JPS6116735B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a metal substituted type A zeolite and a method for producing the same. The aim is to provide unique inorganic powders that can be used as additives, fillers, catalysts, etc. useful for improving the physical properties of various rubbers and synthetic resins, as well as to develop industrially advantageous manufacturing methods. It is on offer. Recently, attention has been paid to the use of sodium A-type zeolite as a builder for various detergents, focusing on its calcium ion exchange ability. However, A in which the sodium ions of the zeolite and other metal ions have been ion-exchanged in advance
Metal-substituted zeolites (hereinafter simply referred to as "substituted zeolites") are only slightly known or proposed as special catalysts or stabilizers for vinyl chloride resins and the like. For example, (1) when using type A zeolite activated by dehydration at a temperature of 300°C or higher (US Patent No. 3,245,946), (2) when using inert zeolite with a water content of 18 to 25% as another fixing agent. Case (U.S. Patent No. 4000100
(3) The ion exchange capacity of the sodium salt is
There is a case where an aluminosilicate of zeolite crystals of 2.1 meq/g or more is used (Japanese Patent Application Laid-open No. 34356/1983). All of these are examples using sodium A-type zeolite, which has Na ⁺ in its crystal structure, and some also suggest equivalently substituted zeolites such as calcium zeolite, but there are no specific examples. is not disclosed at all. Based on these proposals, the present inventors have attempted numerous experiments regarding the thermal stabilization ability of sodium A-type zeolite for halogen-containing resins, especially vinyl chloride resins, but despite the above proposals, the performance is unique to sodium. There were no cases where reddish coloring occurred from the early stage of heating and could be expected to be of practical use. Furthermore, even for the same type of substituted zeolite, which is called calcium substituted zeolite, there are many variations in reproducibility when applied to resins, and in particular, there are drawbacks in that there are large differences in the weather resistance of the resins. Furthermore, on the other hand, there are problems such as significant changes in resin properties when used in combination with other stabilizers.
This fact is not limited to halogen-containing resins, but also applies when compounded as an additive to polyolefin resins, ethylene-vinyl acetate resins, rubbers, etc. In view of the above facts, the present inventors conducted further intensive research and found that the performance of type A zeolite has a quantitative relationship between the substituted metal and residual sodium, and is also influenced by the particle characteristics. Based on this, we succeeded in modifying type A zeolite suitable for various resin additive fields, and completed the present invention. That is, the present invention provides a metal-substituted type A zeolite product in which sodium A-type zeolite is substituted with divalent metal ions through ion exchange, and the residual sodium ions are 10% by weight or less as Na ₂ O. As for particle size characteristics, primary particles are substantially in the range of 0.1 to 10 μm when observed under an electron microscope.
In addition, it has a uniform particle size distribution in which the particle size distribution of particles with a particle size of 6 μm or less is 80% or more according to a light transmission particle size measurement method, and the particle shape of the substituted product is spherical or rounded cubic. The present invention relates to a metal-substituted type A zeolite for resin additives, and further relates to an effective method for producing the same. In general, the term "zeolite" is a general term for aluminosilicates with a unique three-dimensional skeleton structure, and various zeolites are known depending on the molar ratio of SiO ₂ /A ₂ O ₃ and crystal structure. However, the sodium A type zeolite in the present invention is a raw material of substituted zeolite and has the general formula Na ₂ O・A ₂ O ₃・
(1.5 to 2.5) It is a crystalline aluminosilicate having a chemical composition close to SiO ₂ .nH ₂ O (n is 0 to 4.5) and having a cation exchange ability. This A-type zeolite has a crystal structure belonging to equiaxed crystallization, which is easily confirmed from the spectral characteristics of diffraction lines shown by X-ray diffraction. The substituted zeolite according to the present invention is a type A zeolite in which the sodium ion of the above-mentioned sodium A type zeolite is replaced with another metal ion by ion exchange, and its basic crystal skeleton structure is the same as that of the original zeolite. be. One of the characteristics of the substituted zeolite of the present invention is that the residual _sodium ions in the zeolite are
It should be 5% by weight or less, particularly preferably 5% by weight or less.
% by weight or less. The reason for this is that the properties of type A zeolite are influenced by the quantitative balance between sodium ions and other metal ions in the zeolite structure, and the zeolite contains 10% by weight of Na ₂ O.
Below, even if some sodium remains, the characteristics of the substituted zeolite will take priority;
This is because when Na ₂ O exceeds 10% by weight, almost no effect of the substituted zeolite is observed, and the properties of the sodium A-type zeolite tend to take precedence. Therefore, substituted zeolites in which the residual sodium ions in type A zeolite are about 10% by weight or less as Na ₂ O will have the characteristics of the corresponding metal-substituted zeolites, especially if Na ₂ O is about 5% by weight or less. If the amount is less than % by weight, any substituted metal ion will substantially exhibit only the original characteristics of each substituted zeolite, so the effects of each substituted zeolite can be reproducibly determined depending on the desired application. It can be demonstrated. For example, when used as an additive in vinyl chloride resin, sodium is strongly basic and should have excellent hydrogen chloride scavenging ability. The resin is colored red,
Its weather resistance is also significantly reduced. In this regard, sodium in the zeolite crystal structure is no exception, as is the case with other sodium salts; when a vinyl chloride resin containing sodium zeolite is exposed outdoors, it deteriorates rapidly and becomes colored red, which has a significant negative impact on its weather resistance. However, in the case of specific substituted zeolites with residual sodium of about 10% by weight or less, the above phenomenon is not observed, and especially when the residual sodium is 5% by weight or less, they always have a remarkable resin stabilizing ability. . This fact is also true for other resins, and is thought to be due to the characteristics of each substituted zeolite. Note that the amount of residual sodium ions in the present invention is a value analyzed by measurement using an atomic absorption spectrophotometer. In such a substituted zeolite, the metal to be substituted is not particularly limited as long as it is another metal ion capable of ion exchange with the sodium ion of the sodium A-type zeolite. However, although it may be naturally limited from an industrial or usage point of view, for example, elements of Group Group of the Periodic Table such as magnesium, calcium, strontium, barium, zinc or cadmium, Group Group elements of the Periodic Table such as tin or lead, Examples of other elements include nickel,
Examples include cobalt, copper, titanium, manganese, germanium, palladium, platinum, or silver, but in most cases metal ions of divalent elements are suitable, and one or more of these may be used. There isn't. Next, as another feature of the present invention, it is important that the substituted zeolite as described above has the following particle size characteristics. In other words, when observed under an electron microscope, the primary particles are substantially in the range of 0.1 to 1.0 μm, and when measured using a light transmission particle size measurement method, a uniform particle size distribution in which the particle size portion of 6 μm or less accounts for 80% or more is observed. It is a substituted zeolite with The reason for this is that if the primary particles are 0.1 μm or less, the preparation of bulk zeolite is inefficient and impractical, whereas if the primary particles are 10 μm or more, the functions of the substituted zeolite tend to be limited, such as rubber This is because the properties of the substituted zeolite cannot be substantially utilized because the dispersibility and compatibility with the substituted zeolite and resin are extremely poor, the specific surface area becomes small, and the activity ability decreases. For the same reason, a substituted zeolite with a sharp particle size distribution as described above, especially when measured by a light transmission particle size measurement method, can most effectively exhibit the function of a substituted zeolite. Depending on the type of substituted zeolite, due to its nature, fine hydrous oxides of the corresponding metals may be deposited on the surface of the zeolite particles, or may contain partially liberated fine particles.
This is because during ion exchange, metal ions may partially hydrolyze and compete with the ion exchange reaction to generate metal hydroxides, but this does not pose any practical problems and is essentially Substituted zeolite is allowed as long as it does not impair its functionality.
Furthermore, the present invention includes not only substituted zeolite having crystal water but also anhydrous substituted zeolite obtained by dehydrating it. The particle properties of such substituted zeolites are often essentially determined by the particle properties of the bulk sodium A zeolite. Crystallographically, A-type zeolite belongs to the equiaxed crystal system, so normally it is a sugar cube-shaped cubic particle with prominent corners and ridges, but in the present invention, the bulk zeolite is Since it is spherical or rounded cubic, the particle shape of the A-type zeolite metal substitute is a rounded cubic shape in which the corners and ridges of the spherical crystal grains or cube disappear and become smooth curved surfaces. It has the following characteristics. For this reason, the dispersibility of the particles is extremely excellent. Such shapes are easily identified by scanning electron microscopy. If we look at a typical example, Figure 1 is a scanning electron micrograph of bulk sodium A-type zeolite obtained in Example 1, which will be described later, at a molar ratio of SiO ₂ /A ₂ O ₃ of 1.8. Figure 2 also shows 4 examples of calcium-substituted type A zeolite obtained by ion-exchanging this zeolite with a calcium chloride solution.
This is a photo of No. 1-2). As is clear from the figure, they are all unique cubic A-type zeolites with uniform particle size and roundness, and it can be seen that the substituted zeolite essentially inherits the basic skeleton of the original zeolite. This is exactly the same for other substitutions, and all of them are characteristic substitutions. The substituted zeolite according to the present invention is one substituted with an additive, a rubber additive, or a special metal for improving the physical properties of thermoplastic resins such as vinyl chloride resin, polyolefin resin, ethylene-vinyl acetate resin, and polyacetal resin. are useful as catalysts or inorganic pigments. For example, substituted zeolites exchanged with calcium, magnesium, or zinc ions are effective as additives for resins and rubbers, substituted zeolites exchanged with cobalt ions are useful as temperature sensors, or substituted with copper ions. Zeolites are suitable as disinfectants and catalysts. The substituted zeolite according to the present invention is manufactured by the following method which is industrially and performance-advantageous. That is,
Crystals obtained by reacting a sodium silicate aqueous solution and a sodium aluminate aqueous solution without back mixing at a molar ratio SiO ₂ /A ₂ O ₃ in the range of 0.5 to 3 to obtain a gel, and then ripening the gel. The crystal particles are washed with water, and then the crystal particles are brought into contact with an aqueous solution of a divalent metal salt to perform ion exchange in a state where the pH of the slurry system is 5 or more. The raw materials used in the production method according to the present invention are a sodium silicate aqueous solution and a sodium aluminate aqueous solution,
The appropriate concentration is as shown below. Sodium silicate aqueous solution: Na ₂ O 5-20% SiO ₂ 5-20% Sodium aluminate aqueous solution: Na ₂ O 5-15% A ₂ O 5-10% The most important part in the production method of the present invention is sodium aluminate. The present invention concerns gel preparation and gel ripening in a reaction to obtain an amorphous aluminosilicate gel by mixing an aqueous solution and a sodium silicate aqueous solution. First, in preparing the gel, the method is characterized in that a uniform gel is prepared by continuously and completely mixing a sodium aluminate aqueous solution and a sodium silicate aqueous solution without back-mixing. For this purpose, in the present invention, a tubular static mixing device, a centrifugal pump, etc. are used, and a sodium aluminate aqueous solution and a sodium silicate aqueous solution are simultaneously injected into the device to continuously prepare a uniform gel. A reaction without back mixing means that when a reaction is carried out by mixing liquids A and B, the reaction is always carried out by direct contact and mixing of liquids A and B in the reaction system. means the state of being In general, such conditions can be achieved by rapidly draining both reaction solutions into a small volume reaction system with strong stirring effects (i.e., both reactions within an extremely short residence time). In the case of the present invention, it is desirable that the average residence time in the reaction system, i.e., the mixing device, be less than about 10 seconds, as defined below, during which It is necessary that thorough mixing occur. Reactions under such conditions can be carried out by introducing liquids A and B into a reaction system in which a significant amount of reaction products have already accumulated, or by introducing liquids B or A into liquid A or B. This is essentially different from a reaction that is carried out by gradually adding and mixing (both reactions involve back mixing). The latter reaction (reaction accompanied by back mixing)
In both cases, liquid A and liquid B will once mix with the reaction product and have some influence on the liquid concentration and the particle state of the product, and then they will come into contact with each other and react. be. Note that JP-A-50-70289 describes a method for preparing a gel by simultaneously adding a sodium silicate solution and a sodium aluminate solution, but this method is a batch method in which mixing is performed by applying shear force for a long time. Therefore, this method involves back mixing and is essentially different from the manufacturing method of the present invention. In the method of the present invention, a small-volume mixing device that exhibits a strong stirring effect is used as a reactor in order to carry out the reaction continuously without back-mixing. Although a mixing device, a centrifugal pump, etc. are used, the former is particularly preferred. The reaction is carried out by simultaneously injecting a sodium silicate aqueous solution and a sodium aluminate aqueous solution into these reactors and passing them through the reactor.The average residence time θ (seconds) in the reaction system at that time is as follows. It can be calculated based on a relational expression. θ=V/a+b where V represents the container of the reactor (), and a and b represent the injection rate (/sec) of the sodium aluminate aqueous solution and the sodium aluminate aqueous solution, respectively. In the method of the present invention, the quantitative ratio of the sodium aluminate aqueous solution and the sodium silicate aqueous solution injected into the reactor is such that the molar ratio (SiO ₂ /A ₂ O ₃ ) of the reaction system is in the range of 0.5 to 3, preferably 0.8 to 2.5. If it is outside this range, a zeolite having the above-mentioned particle characteristics cannot be obtained regardless of the subsequent aging treatment, but it is also undesirable because it causes operational problems. Although it depends on the aging conditions, within the above range, cubic crystal grains with rounded corners can be obtained, and when the molar ratio is particularly low, uniform crystal grains that are nearly spherical can be obtained. The reaction temperature when preparing the gel, that is, the temperature of the sodium silicate aqueous solution and the sodium aluminate aqueous solution, does not need to be particularly limited and may be appropriately selected depending on the desired particle size of the A-type zeolite. Generally, the higher the reaction temperature, the higher the activity of the gel produced, the crystallization due to subsequent aging is completed in a shorter time, and the particle size of the resulting zeolite tends to be larger. The gel thus obtained is aged as it is for immediate crystallization. This aging process for crystallization does not require any particular changes from the usual method.
Desired conditions may be set as appropriate. Generally, 50
This is carried out by stirring at a temperature of 150°C to 150°C for about 1 to 10 hours. In this case, the lower the temperature, the longer the crystallization time;
Particles also tend to become smaller. The aging operation is generally performed by stirring and mixing, but it is also preferable to mix and age by applying shearing force such as with a homogenizer. In addition, during this ripening, the particle characteristics are also affected by the free alkali concentration, that is, the NaOH concentration, and if the free alkali concentration is higher than the concentration of free alkali produced by the gelation reaction, the particles will become rounded, while on the other hand, if the concentration If it is lower, the particles tend to be cube-shaped like sugar cubes. A feature of the present invention is that the above-described process produces sodium A-type zeolite having substantially uniform particle characteristics with an extremely narrow particle size distribution regardless of its shape. Next, the mother liquor of the crystallized zeolite slurry is separated by filtration, washed with water until the free alkali is substantially removed to obtain a filtration cake, and the zeolite is brought into contact with an aqueous metal salt solution to be replaced and subjected to ion exchange treatment. However, several aspects of this method are possible. For example, there is a method in which the washed cake is redispersed in water to a predetermined slurry concentration and a water-soluble metal salt is added and mixed to the slurry, and a method in which the water-soluble metal salt is continuously or discontinuously passed through the zeolite layer in a column type. In the present invention, any contacting method may be used, but it is important to ensure that the residual sodium ions as Na ₂ O in the zeolite are about 10% by weight or less as a result of ion exchange. In addition, during or before or after this operation, it is preferable to use a shearing force such as a homogenizer, or to use a means that also serves as wet pulverization or classification, as appropriate, in order to adjust the particle characteristics. In this process, the conditions for ion exchange vary depending on the amount of exchange, the type of metal salt, etc., but the important thing in common is that the pH of the reaction system should be weakly acidic or alkaline, with a pH value of about 5 or higher. , other temperature, time, slurry concentration, etc. can be set to desired conditions. The reason for this is that when the pH is below about 5, the crystal structure of type A zeolite is easily destroyed, while the upper limit of pH varies depending on the metal salt aqueous solution to be ion-exchanged, and for example, hydroxides are likely to be generated. Contact in such a pH range will reduce efficiency, so it should be set depending on the nature of the metal salt selected, and other conditions are a matter of the degree of ion exchange and do not affect the essential performance of the substituted zeolite. Since there is no direct influence on this, it is only necessary to set favorable conditions as appropriate. For example, in the present invention, the slurry concentration is at most 30% by weight;
Preferably, the zeolite slurry of 5 to 20% by weight and the metal salt aqueous solution are brought into contact with the metal salt aqueous solution at room temperature or in a humidified state at a temperature of 40°C or higher for at least 10 minutes, preferably 30 minutes to 6 hours, at a pH of 5 or higher. ion exchange with the desired metal ion. In this case, the batch treatment is not limited to one operation, but may need to be repeated two or more times as necessary until the residual sodium ions become 10% by weight or less as Na ₂ O. In this way, substituted zeolite can be obtained by sufficiently contacting the bulk zeolite with an aqueous solution of a soluble salt of the metal to be ion-exchanged. Alternatively, organic acid salts, etc. may be mentioned. Thus, after the ion exchange treatment, the mother liquor can be separated, washed, dried, pulverized, and if necessary classified to obtain a useful substituted zeolite. In addition,
By further performing heat treatment during drying, it is possible to obtain an activated substituted zeolite that has also dehydrated crystal water, and if necessary, the particle surface can be processed with a surfactant or an organic surface treatment agent as desired. and may further improve the functionality of the substituted zeolite. By the production method according to the present invention, useful substituted zeolites with excellent particle properties can be industrially mass-produced, and the reliability and reproducibility of their functions in terms of use are remarkable. Hereinafter, the present invention will be described in more detail with reference to Examples. Example 1 Sodium silicate aqueous solution (Nb ₂ O 8.1%, SiO ₂ 6.6% and sodium aluminate aqueous solution (Na ₂ O 9.3%, A
₂ O ₃ 5.6%) was added to the reaction system via a pump in quantitative proportions such that the molar ratio (SiO ₂ /A ₂ O ₃ ) was 0.8, 1.8, and 2.0, respectively, using a static mixer (Nippon Toki Co., Ltd.). ) was simultaneously and continuously injected into a kind of tubular static mixing device manufactured by ) to produce an aluminosilicate gel by instantaneous complete mixing without back-mixing.
However, the average residence time of the contents in the static mixer during the reaction was all 1.2 seconds or less, and the temperature of each raw material aqueous solution was 80°C. A constant amount of the reaction product continuously flowing out from the static mixer was collected in a receiver. When the gel-like reaction products obtained by the reaction at each molar ratio were heated at 80°C for 2 hours with moderate stirring, a highly fluid slurry consisting of fine particles and an alkaline solution was obtained. . This slurry was filtered and washed to obtain a washed cake separated from the mother liquor. A small portion of this was collected and subjected to X-ray diffraction, and sodium A.
It was confirmed that it was a type zeolite. Next, each cake was dispersed in water to obtain a slurry concentration of 100g/
A sodium A-type zeolite slurry was prepared. Next, a calcium chloride aqueous solution with a concentration of 100g/35
parts were added into 100 parts of each slurry and mixed. At this time, the pH is 9.2, and the temperature is always constant at 40℃, about 30℃.
Ion exchange treatment was performed for 1 minute. Then, they were washed with water in the same manner, dried at a temperature of 120°C, and then ground to obtain powdered calcium type A zeolite. In order to investigate the characteristics of the obtained substituted zeolite, measurements and observations were made using powder X-ray diffraction scanning electron microscopy, light transmission particle size measurement, chemical analysis, and atomic absorption spectrophotometry, and the following results were obtained. Ta.

[Table] Aqueous solution
Approximately 0.5 g of zeolite sample was added to 500 ml, stirred thoroughly to form a uniform suspension, and the sedimentation curve was measured at 25°C using a light transmission particle size distribution analyzer (manufactured by Seijin Enterprise Co., Ltd.). and calculate the distribution for each particle size. Also, the average particle size is determined from the cumulative curve of the particle size distribution. Example 2 In Example 1, the reaction molar ratio (SiO ₂ /A
The washed sodium A-type zeolite obtained with ₂ O ₃ ) of 1.8 is dispersed in water and the slurry concentration is
100 g/slurry (this slurry is referred to as "MR1.8 slurry"). (2-1) ZnC ₂ for 100 parts of “MR1.8 slurry”
After adding and mixing 40 parts of an aqueous solution with a concentration of 100 g/ml, the mixture was stirred at room temperature (427°C) for 30 minutes to perform ion exchange. The pH at this time was 6.2. Next, this was washed with water, and the separated cake was dried at 120°C and crushed to obtain zinc A type zeolite. (2-2) MgC for 100 parts of “MR1.8 slurry”
₂ After adding and mixing 30 parts of 100g/aqueous solution,
Ion exchange was performed by stirring at 60°C for 30 minutes. at this time
The pH was 8.6. This was then washed with water, and the separated cake was dried at 120°C and pulverized to obtain magnesium A-type zeolite. (2-3) For 100 parts of “MR1.8 slurry”
After adding and mixing 100 parts of an aqueous solution containing 100 g of PbNO ₃ , the mixture was stirred at 60° C. for 30 minutes to perform ion exchange. The pH at this time was 7.2. This was then washed with water, and the separated cake was dried at 120°C and pulverized to obtain lead-A type zeolite. (2-4) CoC for 100 parts of “MR1.8 slurry”
After adding and mixing 40 parts of an aqueous solution of 100g/ ₂ , the mixture was stirred at 60°C for 30 minutes to perform ion exchange. The pH at this time was 7.3. Next, this was washed with water, and the separated cake was dried at 120°C and crushed to obtain cobalt-A type zeolite. (2-5) For 100 parts of “MR1.8 slurry”
After adding and mixing 45 parts of an aqueous solution containing 100 g of CuSO ₄ , the mixture was stirred at 60° C. for 30 minutes to perform ion exchange.
The pH at this time was 6.8. Next, this was washed with water, and the separated cake was dried and crushed to obtain a copper-A type zeolite. In order to investigate the characteristics of the above five types of substituted zeolites, we measured or observed them by powder X-ray diffraction, scanning electron microscopy, light transmission method particle size distribution measurement, and chemical analysis, and the results are shown in the following table (Table 2). It has become like that.

[Table] Example 3 50 parts of water was added to 100 parts of the pasty gel obtained at a reaction molar ratio of 0.8 in Example 1, and the mixture was mixed and stirred for 6 hours at a temperature of 95°C to mature, resulting in a fluid slurry. It was done. Then, the mother liquor was separated and washed with water to obtain a filter cake. A portion of this was examined by powder X-ray diffraction, and it was confirmed to be sodium A-type zeolite. After redispersing this supercake in water through a homogenizer (manufactured by Kokusan Seiko Co., Ltd.) to prepare a slurry of 100 g/kg, CaC
Calcium-substituted zeolite was obtained by ion exchange under the same conditions as in Example 1 using 100 g of an aqueous solution of ₂ . Its characteristics are as follows:

[Table] This is the case when
Reference Example 1 In order to investigate the performance of the substituted zeolite obtained in Example 1 as a stabilizer for halogen-containing resins,
The proportions shown in Table 2 (parts by weight, the same below) per 100 parts by weight of vinyl chloride resin (Zeon 103EP)
The various properties of the vinyl chloride resin compositions to which each zeolite sample and other stabilizers and lubricants were added were measured and evaluated using the methods described below, and the results are also shown in Table 4. (1) Static thermal stability The vinyl chloride resin composition of each blending ratio was heated to 160°C.
After kneading for 5 minutes with a test roll, the thickness was 0.5
It was taken out in the form of a mm sheet. The obtained sheet was cut into a rectangular shape of 2 cm x 5 cm to prepare a test piece.
The test piece was placed in a gear oven maintained at 200°C, and the change in thermal coloring over time was observed, and the thermal deterioration of the vinyl chloride resin composition was evaluated using the following six numerical values.

[Table] In addition, the coloring in the gear oven for up to 20 minutes was evaluated separately as the initial coloring resistance. Those without coloring were considered to have good initial coloring resistance. (2) Dynamic thermal stability (long run property) The vinyl chloride resin composition of each blending ratio was heated to 190°C.
Knead continuously for 60 minutes using a test roll.
A sheet was taken out every 10 minutes and the degree of coloring was evaluated on the above 6 scales. (3) Heat storage discoloration resistance The vinyl chloride resin composition was kneaded for 5 minutes with a test roll at 160°C, then two sheets with a thickness of 0.5 mm were formed, and the sheets were stacked and hot-pressed at 170°C and 30 kg/cm ² for 5 minutes for testing. It was made into a piece (1 mm thick). This test piece was left in a gear oven kept at 100°C for 48 hours, and then the degree of thermal discoloration was observed. Those with little thermal discoloration were considered to have good heat storage discoloration resistance. (4) Weather resistance () Outdoor exposure test The above test piece (1 mm thick) was exposed outdoors for 6 months, and the weather resistance of the vinyl chloride resin composition was evaluated from the degree of discoloration of the test piece. Those with a small degree of discoloration were considered to have good weather resistance. () (Ultraviolet irradiation) After irradiating the above test piece with ultraviolet rays for 24 hours using a germicidal lamp, light resistance was evaluated from the degree of discoloration of the test piece. Those with little discoloration were considered to have good light resistance. (5) Blooming resistance The above test piece was immersed in hot water at 70°C for 24 hours, air-dried, and the blooming resistance was evaluated by observing the state of white discharge on the surface of the test piece. Those with a small degree of whitening were judged to have good blooming resistance. (6) Blue-out resistance Each vinyl chloride resin composition further added with 1.0 part of watching red is kneaded for 10 minutes on a test roll at 160°C, taken out in a sheet form, and then the roll surface is cleaned. A separately prepared vinyl chloride resin composition having the following cleaning formulation was kneaded under the same conditions for 5 minutes, then formed into a sheet, and the plate-out resistance was evaluated from the degree of red coloration due to residual adhesion on the roll surface of the sheet. Those with less red coloring were judged to have good brate-out resistance. Cleaning formulation Vinyl chloride resin (Zeon 103EP) 100 parts DOP 40 Calcium carbonate 10 Titanium oxide 1 Cd-Ba complex metal soap 1 In addition, in Table 4, R-1 Na ₂ O 17.0% is an example- 1 without calcium ion exchange (basic sodium A-type zeolite),
For R-2, Na ₂ O 12.3, the same ion exchange conditions as in Example 1 (temperature, time, slurry concentration, raw materials, cleaning,
The sample after comparison was treated with drying. As can be seen from Table 4, the specific zeolite according to the present invention is effective in both thermal stability, weather resistance, and processability, and is found to be excellent as a hard vinyl chloride additive.

【table】

[Table] Reference example 2 5th part per 100 parts by weight of unstabilized high-density polyethylene resin powder (Melt Deluxe 0.9)
The various properties of the polyethylene resin composition to which the substituted zeolite, antioxidants, and lubricating substances obtained in the examples were added at the blending ratios (parts by weight) shown in the table were measured and evaluated using the methods below. It is also shown in Table 5. (1) Heat-resistant stabilizer Polyethylene resin compositions of various blending ratios were kneaded for 5 minutes using test rolls whose front roll surface temperature was adjusted to 160°C and rear roll surface temperature to 120°C, and then taken out in the form of a sheet with a thickness of 0.5 mm. The obtained sheet was cut into a 3 cm x 5 cm rectangle to prepare a test piece. The test piece was placed in a gear oven kept at 200℃, and the change in heat coloring over time was observed.
The heat discoloration resistance of the polyethylene resin composition was evaluated using numerical values in stages.

[Table] ↓ Large
(2) Bleeding resistance The above test piece was irradiated with a germicidal lamp for 24 hours, and the degree of bleeding on the surface was observed with the naked eye and evaluated using the following three numerical values. 1.0 No bleeding 2.0 Slightly observed 3.0 Bleeding (3) Blooming resistance The above test piece was immersed in hot water at 70℃ for 24 hours and then air-dried to determine the degree of discharge on the surface (blooming resistance)
was observed with the naked eye and evaluated using the following three numerical values. 1.0 No blooming 2.0 Slightly observed 3.0 Blooming (4) Roll adhesion When each polyethylene resin composition was kneaded with a test roll, the degree of adhesion to the roll was observed and evaluated using the following three numerical values. 1.0 Not sticky 2.0 Slightly sticky 3.0 Sticky

[Table] Reference Example 3 Ethylene butadiene rubber (SBR) was used as the raw material rubber, and zinc-substituted type A zeolite (Example No.
Sample 2-1) and various rubber compounding agents were blended as shown in Table 6, and kneaded by the method shown below to obtain a vulcanizable rubber composition. For comparison, a rubber composition was obtained by performing the same treatment without adding the zeolite. The vulcanizability of these compositions was measured using a culastometer, and the results shown in Table 6 were obtained.

[Table] Next, these unvulcanized compositions were heated to 150% by a conventional method.
Table 7 shows the results of measuring the physical properties of the rubber compositions obtained by vulcanization at .degree. C. using the methods shown below. From the results in Tables 6 and 7, it is possible to shorten the vulcanization time and improve the properties of the rubber composition, such as elongation, by adding zinc A-type zeolite to SBR.

【table】

【table】 The vulcanization rate test was conducted as follows. Kneading roll: Dimensions 20.3cm x 45.7cm (8 x 18 inches) Rotation speed 18rpm Rotation ratio 1.18 Surface temperature 50±5℃ Vulcanization conditions: 150℃×min Evaluation method Test piece: JIS No. 3 dumbbell Testing machine: Schottsper type tensile testing machine (Capacity 50Kgf) Test method: Compliant with JIS K6301

[Brief explanation of the drawing]

Figure 1 is a sodium A-type zeolite according to the present invention; Figure 2 is a scanning electron micrograph of the calcium-substituted type A zeolite (×
5000).

Claims (1)

[Scope of Claims] 1. A type A zeolite metal-substituted product in which sodium A-type zeolite is replaced with divalent metal ions through ion exchange, and the residual sodium ions are 10% by weight or less as Na ₂ O. The particle size is substantially in the range of 0.1 to 10 μm when observed by electron microscopy, and the particle size is 6 μm when measured by light transmission particle size measurement.
A-type zeolite metal substitution for resin additives characterized by having a uniform particle size distribution with a particle size distribution of 80% or less below μm, and the particle shape of the substituted product being spherical or rounded cubic. body. 2 Divalent metal ions are M ⁺⁺ , Ca ⁺⁺ , Ba ⁺⁺ ,
Sr ⁺⁺ , Mn ⁺⁺ , Co ⁺⁺ , Ni ⁺⁺ , Cu ⁺⁺ , Cd ⁺⁺ ,
Claim 1, which is at least one metal ion selected from Zn ⁺⁺ , Ge ⁺⁺ , Sn ⁺⁺ or Pb ⁺⁺
A-type zeolite metal substituted product for resin additives as described in 1. 3. After generating a gel by reacting an aqueous sodium silicate solution and an aqueous sodium aluminate solution at a molar ratio SiO ₂ /Al ₂ O ₃ in a range of 0.5 to 3 without back mixing, A resin additive consisting of thermally forming the gel, washing the crystals obtained by crystallization with water, and then contacting the crystal particles with an aqueous solution of a divalent metal salt to perform ion exchange in a state where the pH of the slurry system is 5 or more. A method for producing a metal-substituted type A zeolite for use. 4. A method for producing a metal-substituted type A zeolite for resin additives according to claim 3, in which mixing is carried out using a tubular static mixing device without back mixing.