JPS6030695B2 - Polyolefin resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stable polyolefin resin composition that is resistant to heat, light, oxidation, and the like.

Due to their excellent physicochemical properties, olefin polymers are used in many fields in the form of molded products, films, fibers, etc. by various molding or spinning methods.

As is well known, the molding process of olefin polymers is usually carried out at 20 and 0 or more, and during processing or use of the polymer, heat and light change over time, resulting in oxidative deterioration and a decrease in the molecular weight, resulting in mechanical properties. There are drawbacks such as a decrease in color, coloration, and odor. Therefore, it has been almost impossible for olefin polymers to be used alone, and it has usually been necessary to use deterioration inhibitors such as various antioxidants and ultraviolet absorbers as essential compounding agents to provide resistance to heat and light. It is included. However, examples of antioxidants include phenolic,
Sulfur-containing types, amine types, phosphite types, etc. are typically known, but these are not sufficiently satisfactory in terms of stabilizing effect on olefin polymers, compatibility, non-staining properties, etc. In other words, these antioxidants have poor compatibility with the olefin polymer, so they tend to bleed onto the surface of the molded product, contaminating the product.Also, many of these antioxidants have low boiling points, and evaporate during processing by heating the resin. However, there are drawbacks such as not only the effects of the additives cannot be fully exerted, but also the working environment deteriorates due to the generation of foul odors.

Moreover, since these additives are expensive, improvements have been desired so that they can fully demonstrate their original purpose. In view of the above facts, the present inventors conducted intensive research to improve the policy, and found that when a certain type of metallurgical substitution type crystalline aluminum/silicate is blended, a remarkable synergistic effect is exhibited. completed.

That is, the present invention is a metal-substituted synthetic crystalline aluminum/silicate whose residual sodium ion is less than % of blood weight as Nb20 by ion exchange with an olefin polymer (excluding ethylene-vinyl acetate copolymer) and a deterioration inhibitor. A polyolefin resin composition comprising:

The raw material crystalline aluminophosphate that can be applied to the present invention has a so-called zeolite structure and its cations are exchangeable.

This crystal structure is easily confirmed by X-ray diffraction and the substantially amorphous aluminum/lotus salt is impermeable as a bulk material.

The bulk crystalline aluminoformate salts that can be applied to the present invention include, for example, A-type, The manufacturing method does not need to be particularly limited.
Among these, type A zeolites and sodalite group aluminosilicates are particularly preferred from the viewpoint of performance and industrial use. In the aluminotal salts, the cation is usually sodium, and may be potassium or other cations, but the zeolite used in the present invention is a metal-substituted aluminosilicate in which these cations are ion-exchanged with other metal ions. Must.

Such metals include metals from group 0 or group W of the periodic table of elements, and examples of the former include magnesium, calcium, strontium, barium, zinc, or cadmium, and typical examples of the latter include tin or lead. be.
Among these, calcium, magnesium or zinc metal-substituted zeolites are particularly preferred. The metal-substituted zeolite described above can be easily prepared by, for example, the following method by ion exchange of the zeolite. That is, it can be obtained by sufficiently contacting a bulk zeolite such as A-type sodium zeolite with an aqueous solution of a soluble salt of the metal to be ion-exchanged. Examples of metal salts include chlorides, nitrates, sulfates, and organic acid salts. Therefore, a batch method in which the bulk zeolite is immersed in the metal salt aqueous solution for ion exchange, a column method in which the metal salt aqueous solution is passed through the solid layer of the bulk zeolite, or a method in which these are used in combination as appropriate are adopted. A metal-substituted zeolite is obtained by replacing all or most of the cations therein with other cations in an aqueous solution and then washing. In addition, in the metal-substituted zeolite as described above, residual sodium ions in the zeolite are Na20
The amount of N may be about 10% by weight or less, and it is particularly preferable that N is also about 5% by weight or less. The reason for this is that if Na ions are present in the zeolite skeleton in excess of a predetermined amount, as well as in the original zeolite, photodiscoloration may occur when the Na ions are blended into the olefin polymer.

On the other hand, in the present invention, the deterioration inhibitors to be used in combination with the metal-substituted aluminosilicate include oxidation, heat, light, ozone, copper,
It is a resin additive to prevent deterioration of olefin polymers caused by heavy metals such as manganese or mechanical fatigue. Typical examples include antioxidants, but in addition, ultraviolet absorbers and ozone deterioration inhibitors are used. , light stabilizers, etc., and these are not necessarily limited.

Examples of antioxidants include 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,6-di-tert-butyl-4-methylphenol. Tributyl-4-butylphenol, 2
, 4-dimethyl-6-tert-butylphenol, 2,6
-di-tert-butyl-Q-dimethylamino-P-cresol, 6-(4-hydroxy-3,5-di-tert-butylanilino)-2,4-bisoctylthio-1,3,5-
Triazine, n-octadecyl-3-(4'-hydroxy-3',5-di-tert-butylphenyl) propionate, bentaerythrityl-tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] , 2,2-bis(4'-oxyphenyl)propane, 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-dihydroxydiphenyl, 2,2'-methylene-bis(4,-methyl- 6-tert-butylphenol), 2,2'-methylene-bis-
(4-ethyl-6-tertiary butylphenol), 4,4'
-methylene-bis-(2,6-di-tert-butylphenol), hindered pisphenol, tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4,4'-thiobis-(6-tert-butyl-3-day methylphenol) 4,4'-thiobis-(6-tert-butyl-0-crisol), phenolic antioxidants such as dialkyl phenol sulfide, dilauryl thiodipropionate, distearyl thiodipropionate , distearyl m8,8'-thiodibutyrate, lauryl stearyl thiodipropionate, dimyristyl
Thiodipropionate, ditridecyl thiodipropionate, amyl thioglycol, 1,1'-thiobis(2-naphthol), 2-merkabutobenzimidazo-
2-mercaptomethyl benzimidazole, tri(nonylphenyl)phosphite, tris (mixed mono- and di-nonylphenyl)
Examples include phosphite-based antioxidants such as phosphite and alkylated arylphosphite, other amine-based antioxidants, and hydrazine derivative waxes. Examples of ultraviolet absorbers include salicylic acid converters such as p-octylphenyl salicylate, 2-hydroxy-4-
Penzophenone derivatives such as n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 4-dodesio*cy-2-hydroxybenzophenone, 2-(2'-hydroxy-3'-tert-butyl-5' -Methyl-phenyl) -5 days Chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chlorobenzole, 2-(2
Examples include penzotriazole derivatives such as '-hydroxy-4'-n-octoxyphenyl)penzotriazole, oxyanilide derivatives, and 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate.

Examples of light stabilizers include hindered amine type, benzoic acid derivatives, [2,2'-thiobis(4-tertiary octylphenolite)]1-n-butylamine, nickel 0, and nickel chelate compounds. Incidentally, those listed above are typical deterioration inhibitors, and the present invention is not limited to these, and any additives for preventing deterioration of olefin polymers can be practically applied. Examples of polyolefin resins that can be stabilized in the present invention include polyethylene, polypropylene, polybutene-1,
Q-olefin polymers such as poly-3-methylbutene,
Copolymers of Q-olefin and other monomers such as ethylene-propylene copolymers and ethylene-ethyl acrylate copolymers, blends of polyolefins and other synthetic resins, block copolymers and graft copolymers It also includes cross-linked polyolefins obtained by hardening polyolefin resins with peroxide or radiation, and foamed polyolefins obtained by foaming polyolefin resins with a blowing agent. As described above, the present invention provides a polyolefin resin composition containing an anti-deterioration agent, which promotes the original function of the anti-deterioration agent by incorporating aluminum/lotus acid salt as described above, thereby achieving extremely excellent stability. Certain olefin resin compositions can be obtained.

Although the mechanism of action is not clear, the aluminosilicate adsorbs and retains the deterioration inhibitor.
It is thought that it prevents the decomposition and volatilization of antioxidants and the like during the aging of olefin resins and when using finished resins, thereby sustaining their original efficacy. It also has the function of preventing antioxidants and the like from bleeding onto the resin surface, and this seems to be based on the same reason as mentioned above. In the present invention, the amount of the metal-substituted crystalline aluminosilicate added to the olefin resin varies depending on the type and amount of the anti-deterioration agent, the purpose of use of the resin, etc., but is 0.000 parts by weight per 100 parts by weight of the olefin polymer. A range of 0.01 to 5 parts by weight can be applied in many cases.

If the amount is below the lower limit, no effect will be observed, and if it exceeds the upper limit, no effect will be observed.

- The mode of blending of the polyolefin resin composition according to the present invention is not limited as long as it can prepare a uniform composition. In addition, conventional methods can be applied as-is to resin molding. In addition, in the polyolefin resin composition according to the present invention, other resin compounding agents such as stabilizers, lubricants, dispersants, plasticizers, colorants such as pigments, fillers, etc. can be used in combination without any problem.

Thus, in the resin composition of the present invention, oxidative deterioration of the polyolefin resin due to heat or light is prevented, and in particular, discoloration or discoloration of the resin due to acid-G deterioration is significantly suppressed.

It also suppresses the migration (bleeding or blooming) of deterioration inhibitors such as antioxidants or their decomposition products to the resin surface. What is even more interesting is that although zeolite is an inorganic powder, it does not inhibit the transparency of the film-like resin composition, but rather improves the transparency, and in addition, it also has an anti-blocking effect. Significant synergistic effects can be expected. In particular, since the function of the anti-deterioration agent can be efficiently exhibited, it becomes possible to substantially reduce the amount of expensive anti-deterioration agent added, and the present invention has great industrial significance. In the following examples, those shown in Table 1 were used as metal-substituted crystalline aluminosilicates.

Table 1 Example 1 Metal-substituted aluminodate salts, The various properties of the polyethylene resin composition to which antioxidants and tenacity substances have been added are measured and evaluated by the following methods, and the results are shown in Table 2.
It is also shown in .

○) Heat resistance stability The polyethylene resin composition of each blending ratio was tested at a front roll surface temperature of 160 qo and a rear roll surface temperature of 12 qo.
After kneading for 5 minutes using a test roll adjusted to 0 qo, the mixture was taken out into a sheet with a thickness of 0.5 mm.

The obtained sheet was cut into a rectangular shape of 3 strips x 5 strips to prepare a test piece. The test piece was placed in a gear oven maintained at 200°C, and the change in heat coloring over time was observed, and the heat discoloration resistance of the polyethylene resin composition was evaluated using the following three numerical values. ■
Pleading Resistance The above test piece was irradiated with a germicidal lamp for two periods, and the degree of pleading on the surface was observed with the naked eye and evaluated using the following three numerical values.

{3} Blooming Resistance The above test piece was immersed in 70 qo warm water for 2 hours, air-dried, and the degree of discharge (blooming) on the surface was observed with the naked eye and evaluated using the following three numerical values.

{Yoshizuma Kaiji Kenkuraru '4' Roll Adhesiveness The degree of adhesion to the roll when polyethylene resin compositions of each formulation were kneaded with a test roll was observed and evaluated using the following three numerical values.

Table 2 Example 2 Unstabilized polypropylene resin (melt index 1.
5) The properties of a polypropylene resin composition prepared by adding metal-substituted aluminosilicates, antioxidants, and tenacity substances to 10 parts by weight in the proportions (parts by weight) shown in Table 3 were the same as in Example 1. The results were also shown in Table 3.

Table 1 3 Example 3 Stabilized polypropylene resin (melt index 1.
5) Metal-substituted aluminolotus salts, antioxidants, ultraviolet absorbers, and lubricating substances were added to 10 parts by weight in the proportions shown in Table 4 and mixed well.

The polypropylene resin composition of each blending ratio was added to the front roll 16.
After kneading for 5 minutes using a test roll adjusted to 0 qo and a rear roll of 120 qo, a sheet having a thickness of 0.5 ribs was taken out. The sheet was cut into a rectangular shape of 5 arcs x IQ to form a test piece. The test pieces were exposed outdoors for 3 months and changes in their surface conditions were observed. The results are also shown in Table 4. Incidentally, all of the polypropylene resin compositions blended with the metal-substituted aluminosilicate in this example had good heat resistance stability, resistance to bleeding, and resistance to blooming according to the test method described in Example 1.

Table-4

Claims (1)

[Scope of Claims] 1. A metal-substituted synthetic crystalline aluminosilicate containing an olefin polymer (excluding ethylene-vinyl acetate copolymer) with a deterioration inhibitor and ion exchange so that residual sodium ions are 10% by weight or less as Na_2O. A polyolefin resin composition characterized by containing a salt. 2 Metal-substituted synthetic crystalline aluminosilicate is metal-substituted A
The polyolefin resin composition according to claim 1, which is a type zeolite. Metal-substituted synthetic crystalline aluminosilicates are listed in Periodic Table I
3. The polyolefin resin composition according to claim 1 or 2, which is a Group I or Group IV metal-substituted crystalline aluminosilicate. 4 Metal-substituted synthetic crystalline aluminosilicate is Ca-substituted A
The polyolefin resin composition according to claim 1, which is a type zeolite.