of concentrating the low-concentration aqueous sol, it is gelled, filtered, and deflocculated with a dispersant to increase the concentration, so that thickening as in the case of concentration is not achieved. Does not happen. Therefore, when added to the resin emulsion, the processing characteristics of the resin emulsion are not deteriorated, and since the aqueous sol has a high concentration, the emulsion concentration is not significantly decreased.

Further, since there is no need for operations such as a drying step such as spray drying or a concentration step, or a step of removing metal ions such as ion exchange or ultrafiltration, it is possible to inexpensively produce a high-concentration antimony oxide aqueous sol. You can

The details for carrying out the present invention will be described below.

First, the concentration of antimony trioxide when oxidizing antimony trioxide with hydrogen peroxide is 5% to 25%.
Is preferred, with 10% to 20% being particularly preferred. When the concentration of antimony trioxide is lower than 5%, the productivity is lowered, and when the concentration of antimony trioxide is higher than 25%, the particle size of antimony oxide after oxidation is large and the transparency may be lowered. is there.

It is appropriate that the amount of hydrogen peroxide for the oxidation of antimony trioxide is 0.8 to 2.5 mol per 1 mol of antimony trioxide, particularly 1.4.
Molar to 2.2 mol are preferred. When the amount of hydrogen peroxide is less than 0.8 mol per mol of antimony trioxide, an antimony oxide sol having good transparency is not produced, and the amount of hydrogen peroxide is 2. per mol of antimony trioxide. If it exceeds 5 mol, unreacted hydrogen peroxide increases and it is not economical.

The antimony oxide produced by the oxidation of antimony trioxide with hydrogen peroxide as described above is represented by the composition formula Sb ₂ O _{3 + x} (0 <X ≦ 2),
In the present invention, antimony oxide means all of this Sb.
₂ O _{3 + x} (0 <X ≦ 2) is meant. This Sb ₂ O _{3 + x}
The main specific examples of those belonging to (0 <X ≦ 2) are:
For example, Sb ₂ O ₄ , Sb ₆ O ₁₃ , Sb ₂ O _{5 and the} like can be mentioned, and depending on the molar ratio of hydrogen peroxide to antimony trioxide, they are often produced as a mixture thereof or their It is produced as a hydrate, a mixture of those hydrates, a mixture of those oxides and hydrates, and the like. The antimony oxide aqueous sol obtained as described above has a low concentration as in the case of the prior art, and the low concentration usually means 25% or less.

As the inorganic acid for gelling the aqueous sol of antimony oxide produced by the above oxidation, for example, a monovalent or divalent inorganic acid having a high acid strength such as hydrochloric acid, sulfuric acid or nitric acid can be used. Especially, hydrochloric acid and sulfuric acid are preferable.

The ammonium salt for gelling the aqueous sol of antimony oxide produced by the above-mentioned oxidation is, for example, ammonium chloride, ammonium sulfate,
Examples thereof include ammonium acetate, ammonium bromide, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate, and the like, with ammonium chloride, ammonium acetate, ammonium sulfate and the like being particularly preferable.

The addition amount of the inorganic acid or ammonium salt for gelling the above-mentioned antimony oxide sol needs to be 1% by weight or more, preferably 2% by weight or more, based on the antimony oxide. .

If the amount of the inorganic acid or ammonium salt added is less than 1% by weight with respect to antimony oxide, a good gel will not be produced, and filtration failure or filtration time will increase, which is not economical. The amount of the inorganic acid or ammonium salt added is not particularly problematic if it increases, but after filtration, the amount of washing liquid for removing them increases, so an appropriate amount is preferable, and it is preferable that the amount is 10% based on antimony oxide. It is preferably up to about wt%.

Besides the above-mentioned inorganic acid or ammonium salt, an alkali metal compound such as sodium chloride or sodium sulfate can be used as an additive for gelling an aqueous sol of antimony oxide. When a compound is used, an alkali metal is incorporated in the structure of antimony oxide, and the effect of antimony oxide on the flame retardant aid is reduced, which is not preferable.

After the filtration, it is washed with water that does not sol again. Usually, the amount of water is about 10 to 30% of the total volume of the aqueous sol used for filtration.

Examples of the dispersant for peptizing the filter cake of antimony oxide gel obtained by filtration include alkanolamines such as triethanolamine, diethanolamine, monoethanolamine, tripropanolamine and N-ethylaminoethanolamine. Can be mentioned.

In addition to the above alkanolamines,
Alkanolamine salts such as triethanolamine phosphate, aliphatic α-hydroxycarboxylic acids such as tartaric acid,
Aliphatic polyhydric alcohols such as glycerin have a peptizing ability and can be used as a dispersant, but the above-mentioned alkanolamines are particularly preferable.

The amount of the dispersant such as the alkanolamine added is 1 to 50% by weight based on antimony oxide.
And preferably 3 to 30% by weight,
More preferably, it is 3 to 15% by weight. If the added amount of the dispersant such as alkanolamine is less than 1% by weight based on antimony oxide, the deflocculation state is not good, a sol with good transparency is not formed, and the dispersant such as alkanolamine is not formed. If the added amount is more than 50% by weight with respect to antimony oxide, the emulsion characteristics may be adversely affected when added to the resin emulsion, and the concentration of antimony oxide in the aqueous sol should not be higher than 40%. It is not preferable because there is.

The concentration of antimony oxide in the aqueous sol after deflocculation is determined by the squeezing ratio of the filter cake and the amount of water added during deflocculation. If the antimony oxide concentration is 65% or less, it varies depending on the purpose. It is possible to produce an aqueous sol having a concentration of 0.1%, and the present invention is applied when an aqueous sol of antimony oxide is produced at a higher concentration than that of the prior art, that is, a concentration of more than 25%, but especially 40% or more, especially 45% The effect is particularly remarkable when the above-mentioned high-concentration aqueous sol is obtained.

For deflocculation with a dispersant, for example, stirring dispersion, disper dispersion, sand grinder dispersion, or the like can be adopted, but there is no particular limitation.

[0055]

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples.

Example 1 561 ml of water was placed in a container having an internal volume of 1 liter, 114 g of antimony trioxide powder was added thereto, and 60.8 g of 35% hydrogen peroxide solution was further added thereto. The ratio of hydrogen peroxide to antimony trioxide was 1.6 mol per mol of antimony trioxide.

The suspension obtained is heated with stirring,
The temperature was raised to boiling in 5 minutes and the boiling state was maintained for 1 hour to obtain an antimony oxide aqueous sol.

While the obtained antimony oxide aqueous sol was cooled and kept at 80 ° C., ammonium chloride 3.
0 g (about 2.6% by weight based on antimony oxide) was added and stirred for 15 minutes to obtain an antimony oxide aqueous gel.

The obtained antimony oxide aqueous gel was used as No. 1 manufactured by Toyo Roshi Kaisha, Ltd. Diameter with 2 sheets of 5C filter paper 19.
Suction-filter using a 5 cm nutche (Buchnerroth), and immediately after removing the liquid on the nutche, water 100
Additional ml was added and suction filtration was performed subsequently. After the filtration was completed, the antimony oxide wet cake on the filter paper was taken out.

A 10 g portion of the obtained antimony oxide wet cake was dried at 100 ° C. for 4 hours, and the water content of the wet cake was measured. As a result, the water content was 38.3%.

120 g of the obtained antimony oxide wet cake was placed in a 200 ml beaker, 7.2 g of ion-exchanged water and 7.4 g of triethanolamine (about 10% by weight based on antimony oxide) were added, and the mixture was stirred for 1 hour. A high concentration antimony oxide aqueous sol was obtained.

The obtained aqueous sol had a pH of 7.95,
Viscosity: 11 cp, antimony oxide in aqueous sol,
The concentrations of Na ₂ O and Cl are as follows: antimony oxide: 52.6%, Na ₂ O: 0.01% or less, C
1: 80 ppm. In addition, oxidation
Nchimon Sb ⁺⁵ / Sb ⁺³ [pentavalent antimony and trivalent
The ratio with antimony] was 3.9. The viscosity is 2
It was measured at 5 ° C. by a single cylinder type rotational viscometer Vismetron type VS-Al manufactured by Shibaura System Co., Ltd., and the subsequent viscosity was also measured under the same conditions. Also on
Note Sb ⁺⁵ / Sb ⁺³ is obtained as follows.
You. First, the sample (aqueous sol) is dissolved in hydrochloric acid and the atomic absorption
The total Sb content is measured by an analytical method. And S in the sample
b ^{+ 5} was reduced by potassium iodide at room temperature
Sb was determined by titrating arsenic with sodium thiosulfate.
Measure ⁺⁵ amount. From these measured values,
Calculate Sb ⁺⁵ / Sb ⁺³ . Sb ⁺⁵ / Sb ⁺³ = Sb ⁺⁵ amount / (total Sb amount-Sb ⁺⁵ amount) Note that Sb ⁺⁵ / S in the following Examples and Comparative Examples.
b ^{+3 is} also obtained by the same method as above.

The aqueous sol obtained as described above was dried at 95 ° C. for 12 hours, and the specific surface area of the dried material was measured by Multisorb 12 (fully automatic 12-specimen surface area measuring device) manufactured by Yuasa Ionics. However, the specific surface area is 66 m ^2.
It was confirmed that the average primary particle size of antimony oxide in the aqueous sol was very small, since the specific surface area was large.

Further, the aqueous sol obtained as described above was diluted to a concentration of 0.5% and put into a quartz cell having a width of 1 cm, and the total light transmittance and haze were measured by Suga Test Instruments Co., Ltd. As a result of measurement with a direct reading haze computer HGM-2DP type, total light transmittance is 64%, and haze degree is 1
It was 7%, and it was confirmed that the obtained aqueous sol was a transparent aqueous sol.

Moreover, the aqueous sol obtained as described above did not show an increase in viscosity even when stored at room temperature of 30 ° C. for 30 days.

Example 2 When converting the aqueous sol of antimony oxide into a gel, 8.6 g of 35% hydrochloric acid was substituted for the ammonium chloride used in Example 1 (about 2.6 as hydrogen chloride based on antimony oxide). (Wt%) was used, and the same treatment as in Example 1 was performed to obtain a wet cake of antimony oxide.

When the moisture content of this wet cake was measured by the same method as in Example 1, the moisture content was 36.3%.
Met.

Based on the above water content data, 120 g of antimony oxide cake, 11 g of ion-exchanged water and 7.64 g of triethanolamine (about 10% by weight based on antimony oxide) were used in the same manner as in Example 1. After the treatment, a high concentration antimony oxide aqueous sol was obtained.

The obtained aqueous sol had a pH of 7.4 and a viscosity of 10 cp, and contained antimony oxide and N in the aqueous sol.
The concentrations of a ₂ O and Cl are as follows: antimony oxide: 51.9%, Na ₂ O: 0.01% or less, Cl:
It was 110 ppm. Then, the oxidized sol in the aqueous sol
Ntimon's Sb ⁺⁵ / Sb ⁺³ was 4.0. The specific surface area, total light transmittance, and haze of antimony oxide obtained by drying this aqueous sol are as follows: specific surface area: 63 m ² / g, total light transmittance: 66%,
The haze degree was 16%, and it was confirmed that the obtained aqueous sol was a transparent aqueous sol.

The aqueous sol obtained as described above did not show an increase in viscosity even after being stored at 30 ° C. for 30 days.

Example 3 The amount of ammonium chloride used when converting an aqueous sol of antimony oxide into a gel was increased to 30 g (the amount of ammonium chloride was about 26% by weight with respect to antimony oxide) to form a gel. The amount of water when filtering and washing with water is 60
The same treatment as in Example 1 was performed except that the amount was increased to 0 ml to obtain a wet cake of antimony oxide.

When the moisture content of this wet cake was measured by the same method as in Example 1, the moisture content was 39.5%.
Met.

Based on the above water content data, 120 g of antimony oxide cake, 4.7 g of ion-exchanged water, and 7.26 g of triethanolamine (about 10% by weight based on antimony oxide) were used as in Example 1. The same treatment was carried out to obtain a high concentration aqueous sol of antimony oxide.

The obtained aqueous sol had a pH of 7.7 and a viscosity of 13 cp, and contained antimony oxide and N in the aqueous sol.
The concentrations of a ₂ O and Cl are respectively as follows: antimony oxide: 52.3%, Na ₂ O: 0.01% or less, Cl:
It was 90 ppm. Then, the oxidation anxide in the aqueous sol
Simon's Sb ⁺⁵ / Sb ⁺³ was 3.9. Also,
The specific surface area of antimony oxide obtained by drying this aqueous sol, total light transmittance, haze degree, respectively, as follows,
The specific surface area: 65 m ² / g, the total light transmittance: 63%, the haze degree: 19%, and it was confirmed that the obtained aqueous sol was a transparent aqueous sol.

The aqueous sol obtained as described above did not show an increase in viscosity even after being stored at 30 ° C. for 30 days.

Example 4 A wet cake of antimony oxide was obtained in the same manner as in Example 1, except that the amount of 35% hydrogen peroxide that oxidizes the antimony trioxide powder was reduced to 53.2 g. The ratio of hydrogen peroxide to antimony trioxide was 1.4 mol per mol of antimony trioxide.

When the water content of this wet cake was measured by the same method as in Example 1, the water content was 36.8%.
Met.

Based on the above water content data, 120 g of antimony oxide cake, 10 g of ion-exchanged water and 7.58 g of triethanolamine (about 10% by weight based on antimony oxide) were used in the same manner as in Example 1. After the treatment, a high concentration antimony oxide aqueous sol was obtained.

The obtained aqueous sol had a pH of 7.1 and a viscosity of 11 cp, and contained antimony oxide and N in the aqueous sol.
The concentrations of a ₂ O and Cl are respectively as follows: antimony oxide: 52.8%, Na ₂ O: 0.01% or less, Cl:
It was 90 ppm. Then, the oxidation anxide in the aqueous sol
Simon's Sb ⁺⁵ / Sb ⁺³ was 2.3. Also,
The specific surface area of antimony oxide obtained by drying this aqueous sol, total light transmittance, haze degree, respectively, as follows,
The specific surface area: 86 m ² / g, the total light transmittance: 77%, the haze degree: 9%, and it was confirmed that the obtained aqueous sol was a transparent aqueous sol.

The aqueous sol obtained as described above did not show any increase in viscosity even after being stored at 30 ° C. for 30 days.

Example 5 A wet cake of antimony oxide was obtained in the same manner as in Example 1 except that the amount of 35% hydrogen peroxide solution that oxidizes the antimony trioxide powder was increased to 83.6 g. The ratio of hydrogen peroxide to antimony trioxide was 2.2 mol per mol of antimony trioxide.

When the moisture content of this wet cake was measured by the same method as in Example 1, the moisture content was 37.2%.
Met.

Based on the above moisture content data, 120 g of antimony oxide cake, 10 g of deionized water and 7.54 g of triethanolamine (about 10% by weight based on antimony oxide) were used in the same manner as in Example 1. After the treatment, a high concentration antimony oxide aqueous sol was obtained.

The obtained aqueous sol had a pH of 7.1 and a viscosity of 16 cp, and contained antimony oxide and N in the aqueous sol.
The concentrations of a ₂ O and Cl are respectively as follows: antimony oxide: 52.7%, Na ₂ O: 0.01% or less, Cl:
It was 95: ppm. Then, the oxidized sol in the aqueous sol
Ntimon's Sb ⁺⁵ / Sb ⁺³ was 8.8. The specific surface area, total light transmittance, and haze of antimony oxide obtained by drying this aqueous sol are as follows: specific surface area: 58 m ² / g, total light transmittance: 57%,
The haze degree was 25%, and it was confirmed that the obtained aqueous sol was a transparent aqueous sol.

The aqueous sol obtained as described above did not show any increase in viscosity even when stored at 30 ° C. for 30 days. Since the antimony oxide of this example has a large molar ratio of hydrogen peroxide to antimony trioxide, it is estimated that most of the products are Sb ₂ O ₅ (antimony pentoxide). Therefore, the X-ray pattern of the dried antimony oxide was measured, and the known S
When compared with the X-ray pattern of b ₂ O ₅ , they were almost the same.

Example 6 The same treatment as in Example 1 was carried out to obtain a wet cake of antimony oxide having a water content of 37.1%.

Based on the above moisture content data, 120 g of antimony oxide cake, 22 g of ion-exchanged water, and 11.32 g of triethanolamine phosphate (about 15% by weight based on antimony oxide) were used in Example 1. The same treatment was performed to obtain a high concentration antimony oxide aqueous sol.

The obtained aqueous sol had a pH of 3.1 and a viscosity of 15 cp, and contained antimony oxide and Na in the aqueous sol.
The concentrations of ₂ O and Cl are respectively as follows: antimony oxide: 47.8%, Na ₂ O: 0.01% or less, Cl: 9
It was 5 ppm. And the anti-oxidant in the aqueous sol
Mon's Sb ⁺⁵ / Sb ⁺³ was 3.9. The specific surface area, total light transmittance, and haze of antimony oxide obtained by drying this aqueous sol are as follows: specific surface area: 64 m ² / g, total light transmittance: 55%, haze degree. It was 27%, and it was confirmed that the obtained aqueous sol was a transparent aqueous sol.

The aqueous sol obtained as described above did not show an increase in viscosity even after being stored at 30 ° C. for 30 days.

Example 7 The same treatment as in Example 1 was carried out to obtain a wet cake of antimony oxide having a water content of 37.6%.

120 g of antimony oxide cake, 19 g of ion-exchanged water, 11.23 g of tartaric acid (about 15% by weight based on antimony oxide) based on the above water content data.
Was treated in the same manner as in Example 1 to obtain a high concentration aqueous sol of antimony oxide.

The obtained aqueous sol had a pH of 1.2 and a viscosity of 19 cp, and contained antimony oxide and N in the aqueous sol.
The concentrations of a ₂ O and Cl are respectively as follows: antimony oxide: 47.8%, Na ₂ O: 0.01% or less, Cl:
It was 110 ppm. Then, the oxidized sol in the aqueous sol
Ntimon's Sb ⁺⁵ / Sb ⁺³ was 4.0. The specific surface area, total light transmittance, and haze of antimony oxide obtained by drying this aqueous sol are as follows: specific surface area: 66 m ² / g, total light transmittance: 52%,
The haze degree was 29%, and it was confirmed that the obtained aqueous sol was a transparent aqueous sol.

The aqueous sol obtained as described above did not show any increase in viscosity even after being stored at 30 ° C. for 30 days.

Example 8 The same treatment as in Example 1 was carried out to obtain a wet cake of antimony oxide having a water content of 37.9%.

Based on the above moisture content data, the same treatment as in Example 1 was performed using 120 g of an antimony oxide cake, 18 g of ion-exchanged water, and 11.18 g of glycerin (about 15% by weight based on antimony oxide). A high concentration antimony oxide aqueous sol was obtained.

The obtained aqueous sol had a pH of 1.4 and a viscosity of 25 cp, and contained antimony oxide and N in the aqueous sol.
The concentrations of a ₂ O and Cl are respectively as follows: antimony oxide: 48.3%, Na ₂ O: 0.01% or less, Cl:
It was 90 ppm. Then, the oxidation anxide in the aqueous sol
Simon's Sb ⁺⁵ / Sb ⁺³ was 4.0. Also,
The specific surface area of antimony oxide obtained by drying this aqueous sol, total light transmittance, haze degree, respectively, as follows,
The specific surface area was 65 m ² / g, the total light transmittance was 50%, and the haze was 31%. It was confirmed that the obtained aqueous sol was a transparent aqueous sol.

The aqueous sol obtained as described above did not show an increase in viscosity even after being stored at room temperature for 30 days.

Example 9 The same treatment as in Example 1 was carried out to obtain a wet cake of antimony oxide having a water content of 34.5%.

Based on the above water content data, 120 g of antimony oxide cake, 4.7 g of ion-exchanged water, and 23.6 g of triethanolamine (about 30% by weight based on antimony oxide) were used as in Example 1. The same treatment was carried out to obtain a high concentration aqueous sol of antimony oxide.

The obtained aqueous sol had a pH of 7.4 and a viscosity of 12 cp, and contained antimony oxide, N and N in the aqueous sol.
The concentrations of a ₂ O and Cl are as follows: antimony oxide: 50.2%, Na ₂ O: 0.01% or less, Cl:
It was 115 ppm. Then, the oxidized sol in the aqueous sol
Ntimon's Sb ⁺⁵ / Sb ⁺³ was 3.9. The specific surface area, total light transmittance, and haze of antimony oxide obtained by drying this aqueous sol are as follows: specific surface area: 67 m ² / g, total light transmittance: 63%,
The haze degree was 18%, and it was confirmed that the obtained aqueous sol was a transparent aqueous sol.

The aqueous sol obtained as described above did not show an increase in viscosity even after being stored at 30 ° C. for 30 days.

Comparative Example 1 The amount of water put in a container having an internal volume of 1 liter was 205 ml.
And the same treatment as in Example 1 was carried out except that the wet cake was made of antimony oxide having a water content of 38.2%.

Based on the above moisture content data, 120 g of antimony oxide cake, 20 g of ion-exchanged water and 7.42 g of triethanolamine (about 10% by weight based on antimony oxide) were used in the same manner as in Example 1. After the treatment, a high concentration antimony oxide aqueous sol was obtained.

The obtained aqueous sol had a pH of 7.6 and a viscosity of 26 cp, and contained antimony oxide and N in the aqueous sol.
a ₂ O and Cl are respectively as follows: antimony oxide: 46.6%, Na ₂ O: 0.01% or less, Cl: 9
It was 0 ppm. And the anti-oxidant in the aqueous sol
Mon's Sb ⁺⁵ / Sb ⁺³ was 4.0. The specific surface area, total light transmittance, and haze degree of antimony oxide obtained by drying this aqueous sol are as follows: specific surface area: 39 m ² / g, total light transmittance: 33%, haze degree. : 64%, and the obtained aqueous sol was an opaque aqueous sol. It is considered that this is because the specific surface area was 39 m ² / g, which was smaller than that of the example, and that the particle size of antimony oxide increased due to the oxidation at a high concentration.

Comparative Example 2 Wet antimony oxide was treated in the same manner as in Example 1 except that the amount of 35% hydrogen peroxide solution added was reduced to 22.8 g and the amount of hydrogen peroxide was outside the scope of the present invention. Got a cake The ratio of hydrogen peroxide to antimony trioxide is
The amount of hydrogen peroxide was 0.6 mol per mol of antimony trioxide, and the amount of hydrogen peroxide was less than the range specified in the present invention (0.8 to 2.5 mol per mol of antimony trioxide).

When the water content of this wet cake was measured by the same method as in Example 1, the water content was 60.7%.
Met.

Based on the above water content data, 120 g of antimony oxide cake, 32.5 g of ion-exchanged water and 4.72 g of triethanolamine (about 10% by weight based on antimony oxide) were used as in Example 1. The same treatment was carried out to obtain a high concentration aqueous sol of antimony oxide.

The obtained aqueous sol had a pH of 8.0 and a viscosity of 38 cp, and contained antimony oxide and N in the aqueous sol.
The concentrations of a ₂ O and Cl are respectively as follows: antimony oxide: 27.6%, Na ₂ O: 0.01% or less, Cl:
It was 100 ppm. Then, the oxidized sol in the aqueous sol
Ntimon's Sb ⁺⁵ / Sb ⁺³ was 0.4. The specific surface area, total light transmittance, and haze of antimony oxide obtained by drying this aqueous sol are as follows: specific surface area: 67 m ² / g, total light transmittance: 25%,
The haze degree was 90%, and the obtained aqueous sol was an opaque aqueous sol. This is because the amount of hydrogen peroxide with respect to antimony trioxide is small, so that the particles of antimony oxide are strongly aggregated and cannot be dispersed even when redispersed, so that a transparent aqueous sol cannot be obtained. it is conceivable that.

Comparative Example 3 In Comparative Example 3, the following experiment was conducted in order to clarify the problem that occurs when a low-concentration aqueous sol is concentrated to a high concentration.

That is, 561 ml of water was placed in a container having an internal volume of 1 liter, 114 g of antimony trioxide powder was added thereto, and further 60.8 g of 35% hydrogen peroxide solution was added thereto. The obtained suspension is heated with stirring, heated to boiling in 15 minutes, kept in the boiling state for 1 hour, and the concentration of antimony oxide is 16.5.
% Aqueous sol was obtained. The ratio of hydrogen peroxide to antimony trioxide is 1.6 per mol of antimony trioxide.
Mole.

The obtained low-concentration aqueous sol was concentrated using a rotary evaporator so that the concentration of antimony oxide was 40%.
% Aqueous sol was obtained.

The obtained aqueous sol had a pH of 2.6 and a viscosity of 1100 cp, and the concentrations of antimony oxide, Na ₂ O and Cl in the aqueous sol were as follows: antimony oxide: 40.9% , Na ₂ O: 0.01% or less,
Cl was 10 ppm or less. And in the aqueous sol
Sb ⁺⁵ / Sb ⁺³ of the antimony oxide of was 3.9.
Was. The specific surface area, total light transmittance, and haze of antimony oxide obtained by drying this aqueous sol are as follows: specific surface area: 61 m ² / g, total light transmittance: 6
2%, haze: 22%, it was confirmed that the obtained aqueous sol was a transparent aqueous sol, but the viscosity was increased to 1100 cp as described above due to concentration, and To the extent that the characteristics are significantly reduced (about 1000 cp
Above), the viscosity was high.

Comparative Example 4 In Comparative Example 4, the following experiment was conducted in order to clarify the problem that occurs when an alkali metal compound is used in converting an aqueous sol into a gel.

That is, when the aqueous sol was converted into a gel, the procedure was carried out except that 3 g of sodium chloride (about 2.6% by weight based on antimony oxide) was used instead of the ammonium chloride used in Example 1. Perform the same process as in Example 1,
A wet cake of antimony oxide was obtained.

When the water content of this wet cake was measured by the same method as in Example 1, the water content was 40.2%.
Met.

Based on the above water content data, 120 g of antimony oxide cake, 4 g of deionized water, 7.18 g of triethanolamine (about 1% of antimony oxide)
0% by weight) and treated in the same manner as in Example 1 to obtain a high concentration aqueous sol of antimony oxide.

The obtained aqueous sol had a pH of 8.3 and a viscosity of 17 cp, and contained antimony oxide and N in the aqueous sol.
The concentrations of a ₂ O and Cl are respectively as follows: antimony oxide: 52.7%, Na ₂ O: 0.64%, Cl: 12
It was 0 ppm. And the anti-oxidant in the aqueous sol
Mon's Sb ⁺⁵ / Sb ⁺³ was 3.9. The specific surface area, total light transmittance, and haze of antimony oxide obtained by drying this aqueous sol are as follows: specific surface area: 61 m ² / g, total light transmittance: 61%, haze degree. It was confirmed that the obtained aqueous sol was a transparent aqueous sol, but since it gelled with sodium chloride, it was an alkali metal compound Na ₂
O is present in an amount of 0.64%, and Na ₂ is reduced to the extent that the flame retardancy of antimony oxide is deteriorated (about 0.5% or more).
O remained.

Comparative Example 5 In Comparative Example 5, the following experiment was conducted in order to clarify the problem that occurs when the antimonate is acid-decomposed and peptized.

That is, sodium antimonate 120
g was dispersed in 400 ml of water, and while stirring this, 35
After adding 70 g of% hydrochloric acid, the mixture was heated to 40 ° C. and reacted for 4 hours.

Then, the produced antimony oxide gel was suction filtered and washed with 80 ml of water to obtain a wet cake of antimony oxide.

When the moisture content of this wet cake was measured by the same method as in Example 1, the moisture content was 36.4%.
Met.

Based on the above water content data, 120 g of antimony oxide cake, 25 g of ion-exchanged water, and 7.63 g of triethanolamine (about 10% by weight with respect to antimony oxide) were added and mixed, and then 75 ° C. Warm to 5
After time dispersion, a high concentration antimony oxide aqueous sol was obtained.

The obtained aqueous sol had a pH of 8.7 and a viscosity of 16 cp, and contained antimony oxide and N in the aqueous sol.
The concentrations of a ₂ O and Cl are respectively as follows: antimony oxide: 48.0%, Na ₂ O: 2.4%, Cl: 161
It was 0 ppm. Then, the oxidation solution in this aqueous sol
Nchimon is mostly Sb ⁺⁵ in all Sb ,
Since Sb ⁺³ could not be detected, Sb ⁺⁵ / Sb ⁺³
Could not be asked. The specific surface area, total light transmittance, and haze of antimony oxide obtained by drying this aqueous sol are as follows: specific surface area: 71 m
² / g, total light transmittance: 61%, haze degree: 24%, and it was confirmed that the obtained aqueous sol was a transparent aqueous sol, but an antimonate salt was used as a starting material. However, due to the fact that it was acid-decomposed and peptized, 2.4% of Na ₂ O, which is an alkali metal compound, was present in the obtained antimony oxide aqueous sol.

[0124]

As described above, according to the present invention,
A high-concentration antimony oxide aqueous sol in which antimony oxide is dispersed in the form of fine particles can be manufactured at low cost.

Since the antimony oxide aqueous sol produced according to the present invention has a high concentration, it does not remarkably reduce the concentration of the resin emulsion when added to the resin emulsion as a flame retardant aid, so that the resin emulsion Does not deteriorate the processing characteristics, and since the antimony oxide is in the form of fine particles, it does not impair the hue of the object to be processed.

Further, since the above antimony oxide aqueous sol contains substantially no metal compound other than antimony oxide, the flame retardant aid effect of antimony oxide is not reduced.

Claims (1)

(57) [Claims] 1. A low concentration of antimony oxide [compositional formula: Sb ₂ O is prepared by reacting antimony trioxide with 0.8 to 2.5 mol of hydrogen peroxide in 1 mol of antimony trioxide in water.
_{3 + x} (0 <X ≦ 2)] aqueous sol is formed, and then 1% by weight or more of an inorganic acid or an ammonium salt is added to the antimony oxide to form a gel of the antimony oxide, which is separated. After washing with water, at least one selected from the group consisting of alkanolamines, alkanolamine salts, aliphatic α-hydroxycarboxylic acids and aliphatic polyhydric alcohols was used as a dispersant for 1 part of the above antimony oxide.
A method for producing a high-concentration antimony oxide aqueous sol, which comprises adding -50% by weight and peptizing.