JPH041778B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a resin additive, and more specifically, a resin additive comprising an amorphous metal-substituted aluminosilicate powder that is a cation exchanger of amorphous sodium aluminosilicate, which is a precursor of synthetic zeolite. It is related to. [Prior Art] Vinyl chloride resins and olefin resins have been used in many fields in the form of molded products, films, fibers, etc. by various molding or spinning methods because of their excellent physicochemical properties. has been done. As is well known, the molding process of vinyl chloride resin and olefin resin is usually carried out at temperatures above 200℃.
Furthermore, since they are subject to oxidation and deterioration over time due to heat and light during processing or use, they have drawbacks such as a decrease in mechanical properties due to a decrease in molecular weight, coloring, and generation of bad odors. Therefore, conventionally, vinyl chloride resins and olefin resins have rarely been used alone, and are usually mixed with various heat stabilizers, antioxidants, ultraviolet absorbers, and lubricant additives to provide resistance to heat and light. Contains it as an essential compounding agent. Although many inorganic compounds are known as such resin additives, crystalline powders of natural or synthetic zeolites are used in various synthetic resins. For example, it has been proposed that Na-A zeolites be used as heat stabilizers for halogen-containing resins. (Japanese Unexamined Patent Publication No. 54-34356) In addition, A-type zeolite, which is Na-A-type zeolite substituted with other metal cations, especially divalent metal cations such as Ca, Mg, Zn, and Pb, has a high heat resistance against halogen-containing resins. It is proposed to improve stability. (Unexamined Japanese Patent Publication No. 142043/1983, Unexamined Japanese Patent Publication No. 57-
28145) Furthermore, metal substitution A for polyolefin resin
It has been proposed that type zeolites provide anti-degradation effects. (Japanese Unexamined Patent Publication No. 57-67638) On the other hand, as the inorganic amorphous powder, silica powder is mainly used, and a small amount of metal silicate is also used. Recently, as an alumina-silica resin compounding agent,
It has been proposed that amorphous powder, which exhibits amorphous properties in X-ray diffraction, has anti-blocking properties for resins such as polyolefins. (Unexamined Japanese Patent Publication No. 58-213031) [Problems to be solved by the invention] However, deterioration inhibitors such as heat stabilizers, antioxidants, and ultraviolet absorbers are solely blended with vinyl chloride resins and olefin resins. In this case, the anti-deterioration agent has poor compatibility with the resin, so it tends to bleed onto the surface of the molded product and contaminate the product.In addition, the anti-deterioration agent tends to bleed onto the surface of the molded product, contaminating the product.In addition, since the anti-deterioration agent is often low-boiling, it easily evaporates during processing by heating the resin, causing deterioration. There are disadvantages in that not only the effect of adding the inhibitor cannot be fully exhibited, but also the working environment deteriorates due to the generation of foul odors. Moreover, since these additives are expensive, it is essential that they fully demonstrate their intended purpose. For this reason, the above-mentioned drawbacks can be improved by using a deterioration inhibitor and an inorganic crystalline powder such as a certain type of synthetic zeolite in combination with the vinyl chloride resin and olefin resin. The reason for this is that crystalline powders such as zeolite have molecular sieving properties based on their crystal structure, and
It is assumed that the effect of improving the resin, such as stabilization, is exerted by the action of substitutable metal ions and the like included in the crystal structure. Needless to say,
Zeolite is an aluminosilicate with a unique three-dimensional crystal structure, but strangely, no knowledge of amorphous aluminosilicate resins has been obtained so far. In other words, synthetic zeolite is obtained by heating and aging the precursor amorphous sodium aluminosilicate to crystallize it, but although amorphous aluminosilicate has the same chemical composition as zeolite, First, there was no research on it as a resin additive. In view of such conventional technology, the present inventors discovered that the crystal structure of synthetic zeolite such as A-type zeolite and the action based on the substitutable metal ions included in the crystal structure are completely different, and the action is based on the precursor. Based on the fact that certain gel-like amorphous substances also have cation-exchanging properties, similar to zeolites, their metal substitutes can also be used as functional resin additives in the same way as zeolites. I came up with this idea and did some intensive research. As a result, by blending amorphous aluminosilicate powder, which is obtained by cation-exchanging amorphous sodium aluminosilicate, which is a precursor of synthetic zeolite, into resin as a resin additive, or by using it in combination with anti-deterioration agents, etc. It was discovered that zeolite exhibits remarkable effects as a resin stabilizer, a catalyst neutralizer, an anti-blocking agent, an antibacterial agent, a filler, etc. that are equivalent to or better than conventional natural or synthetic zeolites, and the present invention was developed. completed. [Means for Solving the Problems] and [Operation] That is, the present invention is characterized by comprising an amorphous aluminosilicate powder obtained by cation exchange treatment of amorphous sodium aluminosilicate, which is a precursor of synthetic zeolite. This applies to resin additives. The present invention will be explained in detail below. The resin additive according to the present invention satisfies the following conditions: (a) it is amorphous sodium aluminosilicate, which is a precursor of synthetic zeolite, and (b) it is a product obtained by subjecting the precursor to cation exchange treatment. It is made of amorphous aluminosilicate powder. First, the amorphous sodium aluminosilicate that satisfies the requirement (a) consists of a gel-like substance that is a precursor of synthetic zeolite, and the method for producing synthetic zeolite is known, and therefore the method for producing the precursor is also known. Yes, there are no particular restrictions on the manufacturing history. For example, by reacting an aqueous sodium silicate solution and sodium aluminate at a predetermined ratio, an amorphous aluminosilicate gel is immediately generated. Another method involves reacting silica or silica-alumina raw materials with caustic to form a gel. In the present invention, the amorphous sodium aluminosilicate, that is, the precursor, when expressed as an oxide, has the following properties:
Preferably, it is represented by the following general formula (1.0±0.2) _{Na2O.Al2O3 .} (0.8-5) _{SiO2 .} (0-10) _H2O . Among these, precursors _{of synthetic} zeolites of _type A, 0.10) SiO ₂ ·(0-10)H ₂ O is industrially most advantageous. The synthetic zeolite is obtained by crystallizing the above-mentioned amorphous gel through hydrothermal treatment under normal pressure or increased pressure.The precursor in the present invention refers to the starting material before this hydrothermal treatment. It refers to an amorphous gel-like product produced by the reaction of Next, an amorphous metal-substituted aluminosilicate that satisfies the requirement (b) is produced by subjecting the aforementioned precursor to a cation exchange treatment. The above-mentioned precursor has cation exchange ability like general natural or synthetic zeolite, and the resin additive according to the present invention is amorphous aluminium-substituted metal substituted by ion-exchanging the precursor slurry with an aqueous solution of metal ions. Say silicate. Metals to be replaced include alkaline earth metals such as Ca, Mg, and Ba, and other metals selected from divalent metals such as Zn, Pb, or Cu, and monovalent metals such as K, Li, and Ag. More than seeds can be given. The ion exchange treatment is carried out by sufficiently contacting and mixing the soluble salt aqueous solution of the metal to be ion-exchanged with the slurry of the precursor. Examples of soluble salts of metals include chlorides, nitrates, sulfates, and organic acid salts. In addition, this ion exchange is performed using metals such that the molar ratio of M ₂ /nO/Na ₂ O (where M is a substituent metal and n is a valence) is 0.4 or more, preferably a value in the range of 0.5 to 8. It is preferable to carry out the reaction so as to obtain a substituted aluminosilicate. The reason for this is that if it is less than 0.4, no functional effect as a resin additive can be expected. The upper limit is not particularly limited, but in many cases it is because metal substitution with a molar ratio of 8 or more is difficult to obtain industrially. After the metal substitution treatment, the substitute slurry (5g/
It is preferable to wash thoroughly with water so that the equilibrium pH (25°C) of 100ml) is 10.5 or less. As mentioned above, unlike zeolite, this substitute slurry is amorphous and extremely fine particles, so it needs to be thoroughly pulverized after drying. The average particle size in Stokes equivalent diameter based on sedimentation analysis using light transmission method is 3 μm or less, preferably 2.5 ~
It is preferable to adjust the particle size by deagglomeration by intensive shear dispersion so that the particle size falls within the range of 0.1 μm. In addition, in order to further improve the dispersibility of the amorphous metal-substituted aluminosilicate powder obtained in this way, a silane coupling agent,
The surface of the metal substituted product can be modified by appropriately using a surface treatment agent such as an organic silicon compound such as silicone oil, a metal soap, an acidic phosphoric acid ester or a metal salt thereof. The amorphous metal-substituted aluminosilicate powder of the present invention described above is useful as a resin additive for various resins. Various synthetic resins can be used as the resin that can be blended with the resin additive according to the present invention, and there are no particular limitations. For example, halogen-containing resins, α-olefin polymers such as polyethylene, polypropylene, polybutene, α-olefins such as ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, ethylene-acrylate copolymers, etc., and other monomers. Examples include polyolefin resins, polyacetal resins, polyamide resins, silicone resins, and polyester resins that are copolymers with . Examples of the halogen-containing resin used in the present invention include the following. For example, polyvinyl chloride, 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 terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-
Butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride- Vinyl chloride synthetic resins such as maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, internally plasticized polyvinyl chloride, and these chlorinated vinyl resins and polyethylene, polypropylene, α-olefin polymers such as polybutene, poly-3-methylbutene, polyolefins such as ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, and their copolymers, polystyrene, acrylic resins, styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers,
Blend products with acrylic acid ester-butadiene-styrene copolymer and methacrylic acid ester-butadiene-styrene copolymer can be mentioned. The resin additive according to the present invention is a heat stabilizer for halogen-containing resin such as vinyl chloride resin, ethylene,
Stabilizers based on the neutralizing effect of catalysts contained in olefin resins such as propylene, anti-blocking agents for resin films (the above include Ca, Mg, Ba,
It can be used as a filler for Zn, Pb substituted products (particularly Ca is preferred), antibacterial agents (Cu substituted products), and various other synthetic resins. In the present invention, the amount of the resin additive used in the resin varies depending on the purpose of use, the type of resin, the physical properties of the additive, etc., but is 0.01 to 50 parts by weight, preferably 0.05 parts by weight, based on 100 parts by weight of the resin. -30 parts by weight is desirable; if it is less than 0.01 parts by weight, the effects are insufficient; if it exceeds 50 parts by weight, the effects of improving various properties tend to reach a plateau, making it uneconomical. Further, examples of the amount of resin additives suitable for improving various properties of the resin include 50 parts by weight or less as a filler, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the resin. For functional uses such as thermal stabilizers other than agents, stabilizers based on the neutralizing action of catalysts, anti-blocking agents, antibacterial agents, etc., the amount is in the range of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight. is desirable. When using the resin additive according to the present invention, it may be used in combination with other resin additives such as heat stabilizers, plasticizers, lubricants, antioxidants, ultraviolet inhibitors, antistatic agents, colorants, fillers, etc. There is no problem in using these additives in combination, and in fact, in many cases, the functions of these additives are further promoted by using them together. Others as necessary, such as pigments, foaming agents, antistatic agents, antifogging agents, playout prevention agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, antifungal agents, bactericidal agents, metal deactivators, photodeterioration agent, nonmetallic stabilizer,
Borate esters, thiourea derivatives, processing aids, mold release agents, reinforcing agents, and the like can be included. Further, when used, these other well-known resin additives and the resin additive according to the present invention can be mixed in advance and used as a so-called one-pack type resin additive. Plasticizers used when preparing halogen-containing resins using the resin additive according to the present invention include phthalate plasticizers, polyester plasticizers, phosphate plasticizers, epoxy plasticizers, and other plasticizers. The agent can be used as appropriate depending on the purpose. On the other hand, in order to prevent olefin resins from deteriorating due to oxidation, heat, light, ozone, heavy metals such as copper and manganese, or mechanical fatigue, antioxidants such as phenolic or sulfur-containing compounds, benzophenone, and benzophenone are used. When the resin additive according to the present invention is used in combination with anti-deterioration agents such as triazole-based, salicylate-based, substituted acrylonitrile-based, triazine-based, and metal chelate-based ultraviolet absorbers, ozone deterioration inhibitors, and light stabilizers, It can promote the original function of the anti-deterioration agent and impart excellent stability. Although the mechanism of action is not clear, the resin additive is an amorphous fine powder that is highly active, and by adsorbing and retaining the anti-deterioration agent, it is used during heat molding of olefin resins and product resins. It is thought that this prevents the decomposition and volatilization of antioxidants and the like during use, allowing them to maintain their original functions. It also acts to prevent antioxidants and the like from bleeding onto the resin surface, and this is probably due to the same reason as mentioned above. Next, the resin composition according to the present invention is extruded,
It can be formed into films, sheets, plates, pellets, and other desired molded products by ordinary forming methods such as casting, vacuum forming, and low-pressure forming. In these molding methods, first a masterbatch is formed by blending the resin with resin additives and other resin additives such as plasticizers, stabilizers, and colorants, and then the masterbatch is blended with the resin and extruded. By molding by , or other thermal compounding, a molded article in which the resin additive is uniformly dispersed and distributed can be obtained. Since the resin additive according to the present invention has a refractive index almost the same as that of a synthetic resin such as an olefin resin, the olefin resin blended with the resin additive has excellent transparency, and based on its function,
Due to its weather resistance and heat retention properties, it is suitable for use as a non-polluting agricultural film in place of agricultural vinyl chloride film. Although the detailed mechanism by which the resin additive according to the present invention has a functional effect on the resin as described above is completely unknown, it is because it is an amorphous powder made of a precursor of a gel-like substance of synthetic zeolite. Its primary particles are extremely fine, and it is a chemically and physically active powder with cation exchange properties that are different from the molecular sieving properties of zeolite, and it is weakly basic, so it suppresses the deterioration of resins. I think that the. [Examples] Hereinafter, the present invention will be explained in more detail by showing examples. Example 1 Γ sample preparation Sodium silicate aqueous solution (Na ₂ O: 8.1% by weight, SiO ₂ :
6.6% by weight) and an aqueous solution of sodium aluminate (Na ₂ O: 9.3% by weight, Al ₂ O ₃ : 5.6% by weight) at a temperature of 60°C so that the molar ratio of the reaction system (SiO ₂ /Al ₂ O ₃ ) was 2.0. A mixed reaction was carried out at 0.degree. C. to obtain a gel-like reaction product (amorphous sodium aluminosilicate and type A zeolite precursor). Using the type A zeolite precursor obtained above, various samples shown in Table 1 were prepared.

[Table] In order to investigate the performance of each sample shown in Table 1 as a stabilizer for halogen-containing resins, the proportions shown in Table 2 (parts by weight, The various properties of the vinyl chloride resin compositions to which each zeolite sample and other stabilizers and lubricants were added (the same applies hereinafter) were measured and evaluated by the following methods, and the results are also shown in Table 2. (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 opener kept 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. 0.0 Uncolored 1.0 Slightly colored 2.0 Light yellow 3.0 Yellow 4.0 Brown 5.0 Black ｜ ｜ ｜ ｜ ｜ ｜ ↓ Severe thermal deterioration 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) 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.

【table】

[Table] Example 2 Each zeolite sample, antioxidants and lubricant were mixed at the proportions (parts by weight) shown in Table 3 for 100 parts by weight of unstabilized high-density polyethylene resin powder (melt index 0.9). Various properties of the polyethylene resin composition to which the substance was added were measured and evaluated by the following methods, and the results are also shown in Table 3. (1) Heat resistance stability 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 0.5 mm thick sheet. The obtained sheet was cut into a rectangular shape of 3 cm x 5 cm to prepare a test piece. The test piece was placed in a gear open 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. 1.0 Colorless 2.0 Slight yellow 3.0 Yellow ｜ ｜ ｜ ↓ High thermochromicity (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. Evaluation was made on a three-level numerical scale. 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, air-dried, and the degree of discharge (blooming) on the surface was observed with the naked eye. Evaluation was made on a three-level numerical scale. 1.0 No blooming 2.0 Slight blooming 3.0 Blooming

[Table] Note: If bisphenol is added, the color will turn gray.
[Effects of the Invention] A resin composition containing the resin additive according to the present invention can improve various resin properties, such as thermal stability, antioxidant properties, and anti-blocking properties. That is, oxidative deterioration of the resin due to heat and light is prevented, discoloration and discoloration of the resin are significantly suppressed, and migration of antioxidants, decomposition products thereof, etc. to the resin surface (blooming) can be suppressed. Furthermore, the addition of resin additives does not impede the transparency of film-like resin compositions, but rather tends to improve them, and has an anti-blocking effect, making them particularly useful for agricultural films, etc. It is. In particular, when used in combination with a deterioration inhibitor, the function is efficiently exhibited, and the amount of the expensive deterioration inhibitor added can be substantially reduced, which is extremely advantageous industrially. Further, the resin composition according to the present invention can be made of pellets,
It can be easily formed into films, sheets, plates, etc., and can also be easily processed with resin into textiles, paper, etc. Therefore, the resin additive according to the present invention can of course be used in place of conventionally widely used crystalline natural or synthetic zeolites.
Depending on the purpose of use, it can exhibit even more excellent effects.

Claims (1)

[Scope of Claims] 1. A resin additive comprising an amorphous metal-substituted aluminosilicate powder obtained by subjecting amorphous sodium aluminosilicate, which is a precursor of synthetic zeolite, to cation exchange treatment. 2 Amorphous sodium aluminosilicate, when expressed as an oxide, is expressed by the general formula ( _1.0 ±0.2) _Na2O・_Al2O3・(0.8~5) _SiO2・(0~10) _H2O The resin additive according to claim 1. 3 Amorphous sodium aluminosilicate is Na
-The resin additive according to claim 1 or 2, which is a precursor of type A zeolite. 4 Amorphous sodium aluminosilicate contains Ca,
The resin additive according to any one of claims 1 to 3, which is a substituted product of one or more metal ions selected from Mg, Ba, Zn, Pb, or Cu.