JP2007308362A - New aluminum complex hydroxide salt and method for production thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new aluminum complex hydroxide salt which is suitably used as a compounding agent for resins, particularly exerts excellent heat-retaining property and excellent transparency when blended in an agricultural film as a heat-retaining agent. <P>SOLUTION: The aluminum complex hydroxide salt has Al hydroxide octahedral layers and bivalent anions between the octahedral layers. The bivalent anions contain at least an aluminosilicate type anion represented by formula (1): [Na<SB>p</SB>Al<SB>q</SB>Si<SB>r</SB>O<SB>z</SB>]<SP>2-</SP>, wherein p, q, r and z are each a positive number satisfying 5≤z≤20, z=(p/2)+(3q/2)+2r+1, 0<p/q<1, and 0.01≤q/r≤1. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel aluminum composite hydroxide salt and a method for producing the same, and more specifically, a novel aluminum composite hydroxide salt suitable as a resin compounding agent blended as a heat retaining agent in agricultural films and the like, and its It relates to the manufacturing method.

Conventionally, the following formula:
[Al ₂ Li (OH) ₆ ] ₂ · A · mH ₂ O
Where A is a divalent anion.
Lithium aluminum composite hydroxide salt represented by the formula is known. For example, the divalent anion A is a carbonate anion (CO ₃ ²⁻ ) or a silicate anion (Si ₃ O ₇ ²⁻ ). It is blended in agricultural films as an agent (see Patent Documents 1 and 2).
JP-A-7-286052 Japanese Patent No. 2852563

  However, when a conventionally known lithium aluminum composite hydroxide salt is blended in a resin film, there is still room for improvement in terms of low transparency, although the heat retention is at a level that is satisfactory as an agricultural film. For example, as shown in a comparative example described below, the haze (Haze) of an ethylene-vinyl acetate copolymer film (thickness: 100 μm) containing 10% by weight of such a lithium aluminum composite hydroxide salt is The carbonate anion type is about 17% (Comparative Example 1), and the silicate anion type is about 13% (Comparative Example 4).

  Accordingly, the object of the present invention is to provide a novel aluminum composite water which is suitably used as a compounding agent for resins and exhibits excellent transparency as well as excellent heat retaining properties especially when formulated as a heat retaining agent in agricultural films and the like. It is to provide an oxide salt and a method for producing the same.

According to the present invention, in an aluminum composite hydroxide salt having an Al hydroxide octahedral layer and having a divalent anion between the octahedral layers,
As the divalent anion, at least the following general formula (1):
_{[Na p Al q Si r O} z] 2- ... (1)
Where p, q, r and z are
5 ≦ z ≦ 20
z = (p / 2) + (3q / 2) + 2r + 1,
0 <p / q <1,
0.01 ≦ q / r ≦ 1
Is a positive number satisfying
An aluminum composite hydroxide salt characterized by containing an aluminosilicate type anion represented by the formula:

In the aluminum composite hydroxide salt of the present invention, the Al atom in the aluminosilicate type anion is shown as a 4-coordinate Al peak in the range of chemical shift +80 ppm to +50 ppm by ²⁷ Al-solid NMR measurement, Al atoms in the hydroxide octahedron layer are shown as 6-coordinated Al peaks in the chemical shift range of +20 ppm to −20 ppm.

  The aluminosilicate type anion is preferably present at a ratio of 25 mol% or more per divalent anion in the interlayer.

Further, SO ₄ ²⁻ and / or CO ₃ ²⁻ may coexist as the divalent anion in the interlayer.

  The aluminum composite hydroxide salt of the present invention includes a gibbsite structure type and a hydrotalcite type depending on the form of the Al hydroxide octahedral layer.

The Gibbsite structure type is a structure in which the Al hydroxide octahedral layer has a structure in which at least one selected from Li atoms and / or Mg atoms is introduced into vacancies in Gibbsite type aluminum hydroxide. Formula (2):
_{[Al 2 Li (1-x} ) Mg x (OH) 6] 2 2 (1 + x) + · A 2- 1 + x · mH 2 O ... (2)
In the formula, A ²⁻ is a divalent anion between the layers,
x is a number satisfying 0 ≦ x <1;
m is zero or a positive integer;
It is represented by
In such a gibbsite structure type aluminum composite hydroxide salt, the one having an Al hydroxide octahedral layer of a type in which Li atoms are introduced into the vacancies of gibbsite type aluminum hydroxide and no Mg atoms are introduced, The following general formula (2a):
[Al ₂ Li (OH) ₆ ] _{2 2} ⁺ · A ²⁻ · mH ₂ O (2a)
In the formula, A ²⁻ is a divalent anion between the layers,
m is zero or a positive integer;
It is represented by

The hydrotalcite type structure has a hydrotalcite structure in which the Al hydroxide octahedron layer has a part of Mg of the brucite structure replaced with Al. The composite hydroxide salt has the following general formula (3):
^{_{[Al x Mg 3-x (}} OH) 6] x · A 2- x / 2 · mH 2 O ... (3)
In the formula, A ²⁻ is a divalent anion between the layers,
x is a number satisfying 0.6 ≦ x ≦ 1.5,
m is zero or a positive integer;
It is represented by

In the present invention, among the aluminum composite hydroxide salts having the gibbsite structure, those having a structure in which only Li atoms are introduced into vacancies in gibbsite-type aluminum hydroxide, that is, those represented by the general formula (2a) Is
By reacting aluminum hydroxide and lithium carbonate in the presence of an aqueous medium, the following formula (4a):
^{_{[Al 2 Li (OH) 6}} ] 2 2+ · (CO 3) 2- · mH 2 O ... (4a)
Where m is zero or a positive integer.
Lithium aluminum composite hydroxide carbonate represented by
Acid treatment of the lithium aluminum composite hydroxide carbonate with a mineral acid to replace the carbonate radical with a mineral acid anion;
Reacting the obtained substitution product with sodium silicate and sodium aluminate, further substituting the mineral acid anion with an aluminosilicate type anion represented by the formula (1),
Manufactured by.

Of the aluminum composite hydroxide salts having a gibbsite structure, a structure in which Li atoms and Mg atoms are introduced into vacancies in gibbsite type aluminum hydroxide, that is, x ≠ in the general formula (2). Zero ones
Aluminum hydroxide, lithium carbonate and basic magnesium carbonate are reacted in the presence of an aqueous medium to obtain the following formula (4b):
_{[Al 2 Li (1-x} ) Mg x (OH) 6] 2 2 (1 + x) + · (CO 3) 2- 1 + x · mH 2 O
... (4b)
Where x is a number satisfying 0 <x <1.
m is zero or a positive integer;
Lithium magnesium aluminum composite hydroxide carbonate represented by
Acid treatment of the lithium magnesium aluminum composite hydroxide carbonate with a mineral acid to replace the carbonate radical with a mineral acid anion;
Reacting the obtained substitution product with sodium silicate and sodium aluminate, further replacing the mineral acid anion with an aluminosilicate type anion represented by the following formula (1),
Manufactured by.

  In the case of producing an aluminum composite hydroxide salt having a gibbsite structure as described above, it is preferable to use sulfuric acid as the mineral acid.

Furthermore, in the present invention, the Al hydroxide octahedral layer has a hydrotalcite structure, that is, the aluminum composite hydroxide salt represented by the formula (3),
Following formula (5):
^{_{[Al x Mg 3-x (}} OH) 6] x · (SO 4) 2- x / 2 · mH 2 O ... (5)
In the formula, x is a number satisfying 0.6 ≦ x ≦ 1.5,
m is zero or a positive integer;
Prepare magnesium aluminum composite hydroxide sulfate represented by
The magnesium aluminum composite hydroxide sulfate is reacted with sodium silicate and sodium aluminate, and the sulfate anion in the formula (5) is replaced with an aluminosilicate type anion represented by the formula (1). ,
Manufactured by.

The aluminum composite hydroxide salt of the present invention has a structure in which a divalent anion is incorporated between the layers of the octahedral layer in order to supplement the charge of the Al hydroxide octahedral layer. As a valent anion, at least the following general formula (1):
_{[Na p Al q Si r O} z] 2- ... (1)
Where p, q, r and z are
5 ≦ z ≦ 20
z = (p / 2) + (3q / 2) + 2r + 1,
0 <p / q <1,
0.01 ≦ q / r ≦ 1
Is a positive number satisfying
It is an important feature that it contains an aluminosilicate type anion represented by That is, in the conventionally known carbonate type aluminum composite hydroxide salt, a carbonate anion (CO ₃ ²⁻ ) enters between the above layers, and in the conventionally known silicate anion type aluminum composite hydroxide salt, the silicate anion Whereas (Si ₃ O ₇ ²⁻ ) has entered, in the aluminum composite hydroxide salt of the present invention, the aluminosilicate type anion has entered. Due to the presence of such an aluminosilicate type anion, the aluminum composite hydroxide salt of the present invention exhibits excellent heat retention when blended with a resin and can ensure excellent transparency. For example, as apparent from the examples described later, the haze (Haze) of the ethylene-vinyl acetate copolymer film containing the aluminum composite hydroxide salt of the present invention is 6% or less. Compared to aluminum composite hydroxide salt and silicate anion type aluminum composite hydroxide salt, it exhibits extremely high transparency.

  Therefore, the aluminum composite hydroxide salt of the present invention is extremely useful as a heat retaining agent particularly blended in a resin compounding agent, particularly an agricultural film.

  As already mentioned, the aluminum composite hydroxide salt of the present invention has a divalent anion between the layers of the Al hydroxide octahedral layer, and the Al hydroxide octahedral layer has a gibbsite type. Gibbsite type having a structure in which at least one selected from Li atom and / or Mg atom is introduced in the vacancies of aluminum hydroxide, and the Al hydroxide octahedral layer contains a part of Mg of brucite structure. There is a hydrotalcite type having a hydrotalcite structure in which Al is isomorphously substituted.

In the present invention, the gibbsite type aluminum composite hydroxide salt (hereinafter referred to as G-LAHS) is represented by the general formula (2):
_{[Al 2 Li (1-x} ) Mg x (OH) 6] 2 2 (1 + x) + · A 2- 1 + x · mH 2 O ... (2)
In the formula, A ²⁻ is a divalent anion between layers,
x is a number satisfying 0 ≦ x <1;
m is zero or a positive integer;
In particular, in the general formula (2), x = 0 has the following formula (2a):
[Al ₂ Li (OH) ₆ ] _{2 2} ⁺ · A ²⁻ · mH ₂ O (2a)
It is represented by

On the other hand, in the present invention, the hydrotalcite-type aluminum composite hydroxide salt (hereinafter referred to as HT-AHS) is represented by the general formula (3):
^{_{[Al x Mg 3-x (}} OH) 6] x · A 2- x / 2 · mH 2 O ... (3)
In the formula, A ²⁻ is a divalent anion between the layers,
x is a number satisfying 0.6 ≦ x ≦ 1.5,
m is zero or a positive integer;
It is represented by

That is, in the present invention, in any type of aluminum composite hydroxide salt of the general formulas (2) and (3), the following general formula (1):
_{[Na p Al q Si r O} z] 2- ... (1)
Where p, q, r and z are
5 ≦ z ≦ 20
z = (p / 2) + (3q / 2) + 2r + 1,
0 <p / q <1,
0.01 ≦ q / r ≦ 1
Is a positive number satisfying
And an aluminosilicate type anion represented by the formula, and the presence of such an aluminosilicate type anion exhibits excellent transparency when blended in a resin. In addition, since the aluminum composite hydroxide salt of the present invention shows many absorption peaks, as will be apparent from IR analysis described later, it is excellent in heat retention, and particularly as a heat retention agent for agricultural films. It will be used suitably.

  In the aluminum composite hydroxide salt of the present invention obtained as described above, it can be confirmed from the following points that the aluminosilicate type anion of the general formula (1) is present between the layers.

First, the presence of hexacoordinate Al, tetracoordinate Al, and tetracoordinate Si can be confirmed by ²⁷ Al solid MAS-NMR measurement and ²⁹ Si solid MAS-NMR measurement. That is, the presence of hexacoordinate Al indicates the presence of a gibbsite or brucite aluminum hydroxide octahedral base layer, and the presence of tetracoordinate Si indicates the presence of a tetrahedral layer of silica. Show. It can also be seen from the presence of tetracoordinate Al that Al is isomorphously substituted for Si in the tetrahedral layer. For example, an Al atom in an aluminosilicate type anion, which is apparent from Examples described later, is shown as a 4-coordinate Al peak in the range of chemical shift +80 ppm to +50 ppm by ²⁷ Al-solid NMR measurement, Al atoms in the octahedral layer are shown as 6-coordinated Al peaks in the range of chemical shift +20 ppm to −20 ppm (see FIG. 6). Further, from the X-ray diffraction peak, the [001] plane spreads and the interlayer expands. Therefore, a tetrahedral layer in which a part of Si is isomorphously substituted with Al is introduced between the layers of the octahedral base layer. (See Fig. 1).

  By the way, according to elemental analysis, it is found that Li and Na are present together with Al, Si and O in the aluminum composite hydroxide salt (G-LAHS) having a gibbsite structure. Among these, Li exists in the vacancy of the aluminum hydroxide octahedral base layer, but Na has a large atomic size and does not enter this vacancy. From this, it is considered that this Na is introduced in a form that compensates for the charge balance when a part of Si in the tetrahedral layer is isomorphously substituted with Al.

  Therefore, this aluminosilicate type anion is represented by the formula (1), and it can be seen that such an anion exists between the layers.

  In the formula (1) indicating an aluminosilicate type anion, the value of q / r indicating the Al / Si ratio is determined by the quantity ratio of sodium aluminate and sodium silicate used when the anion is introduced. When this value is less than 0.01, the resulting aluminum composite hydroxide salt shows properties close to silicate anion-type LAHS. For example, when blended in a resin, excellent transparency Can no longer be secured. In addition, when the q / r value is larger than 1, a large amount of sodium aluminate must be used, and as in the case of using sodium aluminate alone, anion exchange cannot be performed. In the end, you can't synthesize something like this. (That is, in the present invention, it is necessary to use sodium aluminate and sodium silicate in a quantitative ratio so that the q / r value is in the range of 0.01 to 1.)

In the present invention, the aluminosilicate type anion of the formula (1) is introduced by substituting the sulfate anion. In addition, the sulfate anion may be introduced by substituting the carbonate anion. Further, as the divalent anion between the layers, the carbonate anion is the most stable, and absorbs carbon dioxide in the air, thereby Anions may be introduced. That is, as the divalent anion (A ²⁻ ) in the formula (2) or (3), a sulfate anion or a carbonate anion may coexist with an aluminosilicate type anion, and therefore in the formulas (2) and (3) The divalent anion (A ²⁻ ) has the following formula:
[Q] _a・ [SO ₄ ²⁻ ] _b・ [CO ₃ ²⁻ ] _c
In the formula, Q is an aluminosilicate type anion represented by the formula (1).
It can be expressed as

In the present invention, the aluminosilicate type anion is contained in an anion (A ²⁻ ) in an amount of 25 mol% or more, particularly 50 mol% or more, and most preferably 60 mol% or more (that is, a / A, ( A = a + b + c) is preferably 0.25 or more, preferably 0.5 or more, and most preferably 0.6 or more. This is because when the substitution amount of the aluminosilicate anion is small, the transparency when blended in the resin is impaired, the hygroscopicity is increased, and the compounding agent for the resin may be inappropriate. Therefore, the substitution treatment of the aminosilicate type anion is performed so that such a substitution amount is achieved.

  In addition, although the value of m which shows the moisture content in Formula (2) and (3) is a value of 5 or less normally, this is 200 degreeC in the aluminum complex hydroxide salt obtained by the method mentioned later. It can be made zero by heat treatment to the extent.

The above-described aluminum composite hydroxide salt of the present invention is basically prepared by preparing a precursor salt having an anion (usually a sulfate anion) between Al hydroxide octahedral layers. It is produced by replacing the anion with the aluminosilicate type anion described above.
Hereinafter, the production method will be described separately for a gibbsite type aluminum composite hydroxide salt (G-LAHS) and a hydrotalcite type aluminum composite hydroxide salt (HT-AHS).

<Manufacture of G-LAHS>
In the present invention, to produce a gibbsite type aluminum composite hydroxide salt (G-LAHS), first, aluminum hydroxide and lithium carbonate are reacted to produce an aluminum composite hydroxide carbonate, and then The carbonate anion in the carbonate is substituted with a mineral acid anion, and further, the mineral acid anion is substituted with an aluminosilicate type anion.

(1) Production of aluminum composite hydroxide carbonate:
In the production of this carbonate, the reaction between aluminum hydroxide and lithium carbonate is carried out in an aqueous medium, specifically by adding lithium carbonate into an aqueous slurry of aluminum hydroxide, Following formula (4a):
^{_{[Al 2 Li (OH) 6}} ] 2 2+ · (CO 3) 2- · mH 2 O ... (4a)
Where m is zero or a positive integer.
Lithium aluminum composite hydroxide carbonate (carbonate anion type LAHS) represented by

In the above reaction, the aluminum hydroxide to be used is preferably finely adjusted in particle size. For example, aluminum hydroxide and water are mixed, wet-ground by a ball mill or the like, and the volume average particle diameter D ₅₀ (laser) (By diffraction scattering method) is preferably 0.3 to 1 μm, and in particular, the content of coarse particles of 20 μm or more is preferably 2% by weight or less. That is, by using such fine aluminum hydroxide particles, it is possible to obtain the G-LAHS of the present invention having good transparency especially when dispersed in a resin.

  Water is added to the aluminum hydroxide particles whose particle size has been adjusted as described above, and lithium carbonate is added to this aqueous slurry to carry out the reaction. This reaction is stoichiometric, and aluminum hydroxide and lithium carbonate are used in such a proportion that the atomic ratio of Al / Li is 2.

  The reaction is usually carried out under stirring at a temperature of 80 to 130 ° C. for about 1 to 10 hours, so that lithium enters the vacancies in the aluminum hydroxide octahedron layer of the gibbsite structure so as to compensate for this charge. The carbonate of the formula (4a) having a structure in which carbonate ions are incorporated between the octahedral layers is obtained. That is, lithium ions have the smallest ionic radius among cations, and, as monovalent ions, are exceptionally 6-coordinate ions, so they enter the vacancies and form the structure as described above. .

  An X-ray diffraction image (Comparative Example 1) of such a carbonate anion-type LAHS is as shown in FIG. 1. From the peak on the [001] plane (2θ = 11 to 12 degrees), aluminum hydroxide into which Li has entered. It can be seen that the octahedral base layer has a stacked structure in which the octahedral base layers are stacked in the C-axis direction.

  Here, what is interesting is that, as described above, when the aluminum hydroxide to be used is adjusted to a fine particle size, the G-LAHS of the present invention (that is, the aluminosilicate anion) obtained from the carbonate anion type LAHS as an intermediate. The type LAHS) exhibits excellent transparency when dispersed in a resin, but the particle size of the carbonate anion type LAHS as an intermediate hardly contributes to transparency. That is, the above-described reaction is performed without adjusting the particle size of coarse aluminum hydroxide, the particle size of the obtained carbonate anion-type LAHS is adjusted, and the reaction described later is performed using fine carbonate anion-type LAHS to perform aluminosilicate. When an anionic LAHS is produced, the degree of transparency when blended with the resin is only slightly higher than the carbonate anionic LAHS. The reason for this is unclear, but perhaps when fine-grained aluminum hydroxide with a controlled particle size is used, lithium effectively penetrates into the vacancies in the aluminum hydroxide octahedral layer and the reaction is stoichiometric. It is thought that this is because LAHS having a Li / Al ratio of 2 is formed.

In the above reaction, basic magnesium carbonate can be reacted with lithium carbonate. In this case, the following formula (4b):
_{[Al 2 Li (1-x} ) Mg x (OH) 6] 2 2 (1 + x) + · (CO 3) 2- 1 + x · mH 2 O
... (4b)
Where x is a number satisfying 0 <x <1.
m is zero or a positive integer;
Lithium magnesium aluminum composite hydroxide carbonate represented by That is, the carbonate of the formula (4a) described above is used as an intermediate raw material in the case of producing G = 0 LA in the general formula (2) (salt of the formula (2a)). The carbonate of the above formula (4b) is used as an intermediate raw material when producing G-LAHS of x ≠ 0 in the general formula (2).

  In the production of the carbonate of the formula (4b), the aluminum hydroxide to be used is preferably finely sized as described above, and the reaction of aluminum hydroxide, lithium carbonate and basic magnesium carbonate is aqueous. The reaction is carried out in an autoclave at a temperature of 100 to 180 ° C. for about 1 to 10 hours in the presence of a medium. Lithium carbonate and basic magnesium carbonate are used in stoichiometric amounts, so that, as described above, lithium and magnesium enter the vacancies in the gibbsite-structured aluminum hydroxide octahedral layer to compensate for this charge. A carbonate of the formula (4b) having a structure in which carbonate ions are incorporated between the face layers is obtained.

(2) Substitution with mineral acid anion:
In the present invention, the carbonate of formula (4a) or (4b) obtained above (carbonate anion type LAHS) is treated with a mineral acid, and the carbonate anion is replaced with a mineral acid anion. That is, the carbonate anion type LAHS is extremely stable, and the carbonate anion cannot be directly substituted with the aluminosilicate type anion. For this reason, the carbonate anion is once substituted with the mineral acid anion.

  As the mineral acid, sulfuric acid, nitric acid, hydrochloric acid and the like can be used, but sulfuric acid is preferably used in terms of reactivity. The amount of mineral acid is such that the total amount of carbonate anion can be replaced with mineral acid anion. For example, the mineral acid has the same equivalent amount as lithium carbonate used in the production of carbonate anion type LAHS, or in a slightly excess amount. A mineral acid may be used.

  The mineral acid treatment is performed by adding an aqueous mineral acid solution having an acid concentration of about 2 to 98% by weight to the aqueous slurry of carbonate anion-type LAHS obtained above and stirring for about 0.5 to 10 hours. After the reaction, aging is carried out for about 0.5 to 10 hours, whereby a mineral acid anion-type LAHS in which the carbonate anion is replaced with a mineral acid anion is obtained.

  The mineral acid anion-type LAHS thus obtained has extremely high hygroscopicity and is therefore unsuitable as a resin compounding agent. In the present invention, the mineral acid anion in the mineral acid anion type LAHS is substituted with an aluminosilicate anion to obtain the intended G-LAHS (aluminosilicate anion type LAHS) of the present invention.

(3) Substitution with an aluminosilicate anion In the present invention, the anion substitution is carried out by simultaneously adding sodium silicate and sodium aluminate to the above mineral acid anion type LAHS slurry under stirring and mixing. It is carried out by reacting at a temperature of 95 ° C. for about 0.5 to 10 hours, then aged for about 0.5 to 10 hours, filtered, washed with water, and dried to obtain a mineral acid anion of mineral acid anion type LAHS Is part of the following general formula (1):
_{[Na p Al q Si r O} z] 2- ... (1)
Where p, q, r and z are
5 ≦ z ≦ 20
z = (p / 2) + (3q / 2) + 2r + 1,
0 <p / q <1,
0.01 ≦ q / r ≦ 1
Is a positive number satisfying
The G-LAHS of the present invention represented by the general formula (2) can be obtained by substitution with an aluminosilicate type anion represented by general formula (2).

  In the anion substitution described above, when sodium silicate is used alone, a silicate anion type LAHS is obtained, and this type of LAHS has low transparency when blended in a resin as described above. In addition, sodium aluminate cannot replace aluminate ions with mineral acid anions between layers when used alone because of its high pH. In the present invention, by mixing this sodium silicate and sodium aluminate simultaneously with the slurry of mineral acid anion type LAHS, the mineral acid anion is replaced in the form of silicate aluminosilicate anion instead of silicate anion. Can do it.

In the present invention, as already described, sodium aluminate and sodium silicate are used in a quantitative ratio so that the q / r value in the formula (1) is in the range of 0.01 to 1, and It is used in such an amount that 25 mol% or more, particularly 50 mol% or more, most preferably 60 mol% or more of the divalent anion (A ²⁻ ) is substituted with an aluminosilicate type anion.

<Manufacture of HT-AHS>
In the present invention, a hydrotalcite-type aluminum composite hydroxide salt (HT-AHS) is produced by the following formula (5):
^{_{[Al x Mg 3-x (}} OH) 6] x · (SO 4) 2- x / 2 · mH 2 O ... (5)
In the formula, x is a number satisfying 0.6 ≦ x ≦ 1.5,
m is zero or a positive integer;
A magnesium aluminum composite hydroxide sulfate (abbreviated as MgAl sulfate) represented by the following formula is used as a starting material, sodium silicate and sodium aluminate are reacted with this MgAl sulfate, It is produced by replacing the sulfate anion with an aluminosilicate type anion represented by the above formula (1).

MgAl sulfate used as a starting material is a known compound, and its production method and the like are described in detail, for example, in JP-A No. 2001-2408. For example, NaOH can be added while stirring magnesium chloride and aluminum sulfate and reacted in an autoclave in the presence of an aqueous medium to obtain MgAl sulfate of formula (5) directly.
Further, aluminum chloride is added instead of aluminum sulfate as an aluminum source, sodium carbonate is added instead of NaOH, and the reaction is carried out in an autoclave in the presence of an aqueous medium.
^{_{[Al x Mg 3-x (}} OH) 6] x · (CO 3) 2- x / 2 · mH 2 O
Where x and m are the same as in equation (5),
The MgAl salt of the above formula (5) is obtained by synthesizing a carbonate represented by the following formula and treating the carbonate with sulfuric acid to replace the carbonate anion with a sulfate anion. (Note that the carbonate anion is not used as a raw material and the sulfate is used as a raw material, as described above, the carbonate anion is extremely stable, and this is directly substituted with an aluminosilicate type anion. Because you can't.

In the present invention, by reacting the above MgAl sulfate with sodium silicate and sodium aluminate, the sulfate anion in the formula (5) is converted into an aluminosilicate type anion represented by the formula (1). By substituting, general formula (3):
^{_{[Al x Mg 3-x (}} OH) 6] x · A 2- x / 2 · mH 2 O ... (3)
In the formula, A ²⁻ is a divalent anion between layers,
x is a number satisfying 0.6 ≦ x ≦ 1.5,
m is zero or a positive integer;
A hydrotalcite-type aluminum composite hydroxide salt (HT-AHS) represented by Such a reaction is carried out by simultaneously pouring and mixing sodium silicate and sodium aluminate into a slurry of MgAl sulfate and stirring at a temperature of 5 to 95 ° C. for about 0.5 to 10 hours. Then, the reaction is carried out by aging for about 0.5 to 10 hours. After the reaction, the intended HT-AHS is obtained by filtration, washing with water and drying. Further, the amount of sodium silicate and sodium aluminate used is such that the q / r value in the formula (1) is in the range of 0.01 to 1, as in the case of producing G-LAHS described above. Used in an amount such that 25 mol% or more, particularly 50 mol% or more, most preferably 60 mol% or more of the divalent anion (A ²⁻ ) is substituted with an aluminosilicate type anion. Is done.

<Application>
Aluminum complex hydroxide salt of the present invention obtained as described above, for example, be milled, average particle diameter D ₅₀ is the particle size adjusted to about 0.3 to 1 [mu] m, for use as a compounding agent for resins Can do. The aluminum composite hydroxide salt usually has a bulk density of 0.05 to 0.3 g / cm ³ , a BET specific surface area of 20 to 50 m ² / g, and a refractive index of 1.49 to 1.51. It is in.

  Such an aluminum composite hydroxide salt is represented, for example, by the above-described formula (2) or formula (3). As already described, the aluminum composite hydroxide salt exhibits excellent transparency when blended with a resin, and IR described later. As is clear from the analysis, it shows many absorption peaks, so it is excellent in heat retention and is particularly suitable as a heat retention agent for agricultural films.

  This aluminum composite hydroxide salt can be surface-treated by adding a higher fatty acid or a surfactant during compounding of the resin, thereby improving dispersibility in the resin.

  As higher fatty acids, saturated fatty acids having 10 to 22 carbon atoms, particularly 14 to 18 carbon atoms, such as capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, etc. , Unsaturated fatty acids such as lindelic acid, tuzuic acid, petrothelic acid, oleic acid, linoleic acid, linolenic acid and arachidonic acid. Stearic acid is preferred. Of course, the fatty acid may be a mixed fatty acid such as beef tallow fatty acid, coconut oil fatty acid, or palm oil fatty acid.

  Examples of the anionic surfactant include a primary higher alcohol sulfate, a secondary higher alcohol sulfate, a primary higher alkyl sulfonate, a secondary higher alkyl sulfonate, a higher alkyl disulfonate, Sulfonated higher fatty acid salt, higher fatty acid sulfate ester salt, higher fatty acid ester sulfonate salt, higher alcohol ether sulfate ester salt, higher alcohol ether sulfonate salt, higher fatty acid amide alkylol sulfate ester salt, alkylbenzene sulfonate salt Any anionic surfactant such as alkylphenol sulfonate, alkylnaphthalene sulfonate, and alkylbenzimidazole sulfonate may be used. More specific compound names of these surfactants are disclosed, for example, in “Synthetic Surfactant” written by Hiroshi Horiguchi (Sho 41 Sankyo Publishing).

  As the nonionic surfactant, a nonionic surfactant having a low HLB, particularly one having an HLB of 12 or less, most preferably 8 or less, is used. Generally, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxy Ethylene fatty acid ester, polyoxyethylene fatty acid amide ether, polyhydric alcohol fatty acid ester. Among the polyoxyethylene polyhydric alcohol fatty acid ester, fatty acid sucrose ester, alkylolamide, polyoxyalkylene block copolymer, etc., those having HLB within the above range are used. For example, since these nonionic surfactants generally reduce HLB when the content of polyoxyethylene units decreases, the desired nonionic surfactant of HLB is obtained by adjusting the number of moles of ethylene oxide added. be able to.

  The addition amount of the fatty acid or the surfactant is preferably 0.5 to 15% by weight, particularly 1 to 10% by weight, based on the aluminum composite hydroxide salt.

  The treatment conditions are not particularly limited, but the treatment is generally preferably performed at a temperature of 60 to 100 ° C. with stirring for about 0.5 to 5 hours. In the case of a fatty acid, the fatty acid used reacts with sodium ions present in the reaction system and moves into the aqueous phase in the form of sodium soap, and the surface treatment of the produced aluminum composite hydroxide proceeds. In an anionic surfactant, the same reaction occurs when an organic acid that is not a salt is used. The treated reaction product is subjected to known solid-liquid separation operations such as filtration and centrifugation from the mother liquor, sufficiently washed with water, dried, and pulverized as necessary to obtain a product. The obtained surface-treated aluminum composite hydroxide can be used as it is as a compounding agent for resins, but can be post-treated with known organic and inorganic auxiliaries as necessary.

  Such an aluminum composite hydroxide salt of the present invention is preferably blended in an amount of generally 0.01 to 25 parts by weight with respect to 100 parts by weight of the resin. In particular, as a heat retention agent, excellent heat retention and transparency can be ensured by blending in an amount of 2 to 10 parts by weight.

  The resin to be blended is not particularly limited. For example, polyvinyl chloride, polyvinylidene chloride, chlorinated polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride. -Ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride ternary copolymer Polymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, chlorinated vinyl-propylene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid Ester copolymer, vinyl chloride-maleic ester copolymer, vinyl chloride Polymers such as crylate ester copolymer, vinyl chloride-acrylonitrile copolymer, internally plasticized polyvinyl chloride, and these chlorine-containing polymers and α-olefins such as polyethylene, polypropylene, polybutene and poly-3-methylbutene Polymers or polyolefins such as ethylene-vinyl acetate copolymer and ethylene-propylene copolymer and copolymers thereof, polystyrene, acrylic resin, styrene and other monomers (for example, maleic anhydride, butadiene, acrylonitrile, etc.) And acrylonitrile-butadiene-styrene copolymer, acrylic ester-butadiene-styrene copolymer, and blended product of methacrylic ester-butadiene-styrene copolymer. In particular, the aluminum composite hydroxide salt of the present invention has an absorption spectrum excellent in infrared rays, is excellent in heat retention, and is excellent in transparency. It is extremely suitable as an agricultural film such as a house film.

  The resin composition containing the aluminum composite hydroxide salt of the present invention contains various additives known per se, such as stabilizers, stabilizers, lubricants, plasticizers, ultraviolet absorbers, antioxidants, and light stabilizers. Further, a nucleating agent, an antifogging agent, a drip agent, an antifogging agent, a coloring agent, other heat retaining agents, a filler and the like can be used in combination. Addition amount of these powders that can fulfill each purpose and the aluminum composite hydroxide of the present invention is formed as mixed particles (pellet, granule, spherical, etc.) to generate fine powder dust Prevention and improvement of quantitative feedability can be performed.

  Examples of ultraviolet absorbers include hydroxybenzophenone compounds, hydroxybenzotriazole compounds, and benzoate compounds.

  As the antioxidant, any of phenol-based antioxidants, sulfur-based antioxidants, phosphite-based antioxidants and the like are used. Examples of the phenolic antioxidant include bisphenol type antioxidants and sterically hindered phenolic antioxidants.

  Examples of the light stabilizer include hindered amine light stabilizers (HALS), and examples thereof include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl- 4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecyl succinimide, 1-[(3 , 5-ditert-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, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1, , 2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, N, N′-bis (2,2,6, 6-tetramethyl-4-piperidyl) hexamethylenediamine, 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, bis (1,2,2,6,6-pentamethyl-4 -Piperidyl) .di (tridecyl) butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4- Peridyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1, 2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,5,8,12- Tetrakis [4,6-bis {N- (2,2,6,6-tetramethyl-4-piperidyl) butylamino} -1,3,5-triazin-2-yl] -1,5,8,12 -Tetraazadodecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro- s-Triazine / N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N′-bis (2,2,6,6-tetramethyl- 4-piperidyl) hexamethylenediamine / dibromoethane condensate and the like.

  The film is formed by melt-kneading this resin composition using a Henschel mixer, super mixer, Banbury mixer, ribbon blender, single- or twin-screw extruder, roll or other compounding machine or kneader, and then extruding it through a die. It can be performed by an inflation film forming method, a T-die method or the like. This film may be a single layer film or a multilayer laminate film, and the latter laminate film is obtained by coextrusion.

  When the aluminum composite hydroxide salt of the present invention is blended in the laminated film as a heat retention agent, it is blended mainly in the intermediate layer, but it is blended in the inner layer or outer layer which is the coating layer within a range that does not hinder the transparency. May be.

  Moreover, as a processing method regarding anti-fogging, dropping, and fog prevention of the film, in addition to blending each processing agent into the resin, a method of forming a dropping film on the inner surface of the inner layer can also be mentioned.

  The present invention will be described with reference to the following examples, but the present invention is not limited to the following examples. In addition, the measuring method in an Example is as follows.

(1) Volume average particle diameter (D ₅₀ )
Measurement was performed by a laser diffraction scattering method using LS230 manufactured by Coulter.

(2) Chemical composition Ig-Loss was quantified from the weight loss after baking the sample at 1050 ° C. for 1 hour and then allowing to cool. Sample is decomposed by alkali melting, SiO ₂ is gravimetric, MgO is chelate titration, Al ₂ O ₃ is EDTA-zinc back titration, SO ₄ is Pb (NO ₃ ) ₂ -EDTA titration chelate titration Quantified. Further, the sample was subjected to hydrofluoric acid decomposition and then filtered, and the obtained filtrate was measured for Li ₂ O and Na ₂ O by atomic absorption to quantify each metal component. The sample was decomposed with sulfuric acid, and the generated CO ₂ was quantified by reverse neutralization titration to obtain CO ₃ .
In addition, a sample is based on the thing dried at 110 degreeC for 2 hours.

(3) X-ray diffraction It measured by Cu-K (alpha) using PW1830 by PHILIPS.
Target: Cu
Filter: Curved crystal graphite monochromator Detector: SC
Voltage: 40 kV
Current: 30mA
Step size: 0.03 °
Counting time: 0.03 sec
Slit: DS1 ° RS0.2mm SS1 °

(4) Bulk density It measured based on JISK6721.

(5) BET specific surface area
Nitrogen adsorption isotherm was measured using TriStar 3000 manufactured by Micromeritics. It was determined by the BET method from the adsorption side nitrogen adsorption isotherm with a specific pressure of 0.2 or less.

(6) Refractive index A solvent (α-bromonaphthalene, kerosene) having a known refractive index is adjusted in advance using an Abbe refractometer. Next, according to Larsen's oil immersion method, several mg of sample powder is taken on a slide glass, a drop of a solvent with a known refractive index is added, a cover glass is applied, the solvent is sufficiently immersed, and then the Becke line is observed with an optical microscope. Observe and seek movement.

(7) Cloudiness (Haze) of film and heat retention (infrared absorptivity)
An agricultural film having the following composition was prepared and evaluated for cloudiness (Haze) and heat retention (infrared absorptivity) of the film.
Formulation EVA (vinyl acetate content 15%) 88.8% by weight
Insulating agent (see Table 1) 10.0% by weight
UV absorber (Sumitomo Chemical Sumisorb 130) 0.1% by weight
Antioxidant (Butylhydroxytoluene) 0.3% by weight
Light stabilizer (Cinubain 622-LD manufactured by Ciba Geigy) 0.5% by weight
Lubricant (erucic acid amide) 0.3% by weight
Roll kneading was performed at 120 ° C. to obtain the above resin composition. This was pressed to prepare a 100 μm EVA single layer film. The infrared absorption of the resulting film was measured to range ^2500cm -1 ^~400cm -1 ^{(4μm~25μm),} was determined heat retention by the following formula from the values of the absorption and the black body radiation density at each measurement wavenumber.
Thermal insulation rate (%) =
100 × Σ {(1−transmittance% T / 100) × black body radiation density} / Σblack body radiation density The black body radiation energy used is derived from the following Planck equation.
_{W λ, T = c 1 λ} -5 / {exp (c 2 / λT) -1}
W _{λ, T} : Spectral radiation density at wavelength λ and temperature T (W / cm ² )
c ₁ : 3.7402 × 10 ⁻¹² (W · cm ² , Planck's first radiation constant)
c ₂ : 1.4388 (cm · deg, Planck's second radiation constant)
The heat retention effect is higher as the value of the heat retention rate is larger.
Moreover, the obtained composition was sandwiched between two saran wraps and pressed to prepare a 100 μm pseudo three-layer laminated film. Haze was measured according to ASTM D 1003-95. The smaller the value of Haze, the better the transparency. The apparatus used for the measurement was haze-gard plus manufactured by Gardner.

(Comparative Example 1)
220 g of aluminum hydroxide (B52 manufactured by Nippon Light Metal Co., Ltd.) was dispersed in 3780 g of water. This slurry was transferred to a 15 L pot mill containing 16.5 kg of φ = 2 mm alumina balls, and wet pulverized until the average particle size D ₅₀ = 0.48 μm (the coarse particles of 10 μm or more are 0% by weight).
1818 g (100 g as aluminum hydroxide) was separated from the above pulverized slurry, added to a 3 L beaker together with 282 g of water and 23.75 g of lithium carbonate, then heated to 95 ° C. and subjected to crystallization reaction for 6 hours with stirring. (Referred to as step 1).
8.0 g of stearic acid was added to the reaction slurry and surface treatment was performed for 2 hours, followed by filtration with Nutsche. The cake is dried at 110 ° C, pulverized and carbonated LAHS
[Al ₂ Li (OH) ₆ ] _{2 2} ⁺ · CO ₃ ²⁻ · 1.6H ₂ O
A stearic acid surface-treated product was obtained.
The physical properties were measured, the results are shown in Table 1, the X-ray diffraction diagram is shown in FIG. 1, and the ²⁷ Al-solid NMR measurement diagram is shown in FIG. The bulk density was 0.10 g / ml, the BET specific surface area was 34 m ² / g, and the refractive index was 1.53.

(Comparative Example 2)
41.98 g of 75% sulfuric acid was added dropwise over 1 hour to the reaction slurry obtained in the same manner up to Step 1 of Comparative Example 1, and aging was performed for 1 hour (referred to as Step 2).
Further, 8.0 g of sodium stearate was added to the reaction slurry and surface treatment was performed for 2 hours, followed by filtration with a Nutsche and washing with warm water. When the cake was dried at 110 ° C and pulverized, the chemical composition was analyzed.
^{_{[Al 2 Li (OH) 6}} ] 2 2+ · (SO 4) 2- 0.95 · (CO 3) 2- 0.05 · 1.4H 2 O
It was a sodium stearate surface treatment product.
The physical properties were measured and the results are shown in Table 1.

(Comparative Example 3)
The same process was performed up to Step 2 of Comparative Example 2, and a solution obtained by mixing 144.4 g of sodium aluminate (22.7% as Al ₂ O ₃ and 18.2% as Na ₂ O) and 215.6 g of water in this reaction slurry. Was added dropwise over 1 hour and aged for 1 hour.
Further, 8.0 g of stearic acid was added to the reaction slurry and surface treatment was performed for 2 hours, followed by filtration with Nutsche and washing with warm water. The cake was dried at 110 ° C. and pulverized, and analyzed by X-ray structure diffraction. As a result, it was a mixture of carbonate-type LAHS and aluminum hydroxide (gibbsite) (an X-ray diffraction diagram is shown in FIG. 2). This indicates that the aluminate ion cannot be exchanged alone as the anionic species.

(Comparative Example 4)
A composite hydroxide condensed silicate Optima SS manufactured by Toda Kogyo was used. As a result of chemical composition analysis, silicic acid type composite hydroxide salt [Al ₂ Li _0.92 Mg _0.08 (OH) ₆ ] ₂ ^{2.16 +} · (Si _3.7 O _8.4 ) ²⁻ _{0. 51} · (SO ₄ ) ²⁻ _0.10 · (CO ₃ ) ^{2 −} _0.47 · 2.6H ₂ O
Met.
The physical properties were measured, the results are shown in Table 1, and the X-ray diffraction diagram is shown in FIG.

Example 1
In Comparative Example 2, the same process was performed up to Step 2, and 144.4 g of sodium aluminate (22.7% as Al ₂ O ₃ and 18.2% as Na ₂ O) and 215.6 g of water were mixed into this reaction slurry ( A) liquid, 171.1 g of sodium silicate (23.7% as SiO ₂ , 7.53% as Na ₂ O) and 188.9 g of water (B) were mixed dropwise over 1 hour, Aging was performed for 1 hour.
Further, 8.0 g of stearic acid was added to the reaction slurry and surface treatment was performed for 2 hours, followed by filtration with Nutsche and washing with warm water. The cake was dried at 110 ° C. and pulverized and analyzed for chemical composition. As a result, G-LAHS (aluminosilicate anion type LAHS) was obtained.
[Al ₂ Li (OH) ₆ ] _{2 2} ⁺ · (Na _0.7 Al _2.2 Si _2.8 O _10.3 ) ² _-0.82 · (SO ₄ ) ² _-0.10 · (CO ₃ ) ^2- _0.08・ 3.9H ₂ O
The stearic acid surface-treated product.
The physical properties were measured, the results are shown in Table 1, and the ²⁷ Al-solid NMR measurement diagram is shown in FIG. The bulk density was 0.11 g / ml, and the refractive index was 1.50.

(Example 2)
In Example 1, it carried out similarly except having changed the sodium silicate of the (B) liquid into 244.5g and water to 115.5g, and the aluminosilicate anion type | mold LAHS was carried out.
^{_{[Al 2 Li (OH) 6}} ] 2 2+ · (Na 1.3 Al 2.8 Si 4.0 O 13.9) 2- 0.81 · (SO 4) 2- 0.11 · (CO 3) ^2- _0.08・ 3.6H ₂ O
A stearic acid surface-treated product was obtained.
The physical properties were measured and the results are shown in Table 1. The bulk density was 0.11 g / ml, and the refractive index was 1.50.

(Example 3)
In Example 1, it carried out similarly except having changed the sodium silicate of the (B) liquid to 334.1 g and water to 25.9 g, and an aluminosilicate anion type LAHS.
^{_{[Al 2 Li (OH) 6}} ] 2 2+ · (Na 1.9 Al 3.0 Si 5.2 O 16.9) 2- 0.79 · (SO 4) 2- 0.12 · (CO 3) ^2- _0.09 · 3.4H ₂ O
A stearic acid surface-treated product was obtained.
The physical properties were measured, the results are shown in Table 1, and the X-ray diffraction diagram is shown in FIG. The bulk density was 0.11 g / ml, and the refractive index was 1.50.

Example 4
In Example 1, except that (A) the sodium aluminate of the liquid was changed to 108.3 g, water was changed to 251.7 g, the sodium silicate of the (B) liquid was changed to 122.2 g, and the water was changed to 237.8 g. Aluminosilicate anion type LAHS
^{_{[Al 2 Li (OH) 6}} ] 2 2+ · (Na 0.1 Al 1.8 Si 2.0 O 7.8) 2- 0.83 · (SO 4) 2- 0.09 · (CO 3) ^2- _0.08・ 3.1H ₂ O
A stearic acid surface-treated product was obtained.
The physical properties were measured and the results are shown in Table 1. The bulk density was 0.12 g / ml and the refractive index was 1.50.

(Example 5)
In Example 4, the same procedure was performed except that the sodium silicate in the liquid (B) was changed to 183.4 g and the water was changed to 176.6 g, and an aluminosilicate anion type LAHS was obtained.
^{_{[Al 2 Li (OH) 6}} ] 2 2+ · (Na 0.6 Al 1.8 Si 2.8 O 9.6) 2- 0.84 · (SO 4) 2- 0.09 · (CO 3) ^2- _0.07・ 2.6H ₂ O
A stearic acid surface-treated product was obtained.
The physical properties were measured and the results are shown in Table 1. The bulk density was 0.09 g / ml and the refractive index was 1.50.

(Example 6)
In Example 4, the same procedure was performed except that the sodium silicate in the liquid (B) was changed to 244.5 g and the water was changed to 115.5 g, and an aluminosilicate anion type LAHS
^{_{[Al 2 Li (OH) 6}} ] 2 2+ · (Na 0.9 Al 2.1 Si 3.6 O 11.8) 2- 0.83 · (SO 4) 2- 0.10 · (CO 3) ^2- _0.07・ 2.9H ₂ O
A stearic acid surface-treated product was obtained.
The physical properties were measured and the results are shown in Table 1. The bulk density was 0.12 g / ml and the refractive index was 1.50.

(Example 7)
In Example 4, it was the same except that (A) liquid sodium aluminate was changed to 72.18 g, water was changed to 287.8 g, (B) liquid sodium silicate was changed to 163.0 g, and water was changed to 197.0 g. Aluminosilicate anion type LAHS
^{_{[Al 2 Li (OH) 6}} ] 2 2+ · (Na 0.3 Al 1.4 Si 2.5 O 8.3) 2- 0.84 · (SO 4) 2- 0.10 · (CO 3) ^2- _0.06・ 2.6H ₂ O
A stearic acid surface-treated product was obtained.
The physical properties were measured and the results are shown in Table 1. Moreover, the bulk density was 0.13 g / ml and the refractive index was 1.50.

(Example 8)
In Example 7, it carried out similarly except having changed the sodium silicate of the (B) liquid into 244.5g and water to 115.5g, and the aluminosilicate anion type | mold LAHS was carried out.
[Al ₂ Li (OH) ₆ ] _{2 2} ⁺ · (Na _0.6 Al _1.9 Si _3.5 O _11.2 ) ^{2 −} _0.80 · (SO ₄ ) ^{2 −} _0.13 · (CO ₃ ) ^2- _0.07・ 2.4H ₂ O
A stearic acid surface-treated product was obtained.
The physical properties were measured and the results are shown in Table 1. Further, the BET specific surface area was 39 m ² / g and the refractive index was 1.50.

Example 9
In Example 7, it was the same except that (A) solution sodium aluminate was changed to 43.31 g, water was changed to 316.7 g, (B) solution sodium silicate was changed to 326.0 g, and water was changed to 34.0 g. Aluminosilicate anion type LAHS
^{_{[Al 2 Li (OH) 6}} ] 2 2+ · (Na 0.6 Al 1.1 Si 4.4 O 11.8) 2- 0.75 · (SO 4) 2- 0.18 · (CO 3) ^2- _0.07・ 2.6H ₂ O
A stearic acid surface-treated product was obtained.
The physical properties were measured and the results are shown in Table 1. The BET specific surface area was 29 m ² / g and the refractive index was 1.50.

(Example 10)
In Example 9, the same procedure was performed except that the sodium silicate in the liquid (B) was changed to 244.5 g and the water was changed to 115.5 g, and an aluminosilicate anion type LAHS
[Al ₂ Li (OH) ₆ ] _{2 2} ⁺ · (Na _0.4 Al _1.6 Si _3.7 O _11.0 ) ^{2 −} _0.76 · (SO ₄ ) ^{2 −} _0.17 · (CO ₃ ) ^2- _0.07・ 2.0H ₂ O
A stearic acid surface-treated product was obtained.
The physical properties were measured and the results are shown in Table 1. The BET specific surface area was 31 m ² / g and the refractive index was 1.50.

(Example 11)
In Example 9, the aluminosilicate anion type LAHS was performed in the same manner except that the sodium silicate of the liquid (B) was changed to 163.0 g and the water was changed to 197.0 g.
^{_{[Al 2 Li (OH) 6}} ] 2 2+ · (Na 0.1 Al 1.5 Si 2.6 O 8.5) 2- 0.80 · (SO 4) 2- 0.14 · (CO 3) ^2- _0.06・ 1.6H ₂ O
A stearic acid surface-treated product was obtained.
The physical properties were measured and the results are shown in Table 1. The BET specific surface area was 27 m ² / g and the refractive index was 1.50.

(Example 12)
In Example 9, the same procedure was performed except that the sodium aluminate (A) was changed to 21.66 g and the water was changed to 338.3 g, and an aluminosilicate anion type LAHS was obtained.
[Al ₂ Li (OH) ₆ ] _{2 2} ⁺ · (Na _0.037 Al _0.04 Si _4.0 O _9.1 ) ^{2 −} _0.74 · (SO ₄ ) ^{2 −} _0.20 · (CO ₃ ) ^2- _0.06・ 1.8H ₂ O
A stearic acid surface-treated product was obtained.
The physical properties were measured, the results are shown in Table 1, and the ²⁷ Al-solid NMR measurement diagram is shown in FIG. The BET specific surface area was 23 m ² / g and the refractive index was 1.50.

(Example 13)
In Example 12, the aluminosilicate anion type LAHS was carried out in the same manner except that the sodium silicate in the liquid (B) was changed to 244.5 g and the water was changed to 115.5 g.
^{_{[Al 2 Li (OH) 6}} ] 2 2+ · (Na 0.1 Al 0.6 Si 3.6 O 9.2) 2- 0.73 · (SO 4) 2- 0.21 · (CO 3) ^2- _0.06・ 1.4H ₂ O
A stearic acid surface-treated product was obtained.
The physical properties were measured and the results are shown in Table 1. The BET specific surface area was 29 m ² / g and the refractive index was 1.50.

(Example 14)
In Example 12, the same procedure was performed except that the sodium silicate in the liquid (B) was changed to 163.0 g and water was changed to 197.0 g, and an aluminosilicate anion type LAHS was obtained.
[Al ₂ Li (OH) ₆ ] _{2 2} ⁺ · (Na _0.03 Al _1.1 Si _3.0 O _8.7 ) ² _-0.75 · (SO ₄ ) ² _−0.19 · (CO ₃ ) ^2- _0.06・ 4.0H ₂ O
A stearic acid surface-treated product was obtained.
The physical properties were measured and the results are shown in Table 1. The BET specific surface area was 28 m ² / g and the refractive index was 1.50.

(Example 15)
Water 146.3g magnesium chloride hexahydrate 77.8 g, (17.0% as _A1 2 _{O 3,} 18.4% as SO ₃₎ sulfate with stirring a solution prepared by dissolving 111.4 g, water 316 A solution prepared by dissolving 45.2 g of sodium hydroxide in 0.0 g was slowly poured to precipitate a gel. The slurry was put in a 1 L autoclave and reacted at 170 ° C. for 4 hours with stirring, then filtered through a Nutsche and washed with warm water to obtain a cake. A portion of the cake is dried at 110 ° C. overnight to form sulfuric acid type HT-AHS
[Al _2.1 Mg _0.9 (OH) ₆ ] _0.9 ⁺ · (SO ₄ ) ^{2 −} _0.43 · (CO ₃ ) ^{2 −} _0.02 · 1.4H ₂ O
Got.
A cake equivalent to 10 g in terms of dry matter was placed in a 500 ml beaker and redispersed with 160 ml of water. A solution obtained by mixing 3.72 g of sodium aluminate (23.3% as Al ₂ O ₃ , 19.2% as Na ₂ O) and 21.3 g of water into this slurry, and sodium silicate (as SiO ₂₎ (22.8%, 7.27% as Na ₂ O) (B), which was obtained by mixing 13.44 g of water and 11.6 g of water, was added dropwise simultaneously over 1 hour, and aged for 1 hour.
Further, 0.6 g of stearic acid was added to the reaction slurry and surface treatment was performed for 2 hours, followed by filtration with a Nutsche and washing with warm water. The cake was dried at 110 ° C. and pulverized and analyzed for chemical composition. As a result, HT-AHS (aluminosilicate anion type hydrotalcite) was obtained.
^{_{[Al 2.1 Mg 0.9 (OH)}} 6] 0.9+ · (Na 0.04 Al 1.3 Si 3.7 O 10.4) 2- 0.28 (SO 4) 2- 0.09 ^{_{· (CO 3) 2- 0.08 ·}} 2.0H 2 O
The stearic acid surface-treated product.
The physical properties were measured, the results are shown in Table 1, the X-ray diffraction diagram is shown in FIG. 4, and the ²⁷ Al-solid NMR measurement diagram is shown in FIG.

(Example 16)
In a 1 L autoclave, 39.01 g of aluminum hydroxide (Hidelite H-43M manufactured by Showa Denko), 9.24 g of lithium carbonate, 2.38 g of basic magnesium carbonate (TT manufactured by Tokuyama), 5.30 g of sodium carbonate, and 780 g of water were added. After reacting at 140 ° C. for 4 hours with stirring, the mixture was filtered with Nutsche and washed with warm water to obtain a cake. Lithium magnesium aluminum composite hydroxide salt [Al ₂ Li _0.9 Mg _0.1 (OH) ₆ ] _{2 in} which a part of the cake was dried at 110 ° C. overnight and a part of lithium was isomorphously substituted with magnesium ^{. _{2+ · (CO 3) 2- 1.1}} · 2.5H 2 O
Got.
A cake equivalent to 10 g in terms of dry matter was placed in a 500 ml beaker and redispersed with 160 ml of water. (A) solution in which 4.89 g of sodium aluminate (23.3% as Al ₂ O ₃ and 19.2% as Na ₂ O) and 20.1 g of water were mixed with this slurry, and sodium silicate (as SiO ₂₎ (22.8%, 7.27% as Na ₂ O) 17.64 g of a mixture of 7.4 g of water and 7.4 g of water were simultaneously added dropwise over 1 hour and aged for 1 hour.
Further, 0.6 g of stearic acid was added to the reaction slurry and surface treatment was performed for 2 hours, followed by filtration with a Nutsche and washing with warm water. The cake was dried at 110 ° C. and analyzed for chemical composition. G-LAHS (aluminosilicate anion type lithium magnesium aluminum composite hydroxide salt)
_{[Al 2 Li 0.9 Mg 0.1 (} OH) 6] 2 2.2+ · (Na 0.3 Al 0.8 Si 2.8 O 8.0) 2- 0.90 (SO 4) 2- _0.13 · (CO ₃ ) ^2- _0.07 · 2.0H ₂ O
The stearic acid surface-treated product.
The physical properties were measured, the results are shown in Table 1, and the ²⁷ Al-solid NMR measurement diagram is shown in FIG.

  Hereinafter, a three-layer laminated film using the sample of Example 13 as an intermediate layer was prepared, and heat retention and haze of the film were evaluated.

(Example 17)
Using EVA and LLDPE, the following raw materials for outer layer, intermediate layer and inner layer were formed into an inflation film at a processing temperature of 160 ° C., and LLDPE (30 μm) / EVA (90 μm) / LLDPE (30 μm) having a thickness of 150 μm ) A three-layer laminated film was obtained. The outer layer, the intermediate layer, and the inner layer are referred to as an outer layer, an inner layer as an inner layer, and an intermediate layer as an inner layer when a film is stretched, for example. The same applies to the following laminated films.
(LLDPE (outer layer) / EVA (intermediate layer) / LLDPE (inner layer) -resin composition formula)
Outer layer LLDPE (MFR = 1.1) 98.8% by weight
UV absorber (Sumitomo Chemical Sumisorb 130) 0.1% by weight
Antioxidant (Butylhydroxytoluene) 0.3% by weight
Light stabilizer (Cinubain 622-LD manufactured by Ciba Geigy) 0.5% by weight
Lubricant (erucic acid amide) 0.3% by weight
Intermediate layer LLDPE (metallocene, MFR = 4) 88.8% by weight
Insulating agent (Example 13) 10.0% by weight
UV absorber (Sumitomo Chemical Sumisorb 130) 0.1% by weight
Antioxidant (Butylhydroxytoluene) 0.3% by weight
Light stabilizer (Cinubain 622-LD manufactured by Ciba Geigy) 0.5% by weight
Lubricant (erucic acid amide) 0.3% by weight
Inner layer LLDPE (MFR = 1.1) 95.8 wt%
Antifogging agent (sorbitan monostearate) 3.0% by weight
UV absorber (Sumitomo Chemical Sumisorb 130) 0.1% by weight
Antioxidant (Butylhydroxytoluene) 0.3% by weight
Light stabilizer (Cinubain 622-LD manufactured by Ciba Geigy) 0.5% by weight
Lubricant (erucic acid amide) 0.3% by weight
The obtained laminated film had a Haze value of 3.3% and a heat retention of 80.5%.

(Example 18)
Using LLDPE, the following blending raw materials for outer layer, intermediate layer and inner layer are formed by inflation at a processing temperature of 170 ° C., and LLDPE (30 μm) / LLDPE (90 μm) / LLDPE (30 μm) 3 having a thickness of 150 μm After obtaining a layer laminated film, an alumina sol-100 manufactured by Nissan Chemical Co., Ltd. was applied as an antifogging agent to the inner layer surface using an acrylic resin binder.
(LLDPE (outer layer) / LLDPE (intermediate layer) / LLDPE (inner layer) -resin composition formula)
Outer layer LLDPE (MFR = 1.1) 98.8% by weight
UV absorber (Sumitomo Chemical Sumisorb 130) 0.1% by weight
Antioxidant (Butylhydroxytoluene) 0.3% by weight
Light stabilizer (Cinubain 622-LD manufactured by Ciba Geigy) 0.5% by weight
Lubricant (erucic acid amide) 0.3% by weight
Intermediate layer EVA (vinyl acetate content 15%) 88.8% by weight
Insulating agent (Example 13) 10.0% by weight
UV absorber (Sumitomo Chemical Sumisorb 130) 0.1% by weight
Antioxidant (Butylhydroxytoluene) 0.3% by weight
Light stabilizer (Cinubain 622-LD manufactured by Ciba Geigy) 0.5% by weight
Lubricant (erucic acid amide) 0.3% by weight
Inner layer LLDPE (MFR = 1.1) 98.8% by weight
UV absorber (Sumitomo Chemical Sumisorb 130) 0.1% by weight
Antioxidant (Butylhydroxytoluene) 0.3% by weight
Light stabilizer (Cinubain 622-LD manufactured by Ciba Geigy) 0.5% by weight
Lubricant (erucic acid amide) 0.3% by weight
The laminated film obtained had a Haze value of 3.2% and a heat retention of 69.7%.

X-ray diffractograms of carbonate anion type LAHS (Comparative Example 1) and aluminosilicate anion type LAHS (Example 3) of the present invention. The X-ray-diffraction figure of carbonate anion type | mold LAHS and aluminum hydroxide (gibbsite) (comparative example 3) and carbonate anion type | mold LAHS and aluminum hydroxide (gibbsite). The X-ray diffraction pattern of a silicic acid type complex hydroxide salt (comparative example 4). The X-ray-diffraction figure of the aluminosilicate anion type hydrotalcite (Example 15) of this invention. ²⁷ Al-solid NMR measurement of carbonate anion type LAHS (Comparative Example 1). ²⁷ Al-solid state NMR measurement of the aluminosilicate anion type LAHS of the present invention (Example 1). ²⁷ Al-solid state NMR measurement of the aluminosilicate anion type LAHS of the present invention (Example 12). ²⁷ Al-solid state NMR measurement of the aluminosilicate anion type hydrotalcite of the present invention (Example 15). ²⁷ Al-solid state NMR measurement of the aluminosilicate anion type Mg isomorphous substituted LAHS of the present invention (Example 16).

Claims (13)

In an aluminum composite hydroxide salt having an Al hydroxide octahedral layer and having a divalent anion between the octahedral layers,
As the divalent anion, at least the following general formula (1):
_{[Na p Al q Si r O} z] 2- ... (1)
Where p, q, r and z are
5 ≦ z ≦ 20
z = (p / 2) + (3q / 2) + 2r + 1,
0 <p / q <1,
0.01 ≦ q / r ≦ 1
Is a positive number satisfying
An aluminum composite hydroxide salt comprising an aluminosilicate type anion represented by the formula: ²⁷ Al-solid NMR measurement shows that the Al atom in the aluminosilicate type anion is shown as a 4-coordinate Al peak in the range of chemical shift +80 ppm to +50 ppm, and Al Al in the Al hydroxide octahedral layer
The aluminum composite hydroxide salt according to claim 1, wherein the atoms are shown as a peak of 6-coordinated Al in the range of chemical shift + 20ppm to -20ppm.   The aluminum composite hydroxide salt according to claim 1, wherein the aluminosilicate type anion is present in a proportion of 25 mol% or more per divalent anion in the interlayer. The aluminum composite hydroxide salt according to claim 1, wherein SO ₄ ²⁻ and / or CO ₃ ²⁻ coexists as the divalent anion. The Al hydroxide octahedral layer has a structure in which at least one selected from Li atom and / or Mg atom is introduced into a vacancy of gibbsite type aluminum hydroxide, and the following general formula (2):
_{[Al 2 Li (1-x} ) Mg x (OH) 6] 2 2 (1 + x) + · A 2- 1 + x · mH 2 O ... (2)
In the formula, A ²⁻ is a divalent anion between the layers,
x is a number satisfying 0 ≦ x <1;
m is zero or a positive integer;
The aluminum composite hydroxide salt of Claim 1 represented by these. The following general formula (2a):
[Al ₂ Li (OH) ₆ ] _{2 2} ⁺ · A ²⁻ · mH ₂ O (2a)
In the formula, A ²⁻ is a divalent anion between the layers,
m is zero or a positive integer;
The aluminum composite hydroxide salt according to claim 5, which is represented by: The Al hydroxide octahedral layer has a hydrotalcite structure in which a part of Mg of the brucite structure is isomorphously substituted with Al,
The aluminum composite hydroxide salt has the following general formula (3):
^{_{[Al x Mg 3-x (}} OH) 6] x · A 2- x / 2 · mH 2 O ... (3)
In the formula, A ²⁻ is a divalent anion between the layers,
x is a number satisfying 0.6 ≦ x ≦ 1.5,
m is zero or a positive integer;
The aluminum composite hydroxide salt of Claim 1 represented by these. By reacting aluminum hydroxide and lithium carbonate in the presence of an aqueous medium, the following formula (4a):
^{_{[Al 2 Li (OH) 6}} ] 2 2+ · (CO 3) 2- · mH 2 O ... (4a)
Where m is zero or a positive integer.
Lithium aluminum composite hydroxide carbonate represented by
Acid treatment of the lithium aluminum composite hydroxide carbonate with a mineral acid to replace the carbonate radical with a mineral acid anion;
The obtained substituted product is reacted with sodium silicate and sodium aluminate, and the mineral acid anion is further represented by the following formula (1):
_{[Na p Al q Si r O} z] 2- ... (1)
Where p, q, r and z are
5 ≦ z ≦ 20
z = (p / 2) + (3q / 2) + 2r + 1,
0 <p / q <1,
0.01 ≦ q / r ≦ 1
Is a positive number satisfying
A method for producing an aluminum composite hydroxide salt, characterized by substituting an aluminosilicate type anion represented by the formula:   The production method according to claim 8, wherein sulfuric acid is used as the mineral acid. Aluminum hydroxide, lithium carbonate and basic magnesium carbonate are reacted in the presence of an aqueous medium to obtain the following formula (4b):
_{[Al 2 Li (1-x} ) Mg x (OH) 6] 2 2 (1 + x) + · (CO 3) 2- 1 + x · mH 2 O
... (4b)
Where x is a number satisfying 0 <x <1.
m is zero or a positive integer;
Lithium magnesium aluminum composite hydroxide carbonate represented by
Acid treatment of the lithium magnesium aluminum composite hydroxide carbonate with a mineral acid to replace the carbonate radical with a mineral acid anion;
The obtained substituted product is reacted with sodium silicate and sodium aluminate, and the mineral acid anion is further represented by the following formula (1):
_{[Na p Al q Si r O} z] 2- ... (1)
Where p, q, r and z are
5 ≦ z ≦ 20
z = (p / 2) + (3q / 2) + 2r + 1,
0 <p / q <1,
0.01 ≦ q / r ≦ 1
Is a positive number satisfying
A method for producing an aluminum composite hydroxide salt, characterized by substituting an aluminosilicate type anion represented by the formula:   The production method according to claim 10, wherein sulfuric acid is used as the mineral acid. Following formula (5):
^{_{[Al x Mg 3-x (}} OH) 6] x · (SO 4) 2- x / 2 · mH 2 O ... (5)
In the formula, x is a number satisfying 0.6 ≦ x ≦ 1.5,
m is zero or a positive integer;
Prepare magnesium aluminum composite hydroxide sulfate represented by
The magnesium aluminum composite hydroxide sulfate is reacted with sodium silicate and sodium aluminate to convert the sulfate anion in the formula (5) into the following formula (1):
_{[Na p Al q Si r O} z] 2- ... (1)
Where p, q, r and z are
5 ≦ z ≦ 20
z = (p / 2) + (3q / 2) + 2r + 1,
0 <p / q <1,
0.01 ≦ q / r ≦ 1
Is a positive number satisfying
A method for producing an aluminum composite hydroxide salt, characterized by substituting an aluminosilicate type anion represented by the formula:   The compounding agent for resin according to claim 1.

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