JP2000007326A - Spindle-like or spherical alkali aluminum sulfate hydroxide, its production and compounding agent for resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a spindle-like or spherical alkali aluminum sulfate hydroxide having a specific chemical composition and a crystal structure expressed by a specified X-ray diffraction pattern, substantially insoluble in water, having specific 5% aqueous suspension pH, a BET specific surface area, and a moisture content, comprising substantially independent crystal particles each having a spindle-like or spherical constant shape particle structure, and useful as a compounding agent for resins, etc., to improve the performances of the resins, etc. SOLUTION: This aluminum sulfate hydroxide is substantially expressed by the formula: MAl3(SO4)2(OH)6 (M is an alkali metal or ammonium group). In the crystal structure of the aluminum sulfate hydroxide, a surface index and a relative intensity are expressed by prescribed values, respectively, based on each surface distance value within 5.72-1.49. The strongest line of X-ray diffraction peaks has, for example, a surface distance of 2.99×10-10 m, a relative intensity of 100, and a surface index of 113. The aluminum sulfate hydroxide further has 5% aqueous suspension pH 4-7, a BET specific surface area of <=30 m2/g and a moisture content <=10%, especially <=5%, at 25 deg.C and 90% RH.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a spindle-shaped or spherical alkali or ammonium aluminum sulfate hydroxide,
It relates to the production method and the resin compounding agent, more specifically, each particle has a substantially independent spindle-shaped or spherical regular particle structure, the pH is kept near neutral, there is no hygroscopic, The present invention relates to an alkali or ammonium aluminum sulfate hydroxide excellent in incorporation into a resin and antiblocking properties, and a method for producing the same.

[0002]

2. Description of the Related Art Alnite is also called alunite, and is naturally produced as a mineral, and several synthetic methods are known.

Inoue et al., Journal of the Chemical Society of Japan: 1985 (2) P1
56 to 162, K ₂ is added to the Al ₂ (SO ₄ ) ₃ aqueous solution.
SO ₄ and KOH were added to adjust the K / Al ratio to 5, pH to 3.
7 and reflux for 3 hours, 200-240 m ²
/ G of synthetic alunite having a specific surface area of / g, and the porous alunite is an aggregate of flaky crystals, having slit-like pores having a width of about 15 and 30;
It has been reported that the water adsorption capacity is comparable to that of silica gel, the SO ₂ and NO adsorption capacity is high, and the acid dye is well adsorbed.

Japanese Patent Application Laid-Open No. 64-116 relating to the proposal of the applicant
No. 37 discloses that, in the formula, MM ′ ₃ (SO ₄ ) ₂ (OH) ₆ , wherein M represents a monovalent cation and M ′ represents Al or Fe (I
Represent II), in and a crystal structure of the chemical structure and alunite type shown, 280 meters ² An alunite-type adsorbent characterized by comprising a layered compound having a BET specific surface area of at least / g and a pore volume of at least 0.05 ml / g in the range of 10 to 300 angstroms in pore diameter. In addition, this alunite is subjected to a heat reaction between aluminum sulfate or a combination of aluminum sulfate and ferric sulfate and an alkali sulfate in an aqueous medium to which an alkali hydroxide has been added to produce alunite. At this time, the pH of the system is adjusted to 4.0 to 4.0.
It is described that the compound is produced by maintaining the pH of the system at not more than 3.8 even during the course of the reaction.

[0005]

The present inventors have found that when hydrothermally treating aluminum sulfate, alkali sulfate or ammonium sulfate and aluminum hydroxide, they have an X-ray diffraction image different from that of alunite, and the individual particles are substantially different. Independent fusiform or spherical alkali aluminum sulfate hydroxide having a regular particle structure is formed, and the alkali aluminum sulfate hydroxide has a higher pH, a lower specific surface area and a lower hygroscopicity than known alunite. Have
It has been found that it is useful as a resin compounding agent and the like.

That is, an object of the present invention is to provide a spindle-shaped or spherical newly-defined particle structure in which each particle is substantially independent,
An object of the present invention is to provide an alkali aluminum sulfate hydroxide which has a higher pH, a lower specific surface area and a lower hygroscopicity than known alunite, and is useful as a resin compounding agent and the like.
Another object of the present invention is to provide a production method capable of producing the above-mentioned alkali aluminum sulfate hydroxide with high yield and selectivity in a small number of steps.

[0007]

According to the present invention, substantially according to the formula: MAl ₃ (SO ₄ ) ₂ (OH) ₆ ‥ (1) wherein M is an alkali metal or ammonium group;
And the following X-ray diffraction image Plane spacing (dx, plane index relative intensity angstrom) 5.72 101 10 4.96 012 49 3.51 110 29 2.99 113 100 2.86 006 3 2. 48 024 3 2.27 107 13 2.22 122 5 2.02 214 1 1.91 033 19 1.75 200 9 1.65 312 2 1.57 134 2 1.51 315 1 1.49 0210 1 A substantially water-insoluble,
% Aqueous suspension pH in the range of 4 to 7, B
ET specific surface area is 30m ² / G or less, 25 ° C and 9
An alkali aluminum sulfate hydroxide is provided which has a moisture absorption at 0% RH of 10% or less, particularly 5% or less, and in which each particle has a substantially independent spindle-shaped or spherical shaped particle structure. You. According to the present invention, there is also provided a process for producing spindle-shaped or spherical alkali or ammonium aluminum sulfate hydroxide, which comprises hydrothermally treating aluminum sulfate, alkali sulfate or ammonium sulfate and aluminum hydroxide. According to the present invention, there is further provided a compounding agent for a resin comprising the above alkali or ammonium aluminum sulfate hydroxide. In the alkali aluminum sulfate hydroxide of the present invention, the bulk specific gravity is in the range of 0.5 to 1.0,
The volume-based median diameter is in the range of 0.5 to 10.0 μm, and the refractive index in the immersion method is 1.50 to 1.
57, especially in the range 1.52 to 1.57;
Aspect ratio is 0.5 to 1, sample concentration 2wt%
Of the test solution was circulated through a bronze mesh, and
The degree of abrasion in an NF-type abrasion test for measuring the degree of abrasion from the weight change of the mesh during 0 minutes is preferably 0.5% or less, particularly preferably 0.4% or less.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Action] The present invention relates to a method for treating aluminum aluminum sulfate, alkali sulfate or ammonium sulfate and aluminum hydroxide by hydrothermal treatment. It is based on the surprising finding that it is incorporated into the salt hydroxide.

That is, in this reaction, the following reaction formula (2): M ₂ SO ₄ + Al ₂ (SO ₄ ) ₃ + 4Al (OH) ₃ → 2M Al ₃ (SO ₄ ) ₂ (OH) ₆ (2) M is an alkali metal or ammonium group,
The stoichiometric ratios of aluminum sulfate, alkali sulfate or ammonium sulfate and aluminum hydroxide react to produce alkali aluminum sulfate hydroxide in almost 100% to nearly 100% yield as represented by Therefore, there are many advantages in terms of production and economy such that no by-product salts are generated, the reaction is simple, no purification or washing treatment is required, and the process can be one step of hydrothermal treatment. have.

The alkali aluminum sulfate hydroxide according to the present invention has substantially the chemical composition represented by the above formula (1) and the crystal structure represented by the X-ray diffraction image described above.
FIG. 1 of the accompanying drawings is an X-ray diffraction image of a potassium aluminum sulfate hydroxide according to the present invention, and FIG. 2 is an alkali aluminum sulfate hydroxide of potassium: sodium = 0.5: 0.5. In contrast, FIG. 3 is an X-ray diffraction image of naturally occurring alunite.

That is, alunite and the alkali aluminum sulfate hydroxide according to the present invention have a common point in that they have the chemical composition represented by the above formula (1). This difference is recognized. That is, when the three strong lines of the X-ray diffraction peak of alunite and the three strong lines of the X-ray diffraction peak of the alkali aluminum sulfate hydroxide according to the present invention are compared in the strong order, the following (natural alunite) (product of the present invention: Alkali aluminum sulfate hydroxide) face spacing relative strength face index face spacing relative strength face index 2.99 100 113 2.99 100 113 4.96 49 012 2.89 100 006 3.51 29 110 2.29 80 107 (1.91 19 033) (1.93 70 009), and both are considered to be X-ray diffraction different substances.

[0012] Further, the following differences are also observed in physical properties between the two. That is, alunite is 1.57 to 1.
While having a refractive index of 59, the alkali aluminum sulfate hydroxide of the present invention has a refractive index of 1.50 to 1.57.

The alkali aluminum sulfate hydroxide obtained by the above production method of the present invention has a remarkable feature that each particle has a substantially independent spindle-shaped (elliptical sphere) to spherical regular particle structure. I have. FIG. 6 of the accompanying drawings shows the alkali aluminum sulfate hydroxide according to the present invention,
FIG. 7 is a scanning electron micrograph showing the particle structure of a spindle-shaped (elliptical sphere), while FIG. 7 is a scanning electron micrograph showing the particle structure of a spherical alunite according to the present invention.

From FIGS. 6 and 7, it can be seen that the alkali aluminum sulphate hydroxide according to the invention has a well-defined, regular particle structure and, furthermore, has a particle structure characteristic in which the individual particles are substantially independent. It is understood that. Due to this feature, the alkali aluminum sulfate hydroxide according to the present invention has less aggregation between particles, has excellent fluidity in a powder state, and has excellent handleability as a powder.

Further, when incorporated in a resin or the like, since it is easily dispersed in the resin and the particle shape is spherical or spindle-shaped, excellent anti-blocking properties can be imparted to a molded article such as a film. . In general, it is known that there is a certain relationship between the shape of the particles added to the resin and the anti-blocking performance. ) Particles> Amorphous particles> Geolite-like particles> Plate-like particles. On the other hand, it is known that the degree of dropping of particles in a base film used for running such as a magnetic recording film is also in the above order. Thus, in the present invention, the particle shape can be selected according to the application, when a high degree of anti-blocking property is required, spherical particles may be used, and when falling off prevention of the particles is required,
Spindle-shaped particles may be used. The relationship between the particle shape and the manufacturing conditions will be described later.

Furthermore, the alkali aluminum sulfate hydroxides according to the invention are essentially water-insoluble and
The pH, measured as a% aqueous suspension, is in the range of 4 to 7 and is characterized by being near neutral or weakly acidic. For this reason, the alkali aluminum sulfate hydroxide according to the present invention does not hydrolyze the resin even when blended with a polycondensation type resin such as thermoplastic polyester. For example, it does not react with a phenolic antioxidant and discolors the resin, and is excellent in stability and durability as a compounding agent of a resin, particularly a resin synthesized using a metallocene catalyst.

The alkali aluminum sulfate hydroxide has a BET specific surface area of 30 m ² / g or less and has few pores serving as adsorption sites inside the particles. Further, the alkali aluminum sulfate hydroxide has a moisture absorption at 25 ° C. and 90% RH of 10% or less, particularly 5% or less, and the moisture absorption is suppressed to an extremely small range. For this reason, even when compounded in a resin as a resin compounding agent, there is an advantage that foaming due to release of water vapor does not occur during melt-kneading, and the processability and workability are excellent. Furthermore, the alkali aluminum sulfate hydroxide according to the present invention is relatively stable despite having a large number of hydroxyl groups in the molecule, as is apparent from the composition of the above formula (1).
It has the characteristic that there is no weight loss up to the temperature. FIG.
2 shows a thermogravimetric analysis curve of the alkali aluminum sulfate hydroxide of the present invention.

[Production Method] As already pointed out, the alkali aluminum sulfate hydroxide of the present invention is produced by hydrothermally treating aluminum sulfate, alkali sulfate or ammonium sulfate and aluminum hydroxide.
Each raw material used is characterized in that it can be in a stoichiometric amount as shown in the above reaction formula (2).

As aluminum sulfate, a normal salt is preferable, and a commercially available industrial chemical, for example, having an alumina content of 14 to 30 is preferred.
% Solidified products (mass or powder) and liquid products are both used. In addition, of course, aluminum sulfate produced as a by-product when the clay mineral is acid-treated can also be used.

As a raw material of the monovalent cation (M), sodium sulfate, potassium sulfate and ammonium sulfate are used. These raw materials can be used alone or in combination of two or more. Of these, potassium sulfate is particularly preferred.

As the aluminum hydroxide, one having a composition represented by the general formula (3) Al ₂ O ₃ .xH ₂ O ‥ (3) is used.
Vialite, pseudo-boehmite, diaspore, and the like. Among these, the gibbsite type is preferable.

At the time of hydrothermal synthesis, the raw material concentration in the reaction system can be variously changed.
It is preferably in the range of 5 to 20% by weight, especially 10 to 18% by weight.

It has been found that the concentration of alumina in the reaction system affects the particle shape of the produced alkali aluminum sulfate hydroxide. Generally, when the concentration of alumina in the reaction system is 10% by weight or less, spherical alkali aluminum sulfate hydroxide is produced, while the concentration is 15% by weight.
When the content is more than the weight percentage, a spindle-shaped (elliptical sphere) alkali aluminum sulfate hydroxide tends to be formed.

The hydrothermal synthesis is generally carried out at a temperature of 90 ° C. or higher, especially at 15 ° C.
It is good to carry out at a temperature of 0 ° C. In general, the reaction time is appropriately about 8 hours, including the time for raising the temperature. When the temperature of the reaction system reached the above temperature, it was confirmed that almost 100% of alkali aluminum sulfate hydroxide was generated. The pH of the reaction system is initially in the range of 1.8 to 3.0, and the final pH is in the range of 4.0 to 6.0. Therefore, the end point of the reaction can be confirmed from the change in pH. it can. Of course, in order to stabilize the particle shape and particle diameter, ripening may be performed while maintaining the above temperature even after the completion of the reaction.

In the synthesis method of the present invention, the reaction formula (2)
As shown by, no by-products are generated, so that no particular production treatment such as washing with water is required. However, in order to avoid or reduce the influence of impurities contained in the raw material, purification treatment such as washing with water may be performed.

[Alkali aluminum sulfate hydroxide]
Alkali aluminum sulfate hydroxide according to the present invention,
It has the chemical composition represented by the formula (1), and also has the following additional features. That is, this alkali aluminum sulfate hydroxide has a bulk specific gravity of 0.5 to 1.0, particularly 0.6 to 0.8, as measured according to JIS K-6220.
And generally belongs to the dense category. this is,
This is also related to the fact that the number of pores in the particles is small, and provides an advantage that the compound is excellent in pigmentability when compounded into a resin and the compounding operation is easy.

Further, the volume-based median diameter measured by the Coulter method is in the range of 0.5 to 10.0 μm, particularly 1.0 to 5.0 μm, which is in the particle size range suitable for the resin compounding agent.

Further, in the alkali aluminum sulfate hydroxide according to the present invention, in the following formula Rs = D ₂₅ / D ₇₅ , D ₂₅ represents a particle size at 25% of a volume-based cumulative particle size distribution curve by the Coulter method. , D ₇₅ represent the 75% value of the particle size. Sharpness (R
s) is 1.2 to 2.0, particularly 1.4 to 1.7, the particle size is relatively uniform, and the content of particles contributing to the antiblocking action is large. For this reason, the alkali aluminum sulfate hydroxide of the present invention exhibits a satisfactory anti-blocking action with a relatively small amount.

Further, the alkali aluminum sulfate hydroxide according to the present invention has a spherical or spindle-shaped particle shape, and in relation to the above-mentioned particle shape, the major axis (D _L ) and the minor axis (D _S ) of the particle. The aspect ratio represented by the ratio (D _S / D _L ) is generally 0.5 to 1.0, particularly 0.7 to 1.
It is in the range of 0.

The refractive index of the alkali aluminum sulfate hydroxide in the immersion method is generally in the range of 1.50 to 1.57, particularly 1.52 to 1.54, and is close to that of resin. And the compounded resin composition has an advantage of being excellent in transparency.

Further, this alkali aluminum sulfate hydroxide is subjected to a dispersion abrasion test (NF-type abrasion test) described later.
Is 0.5% or less, particularly in the range of 0.2 to 0.4, and the hardness is lower than that of silica or alumino-silica which is a general-purpose resin compounding agent. Due to the low hardness and the above-mentioned particle shape, even under conditions where the surface of a resin molded product such as a film is rubbed, the surface of the molded product is hardly scratched and has excellent scratch resistance. .

[Post-treatment] The alkali aluminum sulfate hydroxide according to the present invention can be used as it is for applications such as a resin compounding agent. It can be used for various applications.

The surface of the alkali aluminum sulfate hydroxide used in the present invention is an inorganic oxide such as titanium oxide, silicon oxide, aluminum oxide, zirconium oxide, zinc oxide, barium oxide, magnesium oxide, calcium oxide, and basic carbonate. Magnesium, hydrotalcite, alkali aluminum carbonate, inorganic silicate, A
It can be coated or surface-treated with synthetic zeolites of type, X type, P type, etc. and their acid-treated products or metal ion exchange products. Suitable oxides include fumed silica, fumed alumina, and fumed titania, and the fluidity of the powder can be further improved by adding a small amount of these. The compounding amount is suitably 0.01 to 30 parts by weight per 100 parts by weight of the alkali aluminum sulfate hydroxide.

The alkali aluminum sulfate hydroxide may be coated with a metal soap, a resin acid soap, various resins or waxes, a silane-based, aluminum-based, titanium-based or zirconium-based coupling agent, if desired. Can be. The dispersibility in the resin can be further improved by blending these organic substances.
The compounding amount is 100 parts of alkali aluminum sulfate hydroxide.
The appropriate amount is 0.01 to 10 parts by weight per part by weight.

The alkali aluminum sulfate hydroxide according to the present invention can be used as antibacterial particles by incorporating a metal or organic substance having antibacterial properties. The antibacterial metal ions are selected from silver, copper, zinc, tin, mercury, lead, bismuth and thallium metal elements.
Species or two or more can be used. These metal elements are preferably selected from water-soluble salts, and can be selected from general industrial chemicals and complex compounds. Examples thereof include silver nitrate, silver nitrate, silver sulfate, silver perchlorate, silver acetate, diammine silver nitrate, and ammine silver sulfate; and copper ion, copper nitrate (II) and copper perchlorate (II). ), Copper (II) acetate,
Copper (II) sulfate and the like; in the case of zinc ions, zinc nitrate, zinc sulfate, zinc perchlorate, zinc thiocyanate, zinc acetate and the like can be mentioned. Using these, surface coating, ion exchange, mixed crystal and the like can be performed to obtain antibacterial particles.

Examples of the antibacterial organic compound include fungicides and preservatives generally used in the art. Examples thereof include iodophors, tropolones such as hinokitiol, chitosans, paraoxybenzoic acid esters, organic acids such as benzoic acid and dehydroacetic acid, salts of these organic acids, and quaternary ammonium salts such as benzalkonium chloride. And the like. Particularly suitable antibacterial organic compounds include polyvinylpyrrolidone iodine complexes.

[Use] The alkali aluminum sulfate hydroxide according to the present invention can be used as a resin compounding agent for a thermoplastic resin. Examples of the thermoplastic resin include, for example, a resin produced using a metallocene catalyst, as well as low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, polypropylene, and poly1- Α- such as butene, poly 4-methyl-1-pentene or ethylene, propylene, 1-butene, 4-methyl-1-pentene;
Polyolefins such as random or block copolymers of olefins, ethylene / vinyl acetate copolymers, ethylene / vinyl alcohol copolymers, ethylene / vinyl compound copolymers such as ethylene / vinyl chloride copolymers, polystyrene, acrylonitrile / Styrene copolymer, A
BS, styrene resins such as α-methylstyrene / styrene copolymer, polyvinyl chloride, polyvinylidene chloride, vinyl chloride / vinylidene chloride copolymer, polyvinyl compounds such as polymethyl acrylate, polymethyl methacrylate,
Polyamide such as nylon 6, nylon 6-6, nylon 6-10, nylon 11, or nylon 12, thermoplastic polyester such as polyethylene terephthalate or polybutylene terephthalate, polycarbonate, polyphenylene oxide, or a resin thereof. May be.

For such uses, the resin compounding agent of the present invention is used in an amount of 0.001 to 50 parts by weight, particularly 0.01 to 30 parts by weight, per 100 parts by weight of the resin.

Of course, it can be used in combination with a resin compounding agent known per se. For example, a plasticizer, an antioxidant, an ultraviolet absorber, a light stabilizer, an antifogging agent, a warming agent, a nucleating agent for a flame retardant, a lubricant, an antistatic agent, various inorganic auxiliaries and the like can be used together.

Examples of the plasticizer include phthalate plasticizers, ester plasticizers such as adipic acid ester plasticizers, polyester plasticizers, phosphate plasticizers, and chlorine plasticizers.

Examples of the phenolic antioxidants include bisphenol A, bisphenol B, bisphenol F, 2,6-diphenyl-4-octadecyloxyphenol, and stearyl (3,5-ditert-butyl-4-hydroxyphenyl). ) -Propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], bis [3,3-bis (4 -Hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris ( 2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, triethylene glycol bis [ (3-
Tert-butyl-4-hydroxy-5-methylphenyl) propionate].

Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl and distearyl, and polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). β-alkylmercaptopropionates.

Examples of the phosphite-based antioxidant include tris (2,4-di-tert-butylphenyl) phosphite and tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-). 5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite And phosphite and di (nonylphenyl) pentaerythritol diphosphite.

Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2'-hydroxy-
5′-methylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′,
5′-dicumylphenyl) benzotriazole, 2,
2- (2'-hydroxyphenyl) benzotriazoles such as 2'-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol.

Examples of the light stabilizer include hindered amine light stabilizers, such as 1,2,2,6,6-pentamethyl-4-piperidyl stearate and 2,2,2.
6,6-tetramethyl-4-piperidyl benzoate,
N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2 6,6-tetramethyl-4-piperidyl- (3,5-ditert-butyl-4-hydroxyphenyl) propionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetra (2 , 2,
6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetra Methyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-
Piperidyl) .di (tridecyl) butanetetracarboxylate.

Examples of the antifogging agent include stearic acid, monoglyceride, oleic acid monoglyceride, polyglycerin oleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, and sorbitan monooleate.

Specific examples of the inorganic auxiliary agent include finely divided silicon oxide, basic magnesium carbonate, aluminum-containing phyllosilicate, hydrotalcite, lithium aluminum carbonate, dawsonite, nepheline, alunite, calcium silicate, A Type, X-type, P-type, and other synthetic zeolites and their acid-treated products or metal ion exchange products, talc, kaolin, various silicates, and the like.

[0048]

The present invention is further described by the following examples. In addition, the test method was performed according to the following method. (1) BET specific surface area Sortopmatic Series manufactured by Carlo Elba
s 1900 was used and measured by the BET method. (2) pH The 5% aqueous dispersion of the sample was stirred for 5 minutes, and the pH at 20 ° C. was measured with a pH meter manufactured by Toa Denpa Kogyo. (3) Particle size (median diameter) The average particle size (median diameter; μm) was measured using a TAII type manufactured by Coulter Counter Co., Ltd., with an aperture tube diameter of 50 μm. (4) Bulk specific gravity Measured in accordance with Jls-K-6220. (5) Refractive index A solvent (α-bromonaphthalene, kerosene) having a known refractive index is adjusted using an Abbe refractometer in advance. Then Lar
According to Sen's oil immersion method, a few mg of the sample powder is taken on a slide glass, a drop of a solvent having a known refractive index is added, a cover glass is applied, and the solvent is sufficiently immersed. Observe and ask. (6) Hygroscopicity After heating 1 g of a sample at 150 ° C. for 2 hours, a relative humidity of 90 g
%, The water adsorption capacity when left in a temperature atmosphere of 25 ° C. for 24 hours was measured. (7) Aspect ratio From a photographic image obtained by a scanning electron microscope (Hitachi S-570), representative particles are selected, and the major and minor diameters of the particle image are measured using a scale. I asked. Aspect ratio = short diameter (DS) / long diameter (DL) (8) X-ray diffraction image Using a RAD-IB system manufactured by Rigaku Denki,
It was measured by u-Kα. Target Cu filter Curved crystal graphite monochromator Detector SC voltage 40KVP Current 20mA Count full scale 700c / s Smoothing point 25 Scanning speed 1 ° / min Step sampling 0.02 ° Slit DS1 ° RS0.15mm SS1 ° Illumination angle 6 ° (9 ) Differential thermal analysis It was measured using TAS-100-TG8110 manufactured by Rigaku Corporation. The measurement conditions include a standard substance α-Al ₂ O ₃ ,
Thermal analysis was performed at a temperature rising rate of 5 ° C./min and in an air atmosphere at a temperature ranging from 110 to 800 ° C. (10) Infrared absorption spectrum A sample dried at 110 ° C. using a constant temperature drier was used as a sample and measured using an A-302 type infrared absorption spectrum analyzer manufactured by JASCO Corporation. (11) Abrasion test Abrasion was measured using an NF type abrasion tester manufactured by Japan Filcon Corporation. In this measurement method, a test solution having a sample concentration of 2 wt% is circulated and circulated through a bronze mesh, and the degree of wear is measured from the weight change of the mesh for 180 minutes.

Film property test Preparation of sample film (mixing) Linear low-density polyethylene resin * 100 parts by weight Sample 0.5 parts by weight 100 parts by weight of linear polyethylene resin having a melt flow rate of 2.1 g / 10 min and 5 parts by weight Part of the sample was pelletized at 160 ° C. using an extruder. The pellet 1 was mixed with 10 linear polyethylene resins, and
A film having a sample concentration of 0.5 part by weight at a die temperature of ° C was formed. The following physical properties were measured using these pellets and films. (11) Haze degree Measured according to ASTM D1003. JIS K 7105
Conforms to -6.4 (12) Yellow index value Conforms to JIS K 7105-6.3 9 g of film is placed in a mold and heated at 170 ° C and 190 kgf / cm ² for 2 minutes to make a 3 mm thick plate. The YI value of the prepared plate is measured by Nippon Denshoku Industries Co., Ltd.
000. (13) Blocking property Two films were superposed, left under a load of 200 g / cm ² at 40 ° C. for 24 hours, and evaluated by the ease of peeling of the films. ◎ Peeled without resistance ○ Slightly hard to peel off △ Hard to peel off × Extremely hard to peel off (14) Scratch property Five hours after film formation, two films were stacked and rubbed with a finger. Was. ◎ Little scratches ○ Slight scratches △ Slight scratches × Scratch

(Example 1) 1594.3 g of a commercially available sulfuric acid band (Al ₂ O ₃ min. 7.7%) was stirred with potassium sulfate 21
0.4 g and 376.6 g of aluminum hydroxide are added to make a mixed solution (pH 1.9). After stirring, the temperature is raised to 170 ° C. in an autoclave in a stationary state, and a hydrothermal reaction is performed for 6 hours.
The obtained reaction solution (aqueous solution, pH 6.2) was filtered, washed with water, and washed with water.
After drying at 10 ° C., 998 g of potassium aluminum sulfate hydroxide (Sample 1-1) was obtained. Further, the surface was coated with zinc stearate (5%) (sample 1-2). As a result of analysis, the chemical composition of this sample was KAl ₃ (S
O ₄ ) ₂ (OH) ₆ , and various physical properties of this sample are shown in Table 1.
Table 2 shows the properties of the film containing this sample.

Example 2 396.4 g of a commercially available sulfuric acid band (Al ₂ O ₃ min. 7.7%) was stirred with potassium sulfate.
3 g and 93.6 g of aluminum hydroxide are added to form a mixed solution (pH 2.1). After stirring, the temperature is raised to 170 ° C. in an autoclave in a stationary state, and a hydrothermal reaction is performed for 6 hours. The obtained reaction solution (aqueous solution pH 5.5) was filtered, washed with water, and heated at 110 ° C.
Then, 240 g of potassium aluminum sulfate hydroxide (sample 2) was obtained. As a result of the analysis, the chemical composition of this sample was KAl ₃ (SO ₄ ) ₂ (OH) _6. Table 1 shows the physical properties of this sample, and Table 2 shows the properties of the film containing this sample.
Shown to

Example 3 396.4 g of a commercially available sulfuric acid band (Al ₂ O ₃ min. 7.7%) was stirred with potassium sulfate.
3 g, 93.6 g of aluminum hydroxide and 501.7 of water
g to make a mixed solution (pH 2.7). The temperature is raised to 170 ° C. in an autoclave with stirring, and a hydrothermal reaction is performed for 6 hours. The obtained reaction solution (aqueous solution pH 4.1) was filtered,
After washing with water and drying at 110 ° C., 252 g of potassium aluminum sulfate hydroxide (sample 3) was obtained. As a result of the analysis, the chemical composition of this sample was KAl ₃ (SO ₄ ) ₂ (OH) _6. Table 1 shows various physical properties of this sample, and Table 2 shows properties of a film containing this sample.

(Example 4) 35 g of potassium sulfate was stirred with 269.8 g of a commercially available sulfuric acid band (Al ₂ O ₃ min. 7.7%).
And 62.7 g of aluminum hydroxide and 367.4 g of water to obtain a mixed solution (pH 2.8). After stirring, the temperature is raised to 130 ° C. in an autoclave in a stationary state. The reaction was terminated when the temperature reached 130 ° C. The obtained reaction solution (aqueous solution, pH 1.9) was filtered, washed with water, and dried at 110 ° C. to obtain 165 g of potassium aluminum sulfate hydroxide (sample 4). As a result of analysis, the chemical composition of this sample was KAl ₃ (S
O ₄ ) ₂ (OH) ₆ , and various physical properties of this sample are shown in Table 1.
Table 2 shows the properties of the film containing this sample.

Example 5 Example 1 was repeated except that 210.4 g of potassium sulfate used in Example 1 was changed to a mixture of 105.2 g of potassium sulfate and 191.2 g of sodium sulfate.
In the same manner as in the above, potassium sodium aluminum sulfate hydroxide (sample 5) was obtained. As a result of the analysis, the chemical composition of this sample was K _0.5 Na _0.5 Al ₃ (SO ₄ ) ₂ (OH) _6. Table 1 shows the physical properties of this sample, and Table 2 shows the film properties containing this sample.

(Comparative Example 1) 105 g of aluminum sulfate (16.5% Al ₂ O ₃ for JIS water supply) and 150 g of potassium sulfate (first grade reagent) were taken, 800 g of water was added and dissolved, and the pH was 2.8. To obtain a mixed solution of aluminum sulfate and potassium sulfate. A 30% potassium hydroxide solution was added dropwise to this solution with stirring to obtain a milky suspension having a pH of 4, and the pH was measured once every 30 minutes while heating to 95 ° C. And stirred for 5 hours. The obtained white precipitate was filtered, washed with water, and heated to 110 ° C.
To obtain potassium aluminum sulfate hydroxide (Sample 6). Table 1 shows various physical properties of this sample, and Table 2 shows properties of a film containing this sample.

Comparative Example 2 105 g of aluminum sulfate (16.5% Al ₂ O ₃ for JIS water supply) and 125 g of sodium sulfate (reagent grade 1) were taken, dissolved in 800 g of water, and pH 3.2. To obtain a mixed solution of aluminum sulfate and sodium sulfate. A 30% sodium hydroxide solution was added dropwise to this solution with stirring to obtain a milky suspension having a pH of 4,
Measure the pH once every 30 minutes while heating to
The mixture was adjusted to pH 4 with a 0% potassium hydroxide solution and stirred for 5 hours. The resulting white precipitate is filtered, washed with water,
After drying at 10 ° C., sodium aluminum sulfate hydroxide (sample 7) was obtained. Table 1 shows the physical properties of this sample.

Comparative Example 3 An X-ray diffraction image of natural alunite as Sample 8 is shown in FIG. Table 1 shows various physical properties of this sample.

Comparative Example 4 A synthetic spherical aluminosilicate (Silton JC-20: manufactured by Mizusawa Chemical Industries) was used as Sample 9 to compare abrasion tests.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

According to the present invention, by subjecting aluminum sulfate, alkali sulfate or ammonium sulfate and aluminum hydroxide to a hydrothermal treatment, the above-mentioned raw materials react in a stoichiometric amount without producing by-products. The alkali aluminum sulfate hydroxide can be produced with a small number of steps with high yield and selectivity. Further, in the alkali aluminum sulfate hydroxide according to the present invention, the individual particles have a substantially independent spindle-shaped or spherical new defined particle structure, and have a higher pH and suppression compared to known alkali aluminum sulfate hydroxide. It has a specific surface area and hygroscopicity, and is useful as a resin compounding agent.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction image of a potassium aluminum sulfate hydroxide according to the present invention.

FIG. 2 is an X-ray diffraction image of potassium sodium aluminum sulfate hydroxide according to the present invention.

FIG. 3 is an X-ray diffraction image of natural alunite.

FIG. 4 is an infrared absorption spectrum of potassium aluminum sulfate hydroxide according to the present invention.

FIG. 5 is a scanning electron microscope photograph showing the particle structure of a spindle-shaped (elliptical sphere) among the alkali aluminum sulfate hydroxides according to the present invention.

FIG. 6 is a scanning electron micrograph showing a particle structure of a spherical aluminum aluminum sulfate hydroxide according to the present invention.

FIG. 7 is a thermogravimetric analysis curve of the alkali aluminum sulfate hydroxide of the present invention.

FIG. 8 is a chart showing the particle size distribution of potassium aluminum sulfate hydroxide used in Example 1.

FIG. 9 is a scanning electron micrograph showing the particle structure of potassium aluminum sulfate hydroxide used in Comparative Example 1.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masami Kondo 4-1-1, Nihonbashi Muromachi, Chuo-ku, Tokyo Inside Mizusawa Chemical Industry Co., Ltd. (72) Inventor Yasuo Saito 4-1-1, Nihonbashi Muromachi, Chuo-ku, Tokyo No. Mizusawa Chemical Industry Co., Ltd. F-term (reference) 4G076 AA10 AA14 AA18 AA19 BA12 BA43 BC02 BC07 BD02 CA03 CA26 CA27 CA28 CA33 CA40 DA02 DA30 4J002 BB031 BB051 BB061 BB121 BB141 BB151 BB171 BB221 BC031 BC04 BG1BD051 CF061 CF071 CG001 CH071 CL011 CL031 DG046 FA046 FA086 FB076 FD016 GG02

Claims (10)

[Claims] (1) MAL ₃ (SO ₄ ) ₂ (OH) ₆ (1) wherein M is an alkali metal or ammonium group;
And the following X-ray diffraction image Surface spacing (dx, angstrom) Surface index Relative intensity 5.72 101 10 4.96 012 49 3.51 110 29 2.99 113 100 2.86 006 3 2. 48 024 3 2.27 107 13 2.22 122 5 2.02 214 1 1.91 033 19 1.75 200 9 1.65 312 2 1.57 134 2 1.51 315 1 1.49 0210 1 Having a 5% aqueous suspension pH in the range of 4 to 7 and a BET specific surface area of 30 m
² / g or less, an amount of moisture absorption at 25 ° C. and 90% RH is 10% or less, and each particle has a substantially independent spindle-shaped or spherical shaped particle structure. Sulfate hydroxide. 2. The alkali or ammonium aluminum sulfate hydroxide according to claim 1, wherein the bulk specific gravity is in the range of 0.5 to 1.0. 3. The alkali or ammonium aluminum sulfate hydroxide according to claim 1, wherein the volume-based median diameter measured by the Coulter method (electrical resistance method) is in the range of 0.5 to 10.0 μm. 4. Formula Rs = D ₂₅ / D _{75 In the} formula, D ₂₅ represents a particle size at 25% value of a volume-based cumulative particle size distribution curve by the Coulter method, and D ₇₅ represents a particle size at 75% value. The sharpness (R) of the particle size distribution defined by
2. The alkali or ammonium aluminum sulfate hydroxide according to claim 1, wherein s) is from 1.2 to 2.0. 5. The alkali aluminum sulfate according to claim 1, wherein the aspect ratio represented by the ratio (D _S / D _L ) between the major axis (D _L ) and the minor axis (D _S ) of the particles is 0.5 to 1. Salt hydroxide. 6. The alkali or ammonium aluminum sulfate hydroxide according to claim 1, wherein the refractive index in the immersion method is in the range of 1.50 to 1.57. 7. The alkali or ammonium aluminum sulfate hydroxide according to claim 1, wherein the degree of abrasion in a dispersion abrasion test (NF-type abrasion test) is 0.5% or less. 8. A method for producing spindle-shaped or spherical alkali or ammonium aluminum sulfate hydroxide, which comprises hydrothermally treating aluminum sulfate, alkali sulfate or ammonium sulfate and aluminum hydroxide. 9. The method according to claim 8, wherein the hydrothermal treatment is performed at a temperature of 90 ° C. or higher. 10. A resin compounding agent comprising the alkali or ammonium aluminum sulfate hydroxide according to any one of claims 1 to 7.