JPH10273324A - Amorphous basic double hydroxide and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an amorphous basic double hydroxide having positive charge on the solid surface and improved anion-exchanging potency and fine pore properties by coprecipitating a water-soluble aluminum salt and a specific water- soluble metal compound with an alkaline compound and subjecting the obtained coprecipitate to hydrothermal reaction under specific condition. SOLUTION: The objective synthetic amorphous basic double hydroxide of the formula (MaX<+> is Al<3+> , Fe<3+> , Zr<4+> or Ti<4+> : X is valence of metal ion; 0.2<1<2.0; 16<b<28; A<n-> is an inorganic anion selected from SO4 <2-> , HPO4 <2-> , CO3 <2-> , HPO3 <2-> , SO3 <2-> , SiO3 <2-> , H2 PO4 <-> or OH<-> or an organic anion such as acetic acid and oxalic acid anion; 0.4<=c<=3.0: (m) is 1-8) is produced by coprecipitating a water-soluble aluminum salt and at least one kind of compound selected from water-soluble iron salt, zirconium salt and titanium salt with an alkaline compound at pH 3.5-7 and 10-50 deg.C, washing the obtained coprecipitate with water after or without filtration, suspending the washed solid in water and subjecting the hydrothermal reaction at pH 3.5-7 and 60-170 deg.C for 0.5-24 hr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anion adsorbent for adsorbing and removing harmful HPO ₄ ²⁻ , CrO ₄ ²⁻ , MnO ₄ ²⁻ , acidic coloring matters, etc. contained in industrial wastewater, dye waste liquid and the like, and exchange. The present invention relates to an amorphous basic double hydroxide expected to be used for materials, ink jet recording media and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Hydrotalcite-type compounds are typical of adsorbents and anion exchangers for acidic substances.

[0003] Among these hydrotalcite compounds, Mg-Al-CO ₃ compounds, which are widely used in practice, are crystalline, have a positive charge on the solid surface, and have a unique anion exchange ability. However, its pore properties (specific surface area, pore volume) are not particularly excellent (usually measured values, BE
T specific surface area 90-150 m ² / g, pore volume 0.4-0.4.
8 ml / g). In addition, the liquidity is alkaline at pH 9 or more, and the application of a chemical which is likely to be hydrolyzed due to alkalinity as an adsorbent is limited.

In an ink jet recording medium for hard copy, which mainly utilizes the functions of the positive charge and pore physical properties of the solid surface, an aqueous anionic dye is rapidly adsorbed and fixed,
The large adsorption capacity is one of the important factors for improving the quality of color photographic paper, and there is a need for a substance having excellent solid surface positive charge density and fine pore properties.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have found that the solid surface has a positive charge, a high charge density, and an anion exchange ability with a specific anion [Chalcoalumite]. Class compounds [naturally occurring crystalline CuAl ₄ (OH) ₁₂ SO ₄ .3H ₂
O etc.]. As a result of earnestly studying for a substance which is white and has excellent pore physical properties (specific surface area and pore volume) while maintaining the properties of the substance, an amorphous basic double hydroxide represented by the formula (1) was obtained. We found that we could combine them.

The synthetic amorphous basic double hydroxide of the present invention has excellent pore properties, for example, a specific surface area of 557 m ² / g and a pore volume of 2.49 ml / g, and has a large ability to adsorb an aqueous anionic dye ( It has an anion exchange ability (see FIG. 3).

The synthetic amorphous basic double hydroxide of the present invention has the formula (1) M _ax ⁺ Al _2x ³⁺ (OH) _b (A ⁿ⁻ ) _c · mH ₂ O (1) where M ^{x +} is X represents at least one selected from Al ³⁺ , Fe ³⁺ , Zr ⁴⁺ and Ti ⁴⁺ , X represents the valence of M metal ion, and a represents 0.2 <a <2.0. , B is 16 <b <2
Indicates 8, A ^{n-is _{SO 4 2-, HPO 4 2-,}} CO 3 2-, HP
^{_{O 3 2-, SO 3 2-,}} SiO 3 2-, H 2 PO 4 -, OH - inorganic anions and acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, One or more selected from organic anions of isophthalic acid, terephthalic acid, malic acid, tartaric acid, citric acid, benzoic acid, salicylic acid, acrylic acid and benzenesulfonic acid, wherein C is 0.4 ≦ C <3 0.0, and m is 1 to 9.
It is a synthetic amorphous basic double hydroxide represented by

[0008] The amorphous basic double hydroxide of the present invention can be produced by the following method. Water-soluble aluminum salt, water-soluble iron salt (Fe ³⁺ ), zirconium salt (Zr
⁴⁺ ) and at least one compound selected from titanium salts (Ti4 ⁺ ) with an alkaline compound at a pH of 3.5 to 3.5.
7. The coprecipitation reaction is carried out at a temperature of about 10 to 50 ° C., and the reaction pH and the temperature of about 6
A hydrothermal reaction is performed at 0 to 170 ° C. for 0.5 to 24 hours, or a coprecipitate formed under the same conditions as described above is separated by filtration, washed with water, and then the solid is suspended in water. Reaction p
It is produced by a method of performing a hydrothermal reaction at H and a temperature of about 60 to 170 ° C for 0.5 to 24 hours. In this case, the M used
^{The amount of 3+} ions (Al ³⁺ , Fe ³⁺ ) is determined by the atomic ratio M ³⁺ / Al ³⁺
In _^1/12 to _^1/4, a, also M ⁴⁺ ions (Zr ^4+, Ti
⁴⁺ ) is used in an atomic ratio of M4 ⁺ / Al3 ⁺ of 0.025 to 0.25, preferably 0.025 to 0.125. The coprecipitation reaction is performed in an aqueous solution containing at least one metal ion selected from Al ³⁺ , Fe ³⁺ , Zr ⁴⁺ and Ti ⁴⁺ and Al ³⁺ with respect to the sum of trivalent and tetravalent metal ions. 0.8-1.2
An equivalent amount of an alkali compound is reacted at a pH of 3.5 to 7, at a temperature of about 1
It is carried out by adding under stirring at 0-50 ° C.
The temperature of the coprecipitation reaction is not particularly limited, but the temperature is about 10 to 50 ° C.
It is preferably carried out by reacting at about 20 to 40 ° C. for about 10 minutes to about 2 hours.

Next, the hydrothermal reaction is carried out by reacting at a reaction pH of 3.5 to 7 and a temperature of about 60 to 170 ° C., preferably about 80 to 150 ° C. for about 0.5 to 24 hours. In this case, if the temperature is lower than 60 ° C., the formation of the amorphous basic double hydroxide of the present invention having the composition ratio represented by the formula (1) becomes insufficient. (Boehmite) is not preferable because it is generated. The reaction time is usually about 0.5 to 24 hours, preferably about 3 to 12 hours.

In the production of the amorphous basic double hydroxide of the present invention, the reaction pH of both the coprecipitation reaction and the hydrothermal reaction is from 3.5 to 3.5.
When the reaction pH is lower than 3.5, aluminum hydroxide which forms the basic skeleton structure is not precipitated, so that the double hydroxide of the present invention is not formed. On the other hand, when the reaction pH is higher than 7, a crystal phase of aluminum hydroxide such as pseudo-boehmite is generated, which is not preferable.

Examples of the raw materials for the metal ions of Fe ³⁺ , Zr ⁴⁺ , Ti ⁴⁺ and Al ³⁺ include ferric chloride, ferric nitrate, ferric sulfate, and ferric bromide. , Iron compounds such as ferric perchlorate; zirconium compounds such as zirconium oxychloride, zirconium sulfate, zirconium oxynitrate, and zirconium acetate; titanium compounds such as titanium chloride, titanium sulfate, titanium oxychloride, and titanium acetate; aluminum chloride; Examples include aluminum compounds such as aluminum nitrate, aluminum sulfate, sodium aluminate, aluminum acetate, and polyaluminum chloride.

Examples of alkali compounds used for precipitating trivalent and tetravalent metal ions include sodium hydroxide, potassium hydroxide, aqueous ammonia, ammonia gas, calcium hydroxide, magnesium oxide, magnesium hydroxide, and base. Magnesium carbonate and the like.

The amorphous basic double hydroxide of the present invention containing SO ₄ ²⁻ as an anion is one of SO ₄ ² which is an anion.
Parts are HPO ₄ ²⁻ , CO ₃ ²⁻ , HPO ₃ ²⁻ , CrO ₄ ²⁻ , SO
One selected from inorganic anions of ₃ ²⁻ , SiO ₃ ²⁻ , MnO ₄ ² , H ₂ PO ₄ ⁻ , NO ₃ ⁻ and OH ⁻ , and saturated and unsaturated aliphatic and aromatic carboxylic acids; Organic anions of dicarboxylic acids, oxycarboxylic acids and sulfonic acids, for example, acetic acid, butyric acid, oxalic acid, malonic acid, maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid Substitution (ion exchange, ligand exchange) with one selected from acid, malic acid, tartaric acid, citric acid, benzoic acid, salicylic acid, acrylic acid, benzenesulfonic acid and the like.

The inorganic and organic anions intended for substitution are preferably used mainly as water-soluble sodium salts.

It is also possible to incorporate a desired salt containing an anion other than SO ₄ ^2- in an aqueous solution at the time of the reaction, as a part of the anion.

Accordingly, the amorphous basic double hydroxide of the present invention also comprises first an anion (A ⁿ⁻ ) of the formula (1) wherein SO ₄ ^2-
And then substituting a part of the SO ₄ ^2- with at least one anion selected from the above-mentioned inorganic anions and organic anions.

The substitution reaction is carried out at a temperature of about 20 to 80 with an aqueous solution of the desired anion salt or alkali metal hydroxide.
By stirring several minutes to about 1 hour A ^n- is added SO ₄ amorphous basic double hydroxide is ² of the formula (1) at ° C., or Nutsche, drum filter, such as a belt filter This is performed by forming a cake layer of the above-mentioned amorphous basic double hydroxide on a filter cloth and washing with the above-mentioned aqueous solution of anion. The anion solution used for the substitution reaction has a concentration of about 0.05 to 0.5 mol / liter, and an equivalent to 1.5 times equivalent of SO ₄ ^2- to be substituted is used.

The amorphous basic double hydroxide of the present invention is BET
Specific surface area is 30 to 600 m ² / g, total pore volume (N ₂ gas adsorption method) is 0.4 to 2.5 ml / g, and average pore diameter (N ₂ gas adsorption method) is 3.0 to 10.0 nm. And an average particle diameter (measured by a laser diffraction scattering method) of 0.5.
２０20 μm, excellent in pore physical properties, for adsorption and removal of harmful HPO ₄ ²⁻ ions and acidic coloring matters contained in industrial wastewater, dye waste liquid, etc., and light resistance of inkjet recording paper It is expected to be used for improvement. Furthermore, since the liquidity is weakly neutral or less acidic, it is expected to be used as an adsorbent for chemicals sensitive to alkalinity such as hydrolysis and fading, and as a buffer in a weakly acidic region of pH 4 to 7. Things.

[0019]

The present invention will be described below in more detail with reference to examples and reference examples.

The water content of the product described in the examples [expressed as m in the formula (1)] is 2 by the thermogravimetric method of differential thermal analysis.
The weight obtained by subtracting the percent weight loss by the dry moisture measurement method (drying at 105 ° C. for 3 hours) from the percent weight loss up to 00 ° C. was calculated as the water content (m).

Example 1 Reagent grade zirconium oxychloride (ZrCl ₂ O · 8
6.45 g of H ₂ O) and 130 ml of a 1.02 mol / l aqueous solution of aluminum sulfate are dissolved in deionized water to make a total volume of 600 ml. This is put in a 1-liter beaker, and 20.7 g of magnesium hydroxide (content: 99.7%) is added at room temperature while vigorously stirring with a homomixer. Stir for about 30 minutes. The pH of the suspension is 5.96
(27.8 ° C.). Next, the mixture was transferred to an autoclave having a capacity of 0.98 liter and subjected to hydrothermal reaction at 110 ° C. for 4 hours. The pH of the suspension was 4.36 (22.3 ° C). Filter and wash to obtain a solid. 500 ml of deionized water and 19 ml of 3.5N NaOH aqueous solution in a 1 liter beaker
(Molar ratio: NaOH / Al ₂ O ₃ = 0.5), add the above-mentioned solid while stirring with a homomixer, and suspend at room temperature for 15 minutes. After filtration, washing with water and acetone, 75
Dry at 15 ° C. for 15 hours. The yield of the dried product was 24.5 g. The dried product was pulverized and sieved with 100 mesh.

The measured values of the pore properties of the product are shown below.

BET specific surface area 352 m ² / g, total pore volume (N ₂ gas adsorption method) 1.54 ml / g, average pore diameter 7.7 nm, average particle diameter (laser diffraction scattering method) 6.6 μm
m.

The chemical formula determined by the chemical analysis was as follows.

[0025] _{Zr 0. 72 Al 8 (OH} ) 24. 52 (SO 4) 1. 08 (C
_{O 3) 0. 1 · 5.8H} 2 O Example 2 reagent grade zirconium oxychloride (ZrCl ₂ O · 8
9.67 g of H ₂ O) and 118 ml of a 1.02 mol / l aqueous solution of aluminum sulfate are dissolved in deionized water to make a total volume of 600 ml. This is placed in a 1-liter beaker, and 189 ml of a first-grade 3.5N-NaOH aqueous solution is poured at room temperature while vigorously stirring with a homomixer. Stir for about 30 minutes. The pH of the suspension is 6.06
(26.1 ° C.). Next, the mixture was transferred to an autoclave having a volume of 0.98 liter and subjected to hydrothermal reaction at 120 ° C. for 4 hours. The pH of the suspension was 4.31 (21.5 ° C).

The solid obtained by filtration and washing with water was washed with acetone and then dried at 75 ° C. for 15 hours. Dry matter yield is 2
6.6 g. After drying, it was ground and sieved with 100 mesh.

The measured values of the pore properties of the product are shown below.

BET specific surface area value 320 m ² / g, total pore volume (N ₂ gas adsorption method) 1.80 ml / g, average pore diameter 9.8 nm, average particle diameter (laser diffraction scattering method) 7.8 μm
m.

The chemical formula determined by the chemical analysis was as follows.

[0030] _{Zr 0. 92 Al 8 (OH} ) 23. 68 (SO 4) 2 · 7.6H 2 O Example 3 reagent grade zirconium oxychloride (ZrCl ₂ O · 8
9.67 g of H ₂ O) and 118 ml of a 1.02 mol / l aqueous solution of aluminum sulfate are dissolved in deionized water to make a total volume of 600 ml. This is put in a 1-liter beaker, and 19.4 g of magnesium hydroxide (content: 99.6%) is added at room temperature while vigorously stirring with a homomixer. Stir for about 30 minutes. The pH of the suspension is 5.92
(30.1 ° C.). Next, the mixture was transferred to an autoclave having a volume of 0.98 liter and subjected to hydrothermal reaction at 120 ° C. for 4 hours. The pH of the suspension was 4.26 (21.9 ° C).

The solid is obtained by filtration and washing with water.

500 m of deionized water in a 1 liter beaker
1 and 3.5N-NaOH aqueous solution 17.1 ml (Na molar ratio)
OH / Al ₂ O ₃ = 0.5), add the above-mentioned solid while stirring with a homomixer, and suspend at 35 ° C. for 15 minutes. It was separated by filtration, washed with water, washed with acetone, and dried at 75 ° C. for 15 hours. The yield of the dried product was 24 g. The dried product was pulverized and sieved with 100 mesh.

The measured values of the pore properties of the product are shown below.

BET specific surface area 557 m ² / g, total pore volume (N ₂ gas adsorption method) 2.49 ml / g, average pore diameter 7.0 nm, average particle diameter (laser diffraction scattering method) 3.2 μm
m.

The chemical formula determined by the chemical analysis was as follows.

[0036] _{Zr 1. 06 Al 8 (OH} ) 25. 72 (SO 4) 1. 16 (C
_{O 3) 0. 1 · 5.8H} 2 O Example 4 Reagent titanium sulfate solution (about 30% content) 24 g and 1.
Aluminum sulfate aqueous solution having a concentration of 02 mol / liter 11
Dissolve 8 ml in deionized water to make a total volume of 600 ml. This is placed in a 1-liter beaker, and 21.8 g of magnesium hydroxide (content: 99.6%) is added at room temperature with vigorous stirring with a homomixer. Stir for about 30 minutes. The pH of the suspension was 5.42 (28.4 ° C). Next, the sample was transferred to an autoclave having a capacity of 0.98 liters, and
Hydrothermal reaction was performed at 20 ° C. for 4 hours. The pH of the suspension is 4.2
5 (16.8 ° C.). The solid obtained by filtration and washing with water was washed with acetone and dried at 75 ° C. for 15 hours. The yield of the dried product was 25.6 g. Crushed after drying 100
Sieved with a mesh.

The measured values of the pore properties of the product are shown below.

BET specific surface area value 347 m ² / g, total pore volume (N ₂ gas adsorption method) 1.01 ml / g, average pore diameter 7.3 nm, average particle diameter (laser diffraction scattering method) 3.7 μm
m.

The chemical formula determined by the chemical analysis was as follows.

[0040] _{Ti 1. 06 Al 8 (OH} ) 23. 72 (SO 4) 2. 26 · 7.2H 2 O Example 5 reagent grade zirconium oxychloride (ZrCl ₂ O · 8
9.67 g of H ₂ O) and 118 ml of a 1.02 mol / l aqueous solution of aluminum sulfate are dissolved in deionized water to make a total volume of 600 ml. This is put in a 1-liter beaker, and 19.3 g of magnesium hydroxide (content: 99.6%) is added at room temperature with vigorous stirring with a homomixer. Stir for about 30 minutes. The pH of the suspension is 6.47
(26.4 ° C.). Next, the mixture was transferred to an autoclave having a volume of 0.98 liter and subjected to hydrothermal reaction at 120 ° C. for 4 hours. The pH of the suspension was 4.40 (18.7 ° C).

The solid is obtained by filtration and washing with water.

21.5 g of reagent grade disodium hydrogen phosphate (Na ₂ HPO ₄ .12H ₂ O) in a 1 liter beaker
(Equivalent to SO ₄ ^2- contained in the obtained solid, HPO ₄ ^2-
And dissolved in 500 ml of deionized water. Add the above solid substance with stirring with a homomixer, and add
Suspend for a minute. The solid was separated by filtration, washed with water and acetone, and then dried at 75 ° C. for 15 hours. The yield of dried product is 25.
It was 4 g. The dried product was pulverized and sieved with 100 mesh.

The specific surface area of the product was 334 m ² / g, and the average particle size (laser diffraction scattering method) was 2.9 μm.

The chemical formula determined by the chemical analysis was as follows.

[0045] _{Zr 0. 96 Al 8 (OH} ) 22. 92 (HPO 4) 1.
_{82 (SO 4) 0. 54 (} CO 3) potassium chromate instead of the resulting solid is treated with disodium hydrogen phosphate hydrothermal reaction of _0.1 · 6.4H ₂ O Example 6 Example 5 Except having used, it carried out on the same conditions as Example 5.

In a 1-liter beaker, 11.65 g of reagent-grade potassium chromate (K ₂ CrO ₄ ) (equivalent to SO ₄ ^2- in the solid obtained by the hydrothermal reaction of Example 5 with CrO ₄ ^2- equivalent) And dissolve in 500 ml of deionized water. The solid is added with stirring with a homomixer, and suspended at 35 ° C. for 15 minutes. The solid was separated by filtration, washed with water and acetone, and then washed at 75 ° C for 1 hour.
Dry for 5 hours. The yield of the dried product was 24.9 g.
The dried product was pulverized and sieved with 100 mesh.

The specific surface area of the product was 362 m ² / g, and the average particle size (laser diffraction scattering method) was 4.2 μm.

The chemical formula determined by the chemical analysis was as follows.

[0049] _{Zr 0. 98 Al 8 (OH} ) 24. 32 (CrO 4) 0.
_{88 (SO 4) 0. 88} (CO 3) 0.04 · 6.2H 2 O Example 7 Reagent grade zirconium oxychloride (ZrCl ₂ 0 · 8
(H ₂ O) 6.45 g and 130 ml of a 1.02 mol / l aqueous solution of aluminum sulfate are dissolved in deionized water to make a total volume of 600 ml. This is put in a 1-liter beaker, and 20.7 g of magnesium hydroxide (content: 99.6%) is added at room temperature while vigorously stirring with a homomixer. Stir for about 30 minutes. The pH of the suspension is 6.24
(34 ° C.). The temperature is then raised to 90 ° C. and maintained for 6 hours. The pH of the suspension was 5.03 (29.2 ° C). The resulting vacuum filtered solids Nutsuchie, washed with water, SO ₄ ^2-and equivalent C ₆ H ₄ of in sodium salicylate solution [sodium salicylate 21.3 g (solid at room temperature (O
H) COO ^-. Spent wash (800 ml solution of the cleaning time of about 7 minutes or equivalent) which was dissolved in deionized water 800M1] over the), and then washed with water and dried for 6 hours at 75 ° C. after acetone washing. The yield of the dried product was 27.4 g.
The dried product was pulverized and sieved with 100 mesh.

The specific surface area of the product was 286 m ² / g, and the average particle size (laser diffraction scattering method) was 4.8 μm.

The chemical formula determined by the chemical analysis was as follows.

Zr₀.₆₆Al₈(OH)_{twenty four}.₃₈(C₆H_Four(OH)
COO)₁._{twenty two}(SO_Four)₀.₅₂・ 2.4H_TwoO Example 8 Reagent grade zirconium oxychloride (ZrCl_TwoO.8
H_TwoO) 9.67 g and 1.02 mol / l concentration
Dissolve 118 ml of aluminum sulfate aqueous solution in deionized water
To a total volume of 600 ml. This one liter
Into a room, and stir vigorously with a homomixer.
19.3 g of magnesium hydroxide (content 99.6%) under warm conditions
Is added. Stir for about 30 minutes. The pH of the suspension is 5.
35 (26 ° C.). Next is a 0.98 liter capacity
Transfer to autoclave, hydrothermal reaction at 120 ° C for 4 hours
I let it. The pH of the suspension was 4.31 (22.2 ° C).
Was. The solid obtained was filtered off under reduced pressure with a nutsier, washed with water,
An aqueous solution of sodium terephthalate [reagent terephthalate
12 g of acid (SO in solid matter)_Four ^2-Equivalent to 1.2 equivalents of
C₆H_Four(COO^-)_Two) And 48 ml of 3N-NaOH aqueous solution
800m1 with deionized water]
(The washing time of 800 ml required about 8 minutes.)
After washing with acetone, wash with acetone and dry at 75 ° C for 15 hours.
Was. The yield of the dried product was 28.4 g. Dry matter is 10
Sieved with 0 mesh.

The specific surface area of the product was 495 m ² / g, and the average particle size (laser diffraction scattering method) was 6 μm.

The chemical formula determined by the chemical analysis was as follows.

ZrAl ₈ (OH) ₂₅ [C ₆ H ₄ (COO) ₂ ] ₁ .
_{16 (SO 4) 0. 34} · 6.2H 2 O Example 9 Reagent grade zirconium oxychloride (ZrCl ₂ O · 8
9.67 g of H ₂ O) and 118 ml of a 1.02 mol / l aqueous solution of aluminum sulfate are dissolved in deionized water to make a total volume of 600 ml. This is put in a 1-liter beaker, and 19.3 g of magnesium hydroxide (content: 99.6%) is added at room temperature while vigorously stirring with a homomixer. Stir for about 30 minutes. The pH of the suspension is 5.8
6 (29.2 ° C.). Next, the mixture was transferred to an autoclave having a capacity of 0.98 liter, and subjected to a hydrothermal reaction at 120 ° C. for 4 hours. The pH of the suspension was 4.27 (22.9 ° C). The obtained solid was separated by filtration under reduced pressure with Nutchie, washed with water, and then aqueous sodium benzoate solution [reagent grade benzoic acid 1] at room temperature.
4.65 g (equivalent amount of C ₆ H _{5 to} SO ₄ ²⁻ in the obtained solid material)
COO ^- considerable) and those on the total amount 800ml of 3N-NaOH aqueous solution 40ml deionized water] were washed over, then followed by washing with water, after acetone washing, and dried at 75 ° C. 7 hours. The yield of the dried product was 29.5 g. The dried product was sieved with 100 mesh.

The specific surface area of the product was 373 m ² / g, and the average particle size (laser diffraction scattering method) was 6.1 μm.

The chemical formula determined by the chemical analysis was as follows.

[0058] _{Zr 1. 02 Al 8 (OH} ) 25. 74 (C 6 H 5 COO)
_{1. 14 (SO 4) 0} . 60 in · 3.2H ₂ O Example 10 1.02 mol / liter concentration the total amount by dissolving aluminum sulfate aqueous solution 136ml of deionized water to prepare a 600M1. This is placed in a 1-liter beaker, and 21.1 g of magnesium hydroxide (content: 99.6%) is added at room temperature with vigorous stirring with a homomixer. Stir for about 30 minutes. The pH of the suspension was 6.33 (27.6 ° C). Next, the mixture was transferred to an autoclave having a capacity of 0.98 liter, and subjected to a hydrothermal reaction at 120 ° C. for 4 hours. Suspension pH
Was 4.18 (23.7 ° C). The obtained solid was filtered off under reduced pressure with a nutsier, washed with water, and then aqueous sodium terephthalate aqueous solution [reagent terephthalic acid 12 g (S
C ₆ H ₄ (COO ⁻ ) ₂ equivalent to 1.2 times equivalent of O ₄ ^2- ) and 3N
-A total of 800 ml of NaOH aqueous solution is 800
and then washed with water,
After washing with acetone, it was dried at 75 ° C. for 3 days. The yield of the dried product was 25.7 g. The dried product was sieved with 100 mesh.

The specific surface area of the product was 438 m ² / g, and the average particle size (laser diffraction scattering method) was 5.8 μm.

The chemical formula determined by the chemical analysis was as follows.

[0061] AlAl ₆ (OH) _{18. 84} [C ₆ H ₄ (CO
O) _{2] 0. 75 (SO 4) 0} . 33 · 2.7H 2 O Example 11 Reagent titanium sulfate solution (about 30% content) 24 g and 1.
Aluminum sulfate aqueous solution having a concentration of 02 mol / liter 11
Dissolve 8 ml in deionized water to make a total volume of 600 ml. This is placed in a 1-liter beaker, and 21.8 g of magnesium hydroxide (content: 99.6%) is added at room temperature with vigorous stirring with a homomixer. Stir for about 30 minutes. The pH of the suspension was 4.45 (32.7 ° C). Next, transfer to a 0.98 liter autoclave,
Hydrothermal reaction was performed at 120 ° C. for 4 hours. The pH of the suspension was 4.
14 (19.1 ° C.). The obtained solid was filtered off under reduced pressure with a nutsier, washed with water, and then aqueous solution of sodium terephthalate [reagent terephthalic acid 12 g (SO _{4 in} solid
^2- equivalent to 1.2 equivalents of C ₆ H ₄ (COO ⁻ ) ₂ ) and 3N−
48 ml of NaOH aqueous solution is 800 m with deionized water
and then washed with water, washed with acetone, and dried at 75 ° C. for 3 days. The yield of the dried product was 26.7 g. The dried product was sieved with 100 mesh.

The specific surface area of the product was 374 m ² / g, and the average particle size (laser diffraction scattering method) was 1.64 μm.

The chemical formula determined by the chemical analysis was as follows.

[0064] _{Ti 1. 04 Al 8 (OH} ) 24. 28 [C ₆ H ₄ (CO
O) _{2] 1. 21 (SO 4) 0.73} · 6H 2 O Example 12 Reagent primary ferric chloride (FeCl ₃ · 6H ₂ O, the total amount 97
%) 9.75 g and 103 ml of a 1.02 mol / l aqueous solution of aluminum sulfate are dissolved in deionized water to make a total volume of 600 ml. This was put into a 1-liter beaker, and while vigorously stirring with a homomixer, the mixture was poured at room temperature with 180 ml of a 3.4N NaOH solution and stirred for about 30 minutes. The pH of the suspension was 5.84 (28.2 ° C). After filtration and washing with water,
The solid is made up to 700 ml suspension with deionized water. This was transferred to an autoclave and subjected to a hydrothermal reaction at 130 ° C. for 4 hours. After cooling, the pH of the suspension was 3.94 (20.
8 ° C.). Filter off and wash with water. Next, 8.7 g of reagent grade sodium dihydrogen phosphate (NaH ₂ PO ₄ .H ₂ O) (SO ₄ ^{2− in the} resulting hydrothermal reaction product) was placed in a 1 liter beaker. 0.6 equivalents of H ₂ PO ₄ ^- equivalent to)
After dissolving in 500 ml of deionized water, add the washed cake and stir at room temperature for 30 minutes. After filtration, water washing and acetone washing, the resultant was dried at 75 ° C. for 20 hours. The yield of the dried product was 23.8 g. The dried product was pulverized and sieved with 100 mesh. The specific surface area value of the product is 331 m ² /
g, average particle diameter (laser diffraction scattering method) was 1.2 μm.

The chemical formula determined by the chemical analysis was as follows.

[0066] _{Fe 1. 03 Al 6 (OH} ) 18. 13 (H 2 PO 4) 1. 74
_{(SO 4) 0. 61 ·} 4.5H to ₂ O applications inkjet paper to Reference Example 1 inkjet paper is light resistance requirements, the dyes (yellow, magenta, cyan, black) used in the printing The magenta dye has the worst lightfastness. However, when the recording medium contains the synthetic amorphous basic double hydroxide obtained according to the present invention, the light resistance is improved. Thus, the following coating liquid was prepared and applied to base paper (PPC paper) using a bar coater to obtain a recording paper.
Next, the obtained recording paper was solid-printed in magenta using a color inkjet printer (BJC-400J / Canon). The light resistance test was performed by irradiating light for 60 hours using a sunshine weather meter (WEL-SUN-HC-B type / manufactured by Suga Test Instruments) and measuring the color difference before and after the light irradiation with a colorimetric colorimeter (ZE-2000 / Nippon Denki). (Manufactured by Shiki Kogyo Co., Ltd.).

No. 1 Synthetic silica (Fine Seal X-37B / manufactured by Tokuyama)
90 parts, 10 parts of the sample (amorphous basic double hydroxide) obtained in Example 10, 40 parts of polyvinyl alcohol (PVA-117 / Kuraray) as an adhesive, and polyethylene imine as a cationic resin (Epomin P-1000
(Nippon Shokubai Co., Ltd.) and 0.2 part of phosphoric acid as a neutralizing agent were added and mixed to prepare a coating solution having a solid content of 15%.

No. 2 No. No. 1 except that the number of copies of the synthetic silica of No. 1 and the sample obtained in Example 10 were each set to 50 parts. Exactly the same as 1.

No. 3 No. Except that only 100 parts of synthetic silica 1 were used.
o. Exactly the same as 1.

Regarding the comparison of light resistance among the three,
The following Table shows the discoloration rate of No. 3 as 100.

[0071]

[Table 1]

From the above table, it can be seen that the discoloration of the magenta dye is suppressed by the addition of the sample obtained in Example 10, and the discoloration is suppressed by further increasing the amount of the sample added.

[0073]

Industrial Applicability The synthetic amorphous basic double hydroxide of the present invention has an anion adsorbent due to its function of having a solid surface with a positive charge, anion exchange ability and large pore physical properties (specific surface area, pore volume). And new applications to exchange materials, ink jet recording media, etc. are expected.

[Brief description of the drawings]

FIG. 1 is an XRD measurement diagram of a basic double hydroxide of Example 2.

FIG. 2 is an XRD measurement diagram of a basic double hydroxide of Example 8.

[3] Example 1, Example 2, Example 4, Example 8, the basic double hydroxide and KW-1100 (synthetic hydrotalcite of Example _{9, Mg 4. 5 Al 2} (OH) ₁₃ CO ₃
・ 3.5H ₂ O direct dye (chlorazole black LF, C ₃₅ H ₂₇ N ₉ Na ₂ O) commercially available from Kyowa Chemical Industry Co., Ltd.
₇ shows the adsorption isotherm of S ₂ ) (treatment at 30 ° C. for 6 hours).

FIG. 4 shows the adsorption isotherm of HPO ₄ ²⁻ of the basic double hydroxide of Example 2 (30 ° C., 1 hour treatment, reagent Na ₂ HP
O ₄ .12H ₂ O).

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07F 7/00 C07F 7/00 A 7/28 7/28 G 15/02 15/02 C09K 3/00 106 C09K 3/00 106

Claims (8)

[Claims] 1. A Formula _{^{1 M a x + Al 2x 3+}} (OH) b (A n-) c · mH 2 O (1) wherein M ^{x +} is Al ^3+, Fe ^3+, Zr ⁴⁺ and Ti ^{4 +} from selected showed at least one, X is indicates the valence of M metal ions, a is shown the 0.2 <a <2.0, b represents a 16 <b <28, a ^n- Is SO ₄ ^2- , HPO ₄ ^2- , CO ₃ ^2- , HPO ₃ ^2- , SO
_{^{3 2-, SiO 3 2-, H}} 2 PO 4 -, OH - inorganic anions and acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid,
One or more selected from organic anions of succinic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, malic acid, tartaric acid, citric acid, benzoic acid, salicylic acid, acrylic acid and benzenesulfonic acid, C is 0.4 ≦ C <3.0, and m is an amorphous basic double hydroxide represented by 1-9. 2. A BET specific surface area of 30 to 600 m ² / g.
The amorphous basic double hydroxide according to claim 1, which is: 3. The total pore volume (N ₂ gas adsorption method) is from 0.4 to 3.
2. The amorphous basic double hydroxide according to claim 1, wherein the amount is 2.5 ml / g. 4. An average pore diameter (N ₂ gas adsorption method) of 3.0 to 4.
The amorphous basic double hydroxide according to claim 1, which has a thickness of 10.0 nm. 5. The amorphous basic double hydroxide according to claim 1, wherein the average particle diameter is 0.5 to 20 μm as measured by a laser diffraction scattering method. 6. An alkali compound comprising a water-soluble aluminum salt and at least one compound selected from a water-soluble iron salt (Fe ³⁺ ), a zirconium salt (Zr ⁴⁺ ) and a titanium salt (Ti ⁴⁺ ). Reaction pH 3.5-7, temperature 10 ° C-
A coprecipitation reaction is performed at 50 ° C., and then a hydrothermal reaction is performed at a reaction pH and a temperature of 60 ° C. to 170 ° C. for 0.5 hours to 24 hours without filtering the coprecipitate, or under the same conditions as described above. The coprecipitate formed below is filtered off and washed with water, and then the solid is suspended in water and subjected to a hydrothermal reaction at a reaction pH in the above range and a temperature of 60 ° C to 170 ° C for 0.5 hours to 24 hours. The method for producing an amorphous basic double hydroxide of the formula (1) according to claim 1. 7. An aqueous solution containing one metal ion selected from Al ³⁺ , Fe ³⁺ , Zr ⁴⁺ and Ti ⁴⁺ and an Al ³⁺ metal ion, wherein M ³ contained in the aqueous solution ⁺ amount of ions is _^1/12 to _^1/4 in atomic ratio M ³⁺ / Al ^3+, the amount of M ⁴⁺ ions at 0.025 to 0.25 in atomic ratio M ⁴⁺ / Al ³⁺ A certain aqueous solution is reacted with 0.8 to 1.2 equivalents of an alkali compound based on the total of trivalent and tetravalent metal ions at a reaction pH of 3.5.
7. The amorphous basic double water according to claim 6, wherein the coprecipitate formed by adding at a temperature of 10 to 50 ° C. is hydrothermally reacted at a temperature of 60 to 170 ° C. for 0.5 to 24 hours. A method for producing an oxide. 8. The formula (1) according to claim 1, wherein A ⁿ⁻ is SO ₄
^An amorphous basic double hydroxide which is ^2- is produced, and then a part of SO ₄ ^2- of the compound is converted to HPO ₄ ^2- , CO ₃ ^2- , HP
_{^{O 3 2-, SO 3 2-,}} SiO 3 2-, H 2 PO 4 -, OH - inorganic anions and acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, 2. The method according to claim 1, further comprising substituting at least one anion selected from organic anions of isophthalic acid, terephthalic acid, malic acid, tartaric acid, citric acid, benzoic acid, salicylic acid, acrylic acid and benzenesulfonic acid. A method for producing a crystalline basic double hydroxide.