COMPOSITE ALKALI ALUMINUM HYDROXIDE CARBONATE, AND PROCESS FOR PRODUCTION AND USE THEREOF

Abstract: According to this invention, an amorphous or pseudo-boehmite-type hydrated alumina gel and an alkali metal carbonate or bicarbonate as starting materials are reacted in an aqueous medium to give a method of producing a process for producing an alkali aluminum complex hydroxide carbonate salt which is industrially low-cost and has high productivity. Furthermore, by using a gibbsite-type hydrated alumina, a lithium aluminum complex hydroxide carbonate salt can be synthesized by a migration method. The lithium aluminum complex hydroxide carbonate salt and the sodium aluminum complex hydroxide carbonate salt obtained by the processes of the present invention have excellent compoundability in pigments and resins. In addition, these complex salts have no foaming hazards at the time of processing the resins and are useful as resin fillers for halogen capturing property, infrared ray absorbing property and excellent transparency. They are especially useful as a stabilizer (halogen capturing agent) for resin films, a warmth-keeping agent (infrared absorbing agent) and an anti-blocking agent.

Description: This invention relates to an alkali aluminum complex hydroxide carbonate salt having a lithium aluminum complex-type or dawsonite-type crystal structure, a process for producing said salt, and its uses. More specifically, it relates to a lithium aluminum complex hydroxide carbonate salt which is useful as a heat stabilizer (halogen trapping) for olefin resins containing a chlorine-containing polymer or halogen-containing catalyst residues, and an anti-blocking agent or a warmth-retaining agent (infrared absorbing agent) of a thermoplastic resin film, and a process for producing said salt. The present invention also relates to uses of the above-mentioned salt. It especially relates to a resin compounding agent which is easy to compound in film-forming resins and can form warmth-retaining resin films having excellent infrared absorbability and transparency. Chlorine-containing polymers such as a vinyl chloride polymer are liable to be colored by heat-decomposition reaction such as de-hydrochlorination or to be reduced in mechanical properties in heat molding processing or subsequent heat histories. To prevent the above troubles, it is generally required to compound stabilizers. Olefin-type resins produced by using Ziegler-type catalysts contain halogen-containing catalyst residues. These residues generate hydrogen chloride at the time of heating and molding to cause rust in the molding machines or generate deterioration in the resins, for example, yellowing. To prevent this deterioration, stabilizers which trap hydrogen chloride were compounded widely. The use of hydrotalcite as such a stabilizer has been known from old. For example, Japanese Laid-Open Patent Publication No. 80445/1980 describes that hydrotalcite is used as a stabilizer for halogen-containing resins. Further, Japanese Patent Publication No. 36012/1983 shows that a β-diketone compound and a hydrotalcite of formula (1) Mg 1-x ·Al x (OH) 2 ·A x/2 ·mH 2 O - wherein x denotes a number of 0<x≤0.5, A represents CO 3 2- or SO 4 2- , and m represents a positive number are compounded in a halogen-containing resin. Furthermore, Japanese Patent Publication No. 30737/1984 discloses that at least 0.01 % by weight of a complex compound represented by general formula (2) M x Al y (OH) 2x + 3y - 2z (A) z .aH 2 O wherein M represents Mg, Ca or Zn, A represents CO 3 or HPO 4 , x, y and z represent a positive number, and a is zero or a positive number, is compounded in a polyolefin containing halogen-containing catalyst residues produced by using a Ziegler-type catalyst. Hydrotalcites are non-toxic complex hydroxide and carbonate salts of magnesium and aluminum, have excellent heat stability, and are transparent when compounded in a polymer. These hydrotalcites ideally have a chemical composition expressed by formula (3) Mg 6 Al 2 (OH) 16 ·CO 3 ·mH 2 O wherein m is 0 or a positive number. However, Mg and Al, within a very broad range, form a solid solution as shown by formula (1) or (2), and there is a problem in that it is difficult to form a composition having a strictly constant composition. A report of C. J. Serna et al. entitled "Crystal-Chemical Study of Layered [Al 2 Li(OH) 6 ] + X - ·nH 2 O" (Clays and Clay Minerals, Vol. 25, page 384 (1977)) describes that a lithium aluminum complex hydroxide salt is synthesized by adding a benzene solution of aluminum tri(sec-butoxide) (ASB) as liquid drops to an excessive aqueous solution of lithium carbonate, hydrolyzing ASB, washing the resulting gel, and thereafter, hydrothermally treating the washed gel for several days at 130 °C. A report of I. Sissoko et al. entitled "Anion Intercalation and Exchange in Al(OH) 3 -Derived Compounds" (Journal of Solid State Chemistry, Vol. 25, pages 283-288 (1985) describes that a lithium aluminum complex hydroxide salt is produced by adding AlCl 3 as liquid drops to an aqueous solution containing LiOH and Na 2 CO 3 (or Na 2 SO 4 ), changing the pH from 13 in the early period to 10.2 in the last stage to form a gel-like precipitate, and aging the precipitate with stirring (see Comparative Example 6 and Figure 6 to be given below.) U. S. Patents Nos. 4,116,856 and 4,221,767 disclose that crystals of lithium, aluminum complex hydroxide salt are produced by reacting amorphous Al(OH) 3 or crystalline hydrated alumina (such as nordstrandite, bayerite, gibbsite) with LiOH, and then reacting the mixture with LiX (wherein X represents a halide). However, the resulting crystals are sol-like and are very difficult to filter. U. S. Patents Nos. 5,356,567, 5,360,859, and 5,419,883 describe a lithium aluminum complex hydroxide salt (to be referred to as LAHS) of general formula (4) [Al 2 Li(OH) 6 ] n X·mH 2 O wherein X is an inorganic or organic anion, n is the valence of the anion, and m is a number of 3 or below, having at least 10, especially at least 20 of an orientation degree (OD) defined by formula (5) OD=I(002)/I(110) wherein I(002) represents a relative intensity of an X-ray diffraction (Cu-Kα) peak appearing in the index of a plane (002) at a spacing (d) of 7.67 to 7.84 Å, and I(110) represents a relative intensity of an X-ray diffraction (Cu-Kα) peak appearing in the index of a plane (110) at a spacing (d) of 4.41 to 4.45 Å. For example, as typical examples of LAHS, lithium carbonate and aluminum chloride are reacted in an aqueous solution in the presence of sodium carbonate and sodium hydroxide, a higher fatty acid or a surface-active agent is added as an orientation enhancer to the reaction mixture, and the mixture is treated at a temperature of 60 to 100°C so that the degree of orientation becomes at least 10. As another type of the alkali aluminum complex hydroxide carbonate salt, sodium aluminum complex hydroxide carbonate salts having a dawsonite-type crystal structure are known. Methods of synthesizing these salts are known from Japanese Patent Publication No. 38318/1972, Japanese Patent Publication No. 17718/1979, Japanese Laid-Open Patent Publication No. 22628/1981, Japanese Patent Publication No. 44604/1982, Japanese Laid-Open Patent Publication No. 61625/1982, Japanese Laid-Open Patent Publication No. 83933/1984, Japanese Laid-Open Patent Publication No. 100017/1988, Japanese Patent Publication No. 24731/1989, Japanese Patent Publication No. 58205/1990 and Japanese Laid-Open Patent Publication No. 271116/1991. As a synthesizing method of the above product, Japanese Patent Publication 38313/1972 discloses a method of producing dawsonite which comprises reacting an aluminum salt and sodium carbonate using at least 2 moles of CO 2 per mole of Al 2 O 3 , and maintaining the pH of the reaction mixture at 7.2 to 10.5. However, LAHS synthesized by these known methods is in the form of gel-like particles, and the growth of crystals is still insufficient. The shape and size of these particles are non-uniform, and are still unsatisfactory as a compounding agent for resins. Furthermore, dawsonite is fibrous. Many of these fibers are entangled in the form of fibrous ball. Accordingly, they are still unsatisfactory in use as a compounding agent for resins. Furthermore, synthesizing methods for known alkali aluminum complex hydroxide carbonate salts must treat the starting materials and the products as a dilute solution or slurry. Otherwise, the liquids have a high viscosity, and their stirring is difficult. Thus, the productivity is low, and the cost of production is high. Another problem is that the resulting alkali aluminum complex hydroxide carbonate salts are very difficult to filter, and a long period of time is required for the filtration process. The fate of the alkali aluminum complex hydroxide carbonate salts is that it is essential to use alkali metal compounds as a starting material. These resulting products contain free alkali metal components as impurities in addition to alkali metal components charged into the compounds. These free alkali metal components lead to the defect that they may color the resins in which these alkali metal components are compounded. [Disclosure of the Invention] The present inventors have found an unexpected fact that when amorphous or pseudo-boehmite hydrated alumina gel is used as an aluminum component and the concentration of Al 2 O 3 is maintained at a high level in the reaction system, an alkali aluminum complex hydroxide carbonate salt can be synthesized within a relatively short period of reaction time and the filtration of the product can be very easily carried out. Furthermore, the present inventors have found that when gibbsite-type aluminum hydroxide is utilized as a mother or template for LAHS and lithium is migrated to the vacancy of gibbsite, a highly crystalline and dense LAHS can be obtained. An object of this invention is to provide a method for producing a lithium aluminum complex hydroxide carbonate salt in which the reaction can be carried out by maintaining the concentration of the starting material in the reaction mixture at a high level, the synthesis can be performed within a very short period of reaction time, and furthermore, the filtration and washing with water of the reaction product are extremely easy. Another object of this invention is to provide a lithium aluminum complex hydroxide carbonate salt and its uses in which the dispersion in a resin can be easily carried out and the deterioration tendency of the resin is markedly reduced. Yet another object of this invention is to provide a lithium aluminum complex hydroxide carbonate salt in which the crystals are grown to a high level, have a large bulk density, and have excellent pigmentability. A further object of this invention is to provide a process for producing LAHS having excellent producibility and cost, which can be carried out within a very short period of reaction time while maintaining the concentration of the starting material in the reaction system at a high level. An additional object of this invention is to provide a resin compounding agent composed of the lithium aluminum complex hydroxide carbonate salt. According to this invention, there is provided a process for producing a lithium aluminum complex hydroxide carbonate salt (to be referred to simply as a hydrated alumina gel method) which comprises reacting amorphous or pseudo-boehmite hydrated alumina gel and a lithium carbonate or bicarbonate in an aqueous medium under such a condition that the concentration of aluminium calculated as alumina (Al 2 O 3 ), based on the total amount of the aqueous medium and the materials added thereto becomes 1 to 5 % by weight and the pH at the termination of the reaction becomes 7 to 11, wherein the hydrated alumina is reacted with the carbonate or the bicarbonate so that the amount of the carbonic acid ion is at least 0.25 mole based on the total aluminium atoms and wherein the reaction is carried out a temperature of 50 to 90°C. [Simple Description of Drawings] Fig. 1 is an X-ray diffraction pattern of hydrated alumina used as a starting material, wherein (A) is an X-ray diffraction pattern of a gibbsite of hydrated alumina, (B) is an X-ray diffraction pattern of pseudo-boehmite hydrated alumina, and (C) is an X-ray diffraction pattern of amorphous hydrated alumina gel. Fig. 2 is an X-ray diffraction pattern of a lithium aluminum complex hydroxide carbonate salt (LAHCS) according to the production method of this invention. Fig. 3 is an X-ray diffraction pattern of a lithium aluminum complex hydroxide carbonate salt according to a conventional co-precipitating method. Fig. 4 is a scanning-type electron microscopic photograph showing a particle structure of a lithium aluminum complex hydroxide salt according to the production method described in the literature reference of I. Sissoko et al. in Comparative Example 1. Fig. 5 shows enlarged views of peaks of indices of a plane (016) and (017) indicating an X-ray diffrraction pattern of a lithium aluminum complex hydroxide carbonate salt, which also show a method of seeking a laminated asymmetry index. Fig. 6 is a scanning-type electron microscopic photograph showing a particle structure of a lithium aluminum complex hydroxide carbonate salt (LAHCS) according to Example 1 of the present invention. [Best Form for Practising the Present Invention] (A Process for Producing an Alkali Aluminum Complex Hydroxide Carbonate Salt) (1) A hydrated alumina gel method In the production method of this invention, the first characteristic is that amorphous or pseudo-boehmite type hydrated alumina gel is used as an aluminum component. By using the hydrated alumina gel, it is possible to maintain the concentration of Al 2 O 3 in the reaction system at a higher level than when a water-soluble aluminum chloride is used, and the reaction can be carried out within a shorter period of time. Hydrated alumina, generally called aluminum hydroxide, includes various known types such as gibbsite, boehmite and diaspore. In accordance with this synthesizing method, amorphous or pseudo-boehmite is selected, and used. Attached drawings, Fig. 1, (B) shows an X-ray diffraction pattern of pseudo-boehmite-type hydrated alumina gel, and (C) shows an X-ray diffraction pattern of amorphous hydrated alumina gel. In this synthesizing method of this invention, this amorphous or pseudo-boehmite hydrated alumina gel is reacted with a lithium carbonate salt or bicarbonate salt in an aqueous medium, and the second characteristic is that the concentration of alumina (Al 2 O 3 ) becomes 1 to 5% by weight, and the pH at the termination of the reaction is maintained at 7 to 11. This increases the filtrability and washability with water of the resulting alkali aluminum complex hydroxide carbonate salt markedly. For example, as compared with the alkali aluminum complex hydroxide carbonate salt resulting from water-soluble aluminum salt as a starting material; in accordance with the synthesizing method of this invention, the filtration time can be shortened to about 1/10, and the required amount of water to be used can be saved to about 1/2. The fact that an increase of the concentration of alumina results in increasing the filtrability of the resulting alkali aluminum complex hydroxide carbonate salt has been found as a phenomenon. Although the reason for increased filtrability of the resulting carbonate salt is never bound to the above fact, it is presumed that in the reaction system of the present invention, primary particles formed by the reaction of the above carbonate salt or bicarbonate salt grow to secondary particles having relatively large sizes, and this growth contributes to increased filtrability and washability. This agrees with the fact that stirring in the reaction system is easy despite a high solids concentration in the system. The hydrated alumina used in this invention has an amorphous or pseudo-boehmite structure. This is considered to be closely related to a high reactivity. The gel is an assemblage of colloidal particles upon a loss of independency. Since these colloidal particles are in an amorphous state or in a condition near it, and since the gel is hydrated together with a sol which is independent as colloidal particles, it is belived that the hydrated alumina has very high reactivity. In addition, since the gel is an assembly of colloidal particles, even when the concentration of alumina in the reaction system is increased, it is considered that the viscosity in the liquid is lowered, and the stirring can be easily carried out advantageously. The amorphous or pseudo-boehmite hydrated alumina gel may be obtained by using aluminum chloride and aluminum nitrate as the aluminum salt. Preferably, aluminum sulfate or basic aluminum sulfate is reacted with sodium carbonate and/or sodium bicarbonate, especially sodium bicarbonate, for neutralization. The hydrated alumina so obtained has excellent actions mentioned above, and is especially excellent as a starting material for the lithium aluminum complex hydroxide carbonate salt. Generally, by maintaining the pH during neutralization at 4 to 8, the amorphous or pseudo-boehamite hydrated alumina gel is precipitated. It is filtered and washed with water and used as the starting material in this invention. In view of the filtrability and washability with water of the finally neutralized product, the reaction is carried out under heating at a temperature of 50 to 90°C. When basic aluminum sulfate is used as the starting material, the amount of sodium carbonate used for neutralization is small, and the process is advantageous beccause the presence of sodium sulfate is few. This basic sodium sulfate is obtained by adding calcium hydroxide to eliminate a part of the sulfuric acid radical from aluminum sulfate so that water-solubility may not be lost. The number of moles of the sulfuric acid radical is within a range of 0.9 to 3 per Al 2 atom. It is important in this invention that the reaction is carried out so that the concentration of alumina (Al 2 O 3 ) becomes 1 to 5 % by weight, especially 1.5 to 4% by weight. When the concentration of alumina is lower than the above range, it tends to become difficult to obtain a product having good filtrability and washability with water. On the other hand, when the concentration exceeds the above range, the viscosity of the reaction system becomes too high and it is difficult to stirr the reaction system whereby the uniformity of the reaction cannot be obtained. It is also important that the reaction is carried out under such a condition that the pH at the termination of the reaction is maintained at 7 to 11, especially 8.5 to 10.5. If the pH is higher than the above range, the hydrated alumina gel is crystallized or the reactability with the alkali metal carbonate salt or bicarbonate salt is lowered. On the other hand, if the pH is lower than the above range, a carbonic acid ion can no longer exist stably in the system, and the reactability tends to be lowered. The mole ratio of the amorphous or pseudo-boehmite type hydrated alumina gel to the alkali metal carbonate salt or bicarbonate salt [CO 3 /Al] is suitably at least 0.25, especially 0.25 to 4. The reaction time is about 1 to 12 hours. The addition sequence of the starting compounds is not particularly limited. The hydrated alumina gel and the carbonate salt or bicarbonate salt may be simultaneously poured to the reaction system, or the carbonate salt or bicarbonate salt may be added to the hydrated alumina gel, or they may be poured in a reverse sequence. The resulting lithium aluminum complex hydroxide carbonate salt is separated from the reaction mother liquor by filtration, washed with water and dried to form a product. The resulting lithium aluminum complex hydroxide carbonate salt may be surface-treated with surface treating agents to be mentioned later in the reaction mother liquor. The lithium aluminum complex hydroxide carbonate salt crystal as formed contains about 0.5 to 3 moles (m) of water although varying depending upon the synthesis conditions. When this crystal is heated and dried at a temperature of 300 °C or below, the above crystal can be dehydrated partly or completely. (Lithium aluminum complex hydroxide carbonate salt) According to this invention, the above process gives an lithium aluminum complex hydroxide carbonate salt having a unique crystal structure and extremely little alkali metal components as impurities. It has been found that this product has excellent dispersibility in resins, and when the above product is compounded in the resins, an effect of a very little tendency o deteriorate the resins can be obtained. This lithium aluminum complex hydroxide carbonate salt (LAHCS) is obtained by entering a lithium ion into the vacancy of an aluminum hydroxide octahedoral layer having a gibbsite structure, and taking up an anion to make up for its charge. The lithium ion has the smallest ionic radius among cations, and since as a monovalent ion, it is exceptionally a 6-coordinate ion, and this monovalent ion enters in the above vacancy to take up the above structure. Since LAHCS has a layered structure, exhibits ion exchangeability with respect to the anion, and shows a structure and characteristics similar to hydrotalcite, it is called a hydrotalcite-like compound or lithium hydrotalcite. However, LAHCS is quite different from hydrotalcite in chemical commposition and structure because hydrotalcite is obtained by isomorphous-substituting a part of magnesium of the brucite structure with aluminum. LAHCS generally has an X-ray diffraction pattern mentioned above. The lithium aluminum complex hydroxide carbonate salt (LAHCS) according to this invention, whether by the hydrated alumina gel method, is markedly characterized by a lamination asymmetry index (Is) defined by (1) of not larger than 1.0, especially 0.5 to 1.0, at a peak of an index of a plane (016) and not larger than 1.0, especially 0.5 to 1.0, at a peak of an index of a plane (017). Fig. 2 is an X-ray diffraction pattern of LAHCS produced according to the process of this invention in which the alumina starting material is amorphous or pseudo-boehmite hydrated alumina. Fig. 3 represents an X-ray diffraction pattern of LAHS according to a conventional co-precipitation method. A comparison of Fig. 2 and Fig. 3 shows the fact that with LAHCS according to the conventional co-precipitation method, peaks of an index of a plane (016) and an index of a plane (017) are broad and small and have a broad tailing on a broad angle side, whereas with LAHCS according to the synthetic method of this invention, peaks of an index of a plane (016) and an index of a plane (017) become sharp and high, the aforesaid tailing on a broad angle side disappears and the peaks become a nearly symmetrical shape with respect to a peak perpendicular. In Fig. 5 showing a method of seeking the lamination asymmetry index (Is) from the X-ray diffraction patterns of Figs. 2 and 3, the peaks of an index of a plane (016) and an index of a plane (017) are magnified, and with respect to these peaks, a narrow angle maximum inclination peak tangent a and a broard angle maximum inclination peak tangent b of the peaks are drawn, and a perpendicular c is drawn from a point of intersection between the tangent a and b . Then, an angle  1 between the tangent a and the perpendicular c and an angle  2 between the tangent b and the perpendicular c are sought. The lamination asymmetry index (Is) is sought as a value of Is=tan  2 /tan  1 ···(7). This index (Is) is 1.0 when the peak is completely symmetrical, and is a larger value when the degree of symmetry increases. With LAHS according to the co-precipitation method, Is values of indexes of planes (016) and (017) are 2.3 and 1.6 respectively. This shows that aluminum hydroxide octahedral basic layers in which a lithium ion is incorporated form a laminated structure in which the basic layers are laminated in the direction of C axis. By the conventional co-precipitation method, the basic layers are each shifted in four directions (front, behind, right, left) as seen in the direction of the C axis, and the sizes of the basic layers are decreased. On the other hand, in LAHCS according to the hydrated alumina gel method, the basic layers are almost over-lapped and piled in four directions, and the sizes of the basic layers are large and approximately constant. The bulk density of LAHCS produced by this invention is 0.1 to 0.35 g/cm 3 , especially 0.25 to 0.35 g/cm 3 , as measured by JIS K6721. The conventional LAHS shows a BET specific surface area of generally 10 to 40 m 2 /g, whereas LAHCS produced by the present invention has a BET specific surface area of 40 to 70 m 2 /g. The amount of an oil absorbed is as small as 40 to 70 ml/100 g. The above LAHCS has excellent compounding property in resins or paints. The LAHCS produced by the present invention has an orientation degree, defined by the following formula (8) OD=I(002)/I (110) wherein I (002) represents a relative intensity of an X-ray diffraction (Cu-Kα) peak appearing at an index of a plane (002) at a spacing (d) of 7.67 to 7.84 Å, and I (110) represents a relative intensity of an X-ray diffraction (Cu-Kα) peak appearing at an index of a plane (110) at a spacing (d) of 4.41 to 4.45 Å, of smaller than 10 and differs from the orientation degree of at least 10 assigned to LAHCS proposed by the present inventors before. LAHCS produced by the present invention has a pigment volume concentration of 40 to 50%. Since generally PVC of a pigment has a pigment volume concentration of 30 to 70%, it can be said that the LAHCS of this invention has excellent pigmentability. The pigment volume concentration is a value defined by the following formula (9). Pigment volume concentration: PVC = 100Bρ Bρ + 0.01 Or•Pρ Or: The amount of an oil absorbed in the pigment (ml/100 g) Bρ: The density of the resin (g/cm 3 ) Pρ: The density of the pigment (g/cm 3 ) That the pigment volume concentration is high shows that the large amount can be compounded in the coating agent. And also, it shows that in uses as a resin compounding agent, the filling property and pigmentability are good, and it is advantageous that the compounding in the resin is easy. Furthermore, LAHCS produced by the present invention, when formed as an aqueous slurry having a concentration of 5% by weight, has a specific resistance of at least 8000 Ω·cm, especially at least 10000 Ω·cm. Thus, the deterioration of the resin by alkali metal components is markedly suppressed. This fact will become clear by referring to the following example. Fig. 6 is a scanning-type electron microscopic photograph showing the particle structure of the lithium aluminum complex hydroxide carbonate salt (LAHCS) of a lithium aluminum complex type according to the hydrated alumina gel method (Example 5 of this invention). Furthermore, these particles have a median diameter (D 50 ) based on volume standard, measured by a laser scattering diffraction method, of generally 0.1 to 10 µm, especially 0.1 to 3 µm. The lithium aluminum complex hydroxide carbonate salt are useful as a resin compounding agent, for example especially a warmth-keeping agent and a halogen trapping agent for resins. (Uses) LAHCS produced according to this invention can be compounded in resins without any treatment. In order to modify the surface properties of the complex salts, when these compounds are treated in advance with not larger than 10 % by weight, especially 1 to 6 % by weight, of a surface treating agent, it is preferred that their dispersibility in resins increases and transmittance will further be increased. As the surface treating agent, silane-type, aluminum-type, titanium-type,and zirconium-type coupling agents, higher fatty acids, metal soaps, or resin acid soaps, fine powder amorphous silica and surface active agents may be used according to the objects. Generally, a higher fatty acid or a surface active agent is added to the reaction mother liquor containing the lithium aluminum complex hydroxide carbonate salt, and the mixture is treated with stirring. Examples of the higher fatty acid include saturated or unsaturated fatty acids having 10 to 22 carbon atoms, especially 14 to 18 carbon atoms, for example saturated fatty acids such as capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid and arachic acid, and unsaturated fatty acids such as linderic acid, tsuzic acid, petroselinic acid, oleic acid, linoleic acid, linolenic acid, and arachidonic acid. Stearic acid is preferred. The fatty acids may of course be mixed fatty acids such as beef tallow fatty acid, coconut oil fatty acid or palm oil fatty acid. Among the surface active agents, examples of anion surface active agents include primary higher alcohol sulfate ester salts, secondary higher alcohol sulfate ester salts, primary higher alkylsulfonate salts, secondary higher alkylsulfonate salts, higher alkyldisulfonate salts, sulfonated higher fatty acid salts, higher fatty acid sulfate ester salts, higher fatty acid ester sulfonate salts, sulfate ester salts of higher alcohol ethers, sulfonate salts of higher alcohol ethers, alkylolated sulfate ester salts of higher fatty acid amides, alkyl-benzenesulfonate salts, alkylphenolsulfonate salts, akylnaphthalenesulfonate salts and alkylbenzoimidazolesulfonate salts. More specific compounds of such surface active agents are disclosed in Hiroshi Horiguchi, "SYNTHETIC SURFACE ACTIVE AGENTS" (published in 1966 by Sankyo Publishing Company). As nonionic surface active agents, there are used nonionic surface active agents having a low HLB, especially an HLB of 12 or below, more preferably an HLB of 8 or below. Generally, examples of the nonionic surface active agents include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid amide ethers, polyvalent alcohol fatty acid esters, polyoxyethylene polyvalent alcohol fatty acid esters, fatty acid sucrose esters, alkylolamides and polyoxyalkylene block copolymers each with the HLB being within the above range. For example, when the polyoxyethylene unit content of these nonionic surface active agents is decreased, their HLB will be decreased. Therefore, by adjusting the number of moles of ethylene oxide added, it is possible to obtain nonionic surface active agents having the desired HLB. The amount of the fatty acid or the surface active agent to be added may suitably be 0.5 to 10 % by weight, especially 1 to 5 % by weight, based on the lithium aluminum complex hydroxide carbonate salt. The treating conditions are not particularly restricted, but generally the treatment should be suitably carried out with stirring at a temperature of 60 to 100 °C for about 0.5 to 5 hours. When the fatty acid is used, the fatty acid used reacts with a sodium ion present in the reaction system and is transferred to the aqueous phase in the form of a sodium soap, and the surface treatment of the resulting which aluminum complex hydroxide carbonate salt proceeds. When the anionic surface active agent is used, a free acid which is not a salt is used and consequently, a similar reaction takes place. The resulting surface-treated lithium aluminum complex hydroxide carbonate salt as it is may be used as a resin compounding agent. As required, it is surface-treated with an organic or inorganic aid as being after-treated, and then used as a resin stabilizer or a resin compounding agent. Examples of such organic aids are coating agents, for example, metal soaps such as a calcium salt, a zinc salt, a magnesium salt and a barium salt of stearic acid, palmitic acid and lauric acid, silane coupling agents, aluminum coupling agents, titanium coupling agents and zirconium coupling agents, various waxes and unmodified or modified various resins (such as rosin and petroleum resins). These coating agents may be used in an amount of 0.1 to 10 % by weight, especially 0.5 to 5% by weight, based on the lithium aluminum complex hydroxide carbonate salt. As the inorganic aids, fine particle silica such as aerosil and hydrophobic-treated aerosil, silicate salts such as calcium silicate and magnesium silicate, metal oxides such as calcia, magnesia and titania, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, a metal carbonate such as calcium carbonate, hydrotalcite, synthetic zeolites such as A type or P type, acid-treated products thereof, or their metal ion exchanged products thereof are exemplified regular-shaped particles of the inorganic aids may be used as blended or sprinkled with the lithium aluminum complex hydroxide carbonate salts, or may be used as deposited on the surface of the lithium aluminum complex hydroxide carbonate salt particles. By treating the resulting complex hydroxide carbonate salts with the inorganic aids, the refractive indexes of these salts may be adjusted. These inorganic aids may be used in an amount of 0.01 to 10% by weight, especially 0.1 to 5% by weight, based on the lithium aluminum complex hydroxide carbonate salt. When it is used as a compounding agent for resins, the refractive index of the resulting product can be matched with that of the resin used. LAHCS produced according to this invention is useful for regin compounding agent to thermoplatic resins such as a chlorine catcher, a heat stabilizer, an infrared absorption agent or an anti-blocking agent. In general 0.01 to 10 parts by weight of the lithium aluminum complex hydroxide carbonate salt is compounded in 100 parts by weight of a thermoplastic resin. The compounding amount may of course be properly selected according to the type and use of the resin within the above-mentioned range. The lithium aluminum complex hydroxide carbonate salt may be used in an amount of 0.1 to 10 parts by weight, especially 0.5 to 1.0 part by weight, based on 100 parts by weight of a chlorine-containing polymer. Examples of the chlorine-containing polymer include poly(vinyl chloride), poly(vinylidene chloride), chlorinated ply(vinyl chloride), chlorinated polyethylene, chlorinated polypropylene, chlorinated rubbers, a vinyl chloride/vinyl acetate copolymer, a vinyl chloride/ethylene copolymer, a vinyl chloride/propylene copolymer, a vinyl chloride/styrene copolymer, a vinyl chloride/isobutylene copolymer, a vinyl chloride/vinylidene chloride copolymer, a vinyl chloride/styrene/maleic anhydride ternary copolymer, a vinyl chloride/styrene/acrylonitrile copolymer, a vinyl chloride/butadiene copolymer, a chlorinated vinyl/propylene chloride copolymer, a vinyl chloride/vinylidene chloride/vinyl acetate ternary copolymer, a vinyl chloride/acrylic acid ester copolymer, a vinyl chloride/maleic acid ester copolymer, a vinyl chloride/methacrylic ester copolymer, a vinyl chloride/acrylonitrile copolymer, an internally plasticized polyvinyl chloride; and blends of these chlorine-containing polymers and α-olefin polymers such as polyethylene, polypropylene, polybutene and poly-3-methylbutene, polyolefins and copolymers such as an ethylene/vinyl acetate copolymer and an ethylene/propylene copolymer, polystyrene or acrylic resins, copolymers of styrene with another monomer (such as maleic anhydride, butadiene and acrylonitrile), an acrylonitrile-butadiene-styrene copolymer, an acrylic ester/butadiene/styrene copolymer or a methacrylic ester/butadiene/styrene copolymer. In this case, it is desirable to jointly use 0.01 to 10 parts by weight of a zinc salt of a fatty acid and 0.01 to 10 parts by weight of a β-diketone or a β-keto acid ester. Examples of the zinc salt of fatty acids may be as illustrated above. Examples of the β-diketone or the β-keto acid esters are compounds known coventionally in the indicated utility, and include 1,3-cyclohexadione, methylene-bis-1,3-cyclohexadione, 2-benzyl-1,3-cyclohexadione, acetyltetralone, palmitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, 2-acetyl-1,3-cyclohexanedione, benzoyl-p-chlorobenzoylmethane, bis(4-methyl-benzoyl)methane, bis(2-hydroxybenzoyl) methane, benzoylacetone, tribenzoyl-methane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoyl-methane, lauroylbenzoylmethane, dibenzoylmethane, bis(4-chlorobenzoyl)methane, bis(methylene-3,4-dioxybenzoyl)methane, benzoylacetylphenylmethane, stearoyl(4-methoxybenzoyl)methane, butanoylacetone,distearoylmethane, acetylacetone, stearoylacetone, bis(cyclohexanoyl)-methane and dipivaloylmethane. Of course, to use the lithium aluminum complex hydroxide carbonate salt various known additives such as stabilizers or stabilizer assistants, for example, non-metallic stabilizers, organic tin-type stabilizers and basic inorganic acid salts, plasticizers, antioxidants, photostabilizers, fire retardants, nucleus-forming agents, and epoxy stabilizers may be used jointly. Various nucleus-forming agents are conjointly used as additives in the molding of crystalline resins such as polypropylene and polyethylene terephthalate to be mentioned to increase transparency and impact strength or shorten the molding cycle and increase the dimensional stability. Furthermore, in the chlorine-containing resins, a combined use with various stabilizers is possible. For example, it is preferred that an organic tin stabilizer is used in combination. Examples of the organic tin compounds include organic tin mercaptides, organic tin sulfides, organic tin mercaptides sulfides, organic tin mercaptcarboxylates and organic tin carboxylates. (1) Examples of the organic tin mercaptides include diorganic mercaptides such as dibutyltin bis(lauryl mercaptide), dimethyltin bis(stearyl mercaptide), dioctyltin bis(mercaptoethyl tall oil fatty acid ester), dioctyltin bis(2-mercaptoethyl caprylate), dibutyltin bis(mercaptoethyl tall oil fatty acid ester), dimethyltin bis(mercaptoethyl stearate), dioctyltin bis(isooctyl thioglycolate), dioctyltin bis(2-ethylhexyl thioglycolate), dioctyltin bis(dodecyl thioglycolate), dioctyltin bis(tetradecyl thioglycolate), dioctyltin bis(hexadecyl thioglycolate), dioctyltin bis(octadecyl thioglycolate), dioctyltin bis(C 12-16 mixed alkyl thioglycolate), dibutyltin bis(isooctyl thioglycolate), dimethyltin bis(isooctyl mercaptopropionate), bis(2-mercaptocarbonylethyl)tinbis(isooctyl thioglycolate), bis(2-butoxycarbonyl ethyl)tin bis(butyl thioglycolate); mono organic mercaptides such as monobutyltin tris(lauryl mercaptide), monobutyl monochlorotin bis(lauryl mercaptide), momooctyltintris(2-mercaptoethyl caprylate), monobutyltintris(mercaptoethyl tall oil fatty acid ester), monomethyltintris(mercaptoethyl tall oil fatty acid ester), monomethyl-tintris(mercaptoethyl laurate), monomethyltintris(mercaptoethyl stearate), monomethyltintris(mercaptoethyl oleate), monooctyltintris(isooctyl thioglycolate), monooctyltintris(2-ethylhexyl thioglycolate), monooctyltintris(dodecyl thioglycolate), monooctyltintris(dodecyl thioglycolate), monooctyltintris(tetradecyl thioglycolate), monooctyltintris(hexadecyl thioglycolate), monooctyltintris(C 12-16 mixed alkyl thioglycolate), monooctyltintris(octadecyl thioglycolate), monobutyltintris(isooctyl thioglycolate), monobutyltintris(isooctyl mercapto propionate), monomethyltintris(isooctyl thioglycollate), monomethyltintris(tetra decyl thioglycollate), 2-methoxycarbonylethyl tin tris(isooctyl thioglycollate) and 2-butoxycarbonylethyltintris(2-ethylhexylthioglycollate). (2) Examples of the organic tin sulfides include methylthiostannic acid, butylthiostannic acid, octylthiostannic acid, dimethyltin sulfide, dibutyltin sulfide, dioctyltin sulfide, dicyclohexyltin sulfide, monobutyltin sulfide, oxide, 2-methoxycarbonylethyltin sulfide, 2-ethoxycarbonyltin sulfide, 2-butoxycarbonyltin sulfide, 2-isopropoxycarbonylethyltin sulfide, bis(2-methoxycarbonylethyl)tin sulfide and bis(2-propoxycarbonylethyl)tin sulfide. (3) Examples of the organic tin mercaptide. sulfides include bis[monobutyl.di(isooctoxycarbonylmethylenethio)tin]-sulfide, bis[dibutylmono(isooctoxycarbonylmethylenethio)tin] sulfide, bis[bis(2-methoxycarbonylethyl)tin isooctylthioglycolate] sulfide, bis(methyltin diisooctylthioglycolate) disulfide, bis(methyl/dimethyltin mono/diisooctyl thioglycolate) disulfide, bis(methyltin diisooctyl thioglycolate) trisulfide, bis(butyltin diisooctyl thioglycolate) trisulfide, bis[methyltin di(2-mercaptoethyl caprylate) sulfide and bis[methyltin di(2-mercaptoethyl caprylate) disulfide. (4) Examples of the organic tin mercapto carboxylates include dibutyltin-β-mercaptopropionate, dioctyltin-β-mercaptopropionate, dibutyltin mercaptoacetate, bis(2-methoxycarbonylethyl)tin thioglycolate, and bis(2-methoxycarbonylethyl)tin mercaptopropionate. (5) Examples of the organic tin carobylates include aliphatic monovalent carboxylates such as an octoate, laurate, myristate, palmitate, stearate and isostearate of a mono- or di-methyltin, mono- or di-butyltin, mono- or di-octyl-tin or mono- or bis(butoxycarbonylethyl)tin; a maleate polymer, and a maleate such as butyl maleate, benzyl maleate, oleyl maleate, and stearyl maleate; and mixed salts or basic salts of the above compounds. The plasticizers include ester-type plasticizers such as phthalate ester type plasticizers and adipate ester type plasticizers, polyester-type plasticizers, phosphate ester-type plasticizers, and chlorine-type plasticizers. Example of the phenol-type antioxidants include 2,6-diphenyl-4-octa-desiloxyphenol, stearyl(3,5-ditert.butyl-4-hydroxyphenyl)-propionate, distearyl(3,5-di-tert.butyl-4-hydroxybenzyl) phosphonate, 1,6-hexamethylene-bis[(3,5-di-tert. butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylenebis-[(3, 5)-di-tert.butyl-4-hydroxyphenyl)proponic acid amide], 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, and triethyleneglycol bis[(3-tert butyl-4-hydroxy-5-methylphenyl)propionate]. Examples of the sulfur-type antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl or distearyl thiopropionate, and β-alkylmercaptopropionate ester of polyol such as pentaerythritol tetra(β-dodecylmercapto-propionate). Examples of the phosphite-type antioxidants include tris(2, 4-di-tert butylphenyl) phosphite, tris[2-tert butyl-4-(3-tert butyl-4-hydroxy-5-methyl phenylthio)-5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di(decyl)monophenyl phosphite, di(tridecyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and di(nonylphenyl)pentaerythrotol diphosphite. Examples of ultraviolet absorbing agents include 2-hydroxybenzophenones such as 2,4-dihydroxybenzo-phenone, 2-hydroxy-4-methoxybenzophenone and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); and 2-(2'-hydroxyphenyl)benzotriazoles such as 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, and 2,2'-methylenebis(4-tert octyl-6-benzotriazolyl) phenol. Hindered amine-type photo-stabilizers may be illustrated as a photo-stabilizer. They include 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, N-(2,2,6,6-tetramethyl-4-piperidyl) dodecyl succinic imide, 1-[(3,5-di-tert butyl-4-hydroxyphenyl)propionyloxyethyl]-2, 2, 6,6-tetramethyl-4-piperidyl-(3,5-di-tert 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-tetramethyl-4-piperidyl) di(tridecyl)butanetetracarboxylate and bis(1,2,2,6,6-pentamethyl-4-piperidy) di(tridecyl)butanetetracarboxylate. Examples of the fire retardants include tetrabromobisphenol A (TBA), 2,2-bis(4-hyroxy-3,5-dibromophenyl)propane, hexabromobenzene (HBB), tris(2,3-dibromopropyl) isocyanurate (TAIC-bB), 2,2-bis(4-hydroxyethoxy-3,5-dibromo.phenyl)propane (TBA-EO), decabromodiphenyloxide (DBDPO), decabromodiphenyl ether (DBDE), 1,2-bis(pentabromophenyl)ethane (PBPE), N, N'-ethylenebis(tetrarbromophthalimide) (ETBP), 1,2,5,6,9,10-hexabromo-cyclododecane, 2,2-bis(3,5-dibromo-4-[2,3-dibromopropoxy]phenyl) propane (TBA-BP), bis(3,5-dibromo-4-[2,3-dibromopropoxy]phenyl) (TBS-BP), polydibromophenylene oxide, bis(tribromophenoxy)ethane, ethylenebis.dibromo-norbornane dicaroxyimide, dibromoethyl.dibromocyclohexane, dibromoneopentyl glycol, 2,4,6-tribromophenol, tribromophenyl allyl ether, tetrabromobisphenol S, tetradecabromo.diphenoxybenzene, 2,2-bis(4-hydroxyethoxy-3,5-di-bromophenyl) propane, poly(pentabromobenzyl) acrylate, tribromostyrene, tribromophenyl maleimide, tribromoneopentyl alcohol, tetrabromodipenta-erythritol, pentabromobenzyl acrylate, pentabromophenol, pentabromotoluene, pentabromophenyl oxide, hexabromocyclododecane, hexabromodiphenyl ether, octabromophenol ether, octabromophenyl ether, octabromodiphenyl oxide, dibromoneopentyl glycol tetracarbonate, bis(tribromophenyl)fumaric acid amide, N-methylhexabromo diphenylamine, halogen-containing polyphosphate, aromatic bromine compounds, brominated epoxy resins, and brominated polystyrene. Examples of the nucleus-forming agents include aluminum-p-tert-butyl benzoate, dibenzylidene sorbitol, bis(4-tert.butylphenyl) phosphate sodium salt, 2,2'-methylenebis(4,6-di-tert butylphenyl)phosphate sodium salt, 2,2'-methylenebis(4,6-di-tert.butylphenyl) phosphate calcium salt and 2,2'-methylenebis(4,6-di-tert.butylphenyl) phosphate basic aluminum salt. Examples of the epoxy compounds include epoxydized soybean oil, epoxydized linseed oil, epoxydized fish oils, epoxydized tall oil fatty acid esters, epoxydized beef tallow oil, epoxydized castor oil, epoxydized safflower oil, epoxydized linseed oil fatty acid butyl, tris(epoxypropyl) isocyanurate, 3-(2-xenoxy)-1,2-epoxypropane, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide and 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate. In another typical use, the lithium aluminum complex hydroxide carbonate salt is compounded in an olefin resin in order to prevent the deterioration of the resin due to the halogen-type catalyst residues. The compounding agent may be used preferably in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the olefin resin. Examples of the olefin type resins include polypropylene, low-, medium-, and high-density or linear low-density polyethylenes, a crystalline propylene/ethylene copolymer, ionically crosslinked olefin copolymers, an ethylene/vinyl acetate copolymer, an ethylene/acrylate copolymer, a low-density ethylene/butene-1 copolymer and a low-density ethylene/hexene-1 copolymer. The olefin type resins include those synthesized by using metallocene catalysts. In still further usages of the LAHCS, the lithium aluminum complex hydroxide carbonate salt is compounded in an amount of 1 to 30 parts by weight per 100 parts by weight of an olefin resin for the formation of an agricultural film together with an anticlouding agent. The olefin resin suitably includes the above illustrated resins. The present invention will be illustrated by citing Examples, but the invention is not limited by such examples. [Examples] Fine powders of the lithium aluminium complex hydroxide carbonate salt ((LAHCS), methods of producing these carbonate salts, and their uses will be explained below. (Measuring Methods) (1) X-ray diffraction The X-ray diffraction was measured by using Geigerflex (goniometer: Cat No. 2125D1) made by Rigaku Co. under the following conditions. Target Cu Filter Ni Detector SC Voltage 35 KV Current 15 mA Count flull scale 8000 c/s Scanning speed 2 deg/min. Time constant 1 sec Slit DS 1 deg. RS 0.3 mm SS 1 deg Irradiation 6 degree (2) Lamination asymmetry index (Is) The index was measured by using Geigerflex (goniometer: Cat No. 2125D1) made by Rigaku Co. under the following conditions. Target Cu Filter Ni Detector SC Voltage 40 KVP Current 20 mA Count full scale 1000 c/s Scanning speed 1 deg/min. Time constant 1 sec Slit DS 1 degree RS 0.3 mm SS 1 deg Irradiation 6 deg Measured diffraction angles 35 to 55 (2 degree) The method of calculating the lamination asymmetry index(Is) comprises drawing peak tangents (a, b) on a narrow angle side and a broad angle side with respect to both peaks at diffraction angles (2) of 36° to 44° and 44° to 53° obtained by the above X-ray diffractions so that the absolute values of the inclinations become maximum. Next, a perpendicular c is drawn from a point of intersection between the peak tangent a on the narrow angle and the peak tangent b on the broad angle. Thus, an angle  1 formed between the tangent a and the perpendicular c and an angle  2 formed between the tangent b and the perpendicular c are measured, and the lamination asymmetry index (Is) is measured from the following formula. Is=tan  2 /tan  1 (3) Orientation degree (OD) The orientation degree (OD) is defined by the following formula OD=I(002)/I(110) wherein I(002) is a relative intensity of a peak in an X-ray diffraction (Cu-Kα) appearing in an index of the plane (002) at a spacing (d) of 7.67 to 7.84 Å, and I(110) is a relative intensity of a peak in an X-ray diffraction (Cu-Kα) appearing in an index of the plane (110) at a spacing (d) of 4.41 to 4.45 Å. (4) Thermal analysis A measurement sample was in advance treated with ethyl alcohol to remove the surface treating agent, and dried at 110 °C by using a constant temperature dryer. Then, the thermal analysis was carried out by using TAS100-TG8110 thermal analysis system made by Rigaku Co. The measuring conditions included α-Al 2 O 3 as a standard substance, a temperature raising speed of 10 °C/min. and air as an atmosphere, and under the above conditions, and a weight decrease ratio was measured at a temperature of 250 °C or below. (5) Infrared absorption spectrum analysis A measuring sample was in advance treated with ethyl alcohol to remove the surface treating agent, and dried at 110 °C by using a constant temperature dryer. Then, the measurement was carried out by using an A-302 type infrared absorption spectrum analyzing instrument made by Nippon Bunko Co. (6) Fiber diameter and aspect ratio Using a scanning electron microscope (S-570) made by Hitachi Co, the fiber diameter in a restricted visual image and the aspect ratio were calculated. (7) Apparent density Measured in accordance with JIS K-6220. (8) Amount of an oil absorbed Measured in accordance with JIS K-5101-19. (9) Specific surface area Using Sorptomatic Series 1900 made by Carlo Erba Co., a specific surface area by BET was measured. (10) Average particle diameter The average particle diameter (median diameter: µm) was measured by using a laser diffraction-type particle size analyzer (Coulter RLS130) produced by Coulter Counter Co. (11) Pigment volume concentration DOP (dioctyl phthalate) was used as a vehicle, and the concentration was calculated by the following formula. Pigment volume concentration=100Bρ/(Bρ + 0.01 Or Pρ) Bρ: the density (g/ml) of the resin (vehicle), (DEP: 0.9861) Pρ: the density (g/ml) of the sample Or: the amount of an oil absorbed in the sample (ml/100 g) (Process by the hydrated alumina gel method, the product and its properties) (Example 1) 789.4 g of aluminum sulfate (7.75% of Al 2 O 3 ) was added to distilled water to prepare 700 mL of an aqueous solution. Separately, distilled water was added to 188.4 g of sodium carbonate (99.7% of Na 2 CO 3 ) to prepare 700 mL of an aqueous solution. Two hundred mL of warm water at 60 °C was added to a 2-liter beaker and with stirring, the above distilled waters were added simultaneously. Furthermore, 2 g of sodium hydroxide was added to the above mixture to adjust the pH of the aqueous solution to 10. The mixture was heated to 60 °C to obtain a pseudo-boehmite type hydrated alumina gel having a concentration of 3.6% as alumina (Al 2 O 3 ). Thereafter, 22.4 g of a lithium carbonate powder was added to the slurry solution so that the Al/Li mole ratio became 2 (or the carbonic acid ion based on the total aluminum atoms became 0.67 mole ratio), and the reaction was performed at 90 °C for 10 hours. The pH after addition was 10.1. After the end of the reaction, 12.1 g of stearic acid was added, and the surface of the product was treated by stirring. The resultant reaction suspension was filtered, washed with water, dried at 110 °C and pulverized with a small sample mill to give a lithium aluminum complex-type LAHCS (yield 98.6%) as a sample No. 1. (Comparative Example 1) Distilled water (400 ml) was put in advance in a 2-liter beaker, and 500 ml of a 1 mol/l aqueous solution of aluminum chloride and 500 ml of a 4 mol/l aqeuous ammonia were simultaneously added with stirring at room temperature to give a sol of hydrated alumina. The pH of the resulting suspension was 8.2. The reaction suspension was filtered and washed with water over one week to obtain an amorphous hydrated alumina gel. To the resulting aqueous slurry of hydrated alumina gel, 10.5 g of lithium hydroxide (monohydrate) was added, and the mixture was reacted at 95 °C for 8 hours. Thereafter, 2.7 g of stearic acid was added under heating with stirring to perform the surface treatment for about 2 hours. After filtration, the product was dried at 110 °C, and pulverized and classified to give 617 g of a powder sample No. H-1. X-ray diffraction showed that the resulting product was a mixture of Li 2 CO 3 ·4Al(OH) 3 ·nH 2 O and nordstrandite-type aluminum hydroxide. Sample No. 1 H-1 Specific surface area (m 2 /g) 51 20 Apparent density (g/ml) 0.105 0.119 Oil absorption amount (ml/100g) 65 55 Lamination asymmetry index (about 40 deg) 0.65 0.71 Lamination asymmetry index (about 48 deg) 0.65 0.93 Pigment volume concentration (%) 43.5 - [Application Examples] In the following application example, the heat stability effect, when a stabilizer or warm-keeping agent of a lithium aluminum complex hydroxide carbonate salt obtained in Example 1 is compounded into a chlorine containing resin; the resin stability (yellowness preventing effect, halogen capturing property) and the dispersibility in a resin, when the stabilizer or warm-keeping agent is compounded into a polyolefin resin comprising a halogen-containing catalyst residue; and further the warmth-keeping effect in an ethylene/vinyl acetate copolymer resin; will be explained. (Testing Method) (12) V.R and H.T The volume resistance (V.R) and the heat stability (H.T) [Congo Red test paper] of a sheet were tested in accordance with JIS K6723. A sheet was prepared under the same conditions and pressed at 190 °C to produce a sheet having a thickness of 1 mm, and its coloring properties (whiteness, color difference, yellowness) were measured. (13) Heat stability duration test A sample sheet was placed on a glass plate and put in a Geer's heat aging tester adjusted to 185 °C and taken up every 15 minutes. The coloration degree was evaluated with the eye, and the time required for completing a black decomposition was measured. (14) Blocking property Two pieces of films were overlapped one upon the other, left to stand at 40 °C under a load of 200 g/cm 2 for 24 houes, and their peeling was evaluated as follows. o ○ : Peel without resistance. ○: Peel with slight difficulty. Δ : Peel with difficulty. × : Peel with considerable difficulty. (15) Fish eye By observation with an optical microscope, the number of at least 0.1 mm in 400 cm 2 of a film was measured. (16) Scratch property A load of 10 kg was applied to a film having a section of 10 x 10 and was rubbed three times. A scratch prioerty was sought from a haze difference before and after the rubbing. (17) Transparency A white light transmission factor of a sample sheet was measured by using a 1001 DP color-difference meter manufactured by Nippon Denshoku Kogyo Co., Ltd. (18) Yellowness resistance test The above molded sheet was put into a constant temperature constant humidity tank kept at 85 °C and 90% RH and left to stand for 24 days. The surface color phase of the molded sheet was measured by a color-difference meter Model 1001 DP manufactured by Nippon Denshoku Kogyo Co., Ltd. and an N value (yellowness degree) was sought. As the N value is smaller, the yellowness degree resistance is better. (19) Haze Evaluated in accordance with ASTM-D-1003. (20) Warmth-keeping property A tunnel frame with a semicircular cylinder having a diameter of 20 cm and a length of 1 m was constructed with the above sample film and placed over the ground, and the temperature of the central portion of the tunnel frame was measured at night (at 3 o'clock in the morning). Based on the temperature of a tunnel frame made from an EVA film which did not contain a warmth-keeping agent as a standard, a temperature difference (ΔT) was measured to evaluate a warmth-keeping effect. In the present invention, as the ΔT value is larger, the warmth-keeping effect is higher. (Application Example 1) The heat stabilizing effect of adding the resin warmth-keeping agents composed of lithium aluminum complex type LAHCS (sample No. 1) obtained in Example 1 to a chlorine-containing resin, the yellowness preventing effect and the dispersibility in the resin of adding each of the above complex-type hydroxide carbonate salts to a polyolefin resin containing a halogen-remaining catalyst residue, and the resin warmth-keeping effect of adding each of the above complex-type hydroxide carbonate salts to an ethylene/vinyl acetate copolymer resin will be explained. (Warmth-keeping effect on an ethylene/vinyl acetate copolymer resin (EVA)) A warmth-keeping effect of adding the resin warmth-keeping agent (Example 1) of this invention to EVA will be described. (Compounding and molding) EVA (vinyl acetate content = 15%, Ml = 1.5) 100 parts by weight Ultraviolet absorbing agent 0.1 part by weight Antioxidant 0.1 part by weight Warmth-keeping agent 5 parts by weight The above starting materials were kneaded with stirring in a Henschel mixer. The resulting kneaded product was fed into a biaxial extruder and pelletized at a processing temperature of 150 °C, and then the pellet was inflation-molded to give a film having a width of 250 mm and a thickness of 100 µm. The warmth-keeping property of the resulting film was evaluated, and the results are shown in Table 2. Type warmth-keeping agent (sample No.) 1 Haze 10 Warmth-keeping property(ΔT) 1.7 [Effect of the Invention] According to this invention, by using amorphous or pseudo-boehmite hydrated alumina as a starting aluminum component and aluminum metal carbonate salt or bicarbonate salt, and maintaining the Al 2 O 3 concentration in the reaction system in a high condition, it was possible to synthesize the lithium aluminum complex hydroxide carbonate salt. By maintaining the concentration of the starting material in the reaction system high, the synthesis in a relatively short period of time becomes possible, and the filtration and washing of the product can be extremely easy and an economically and industrially advatageous production method can be provided with good productivity and efficiency. The lithium aluminum complex hydroxide carbonate salts (LAHCS) in produced accordance with this invention are useful as compounding agents such as a stabilizer (halogen capturing agent), an anti-blocking agent, and a warmth-keeping agent (infrared absorbing agent) for thermoplastic resins, especially olefin resins.

Claims: A process for producing a lithium aluminum complex hydroxide carbonate salt, which comprises reacting amorphous or pseudo-boehmite hydrated alumina gel and a lithium carbonate or bicarbonate in an aqueous medium under such a condition that the concentration of aluminium, calculated as alumina (Al 2 O 3 ), based on the total amount of the aqueous medium and the materials added thereto, becomes 1 to 5% by weight, and the pH at the termination of the reaction becomes 7 to 11, wherein the hydrated alumina is reacted with the carbonate or the bicarbonate so that the amount of the carbonic acid ion is at least 0.25 mole based on the total aluminum atoms and wherein the reaction is carried out at a temperature of 50 to 90°C. A process according to claim 1 wherein the amorphous or pseudo-boehmite hydrated alumina gel is obtained by simultaneously mixing basic aluminum sulfate or aluminum sulfate and an alkali carbonate, said alkali carbonate being present in an amount sufficient to form a hydrated gel with the aluminum salt, forming the hydrated alumina gel, and separating and washing the gel with water.

Inventors: HIGUCHI KATSUMI, KOMATSU YOSHINOBU, KONDO MASAMI, SATO TEIJI, TATEBE AKIRA, HIGUCHI, KATSUMI, KOMATSU, YOSHINOBU, KONDO, MASAMI, SATO, TEIJI, TATEBE, AKIRA, HIGUCHI, Katsumi Mizusawa Industrial Chemicals,, KOMATSU, Yoshinobu Mizusawa Industrial Chemicals,, KONDO, Masami Mizusawa Industrial Chemicals, Ltd., SATO, Teiji Mizusawa Industrial Chemicals, Ltd., TATEBE, Akira Mizusawa Industrial Chemicals, Ltd.
Applicants: MIZUSAWA INDUSTRIAL CHEM, MIZUSAWA INDUSTRIAL CHEMICALS, LTD.
Application year: 1996
Main classification: C01F7
IPC codes: C08K3, C01F7, C08K9