JPS6358173B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an inorganic-filled polyolefin resin composition. Polyolefin resins are known as resins with excellent various properties, and are used in large quantities for a very wide range of applications. In recent years, for such polyolefin resins,
Various attempts have been made to fill large amounts of various inorganic compounds for the purposes of so-called pollution-free, resource saving, and flame retardancy. However, on the other hand, the blending of fillers tends to significantly impair the elongation at break and impact strength of the polyolefin resin. For this reason, there is a tendency to actively utilize fillers not only as fillers but also as reinforcing agents by modifying the surface of filler particles and creating some kind of bond between them and the plastic, and these technological trends is attracting attention. For example, when dispersing naturally occurring or synthetic calcium carbonate in plastics, it is treated with surfactants, i.e. saturated and unsaturated fatty acids of medium or high molecular weight, in order to improve its dispersibility. (West German Patent No. 958830) and the use of an alkaline earth metal carbonate together with at least one unsaturated carboxylic acid for surface modification of inorganic materials are known. However, even in these processing methods,
A decline in overall resin properties cannot be avoided. As a result of intensive research, the present inventors have found that when treating inorganic fillers, by blending a phosphate ester type reaction activator with the inorganic filler, the filling amount can be improved, and the moldability of polyolefin resin can be improved. The present invention was achieved by discovering that mechanical strength can be increased without impairing properties, and flame retardancy can be imparted if desired. That is, in a polyolefin resin composition prepared by blending 10 to 300 parts by weight of a powdered inorganic compound and, if necessary, various additives in desired amounts with respect to 100 parts by weight of the polyolefin resin, the inorganic compound General formula of 1 to 50 parts by weight per 100 parts by weight, (However, in the formula, R represents H or a methyl group, R ₁ is a -CH ₂ CH ₂ - group,

[Formula] group, or

[Formula] Any of the groups or a mixture thereof, R ₂ is an OH group,

[Formula] or indicates OR ₃ . Note that R ₃ is represented by the general formula (R ₁ O) _n OR ₄ ,
R ₄ is a residue of a saturated or unsaturated alkyl having 3 to 18 carbon atoms or a saturated or unsaturated alkylphenol having 1 to 12 carbon atoms. Further, n is an integer of 1 to 50, and m is 0 or an integer of 1 to 50. ) An inorganic-filled polyolefin-based resin composition is provided, which is characterized in that it contains a phosphoric acid ester having the following as a main component. In addition to the components shown in the general formula above, the general formula

A phosphoric acid ester represented by the formula (where R ₅ is H or R ₄ O (R ₁ O) _n group) may be blended. These phosphoric acid esters can be synthesized by a conventionally known phosphoric acid esterification method, and typical synthetic examples will be described below. That is, the general formula

The compound represented by the formula and phosphoric anhydride are mixed at a molar ratio of 3/1 to 1/1 at a temperature of 30°C.
~100℃ Preferably, the reaction is carried out at a temperature of 40℃ to 70℃, and if necessary, R ₄ OH is used at a ratio of 3/1 to 1/1 to phosphoric anhydride at a temperature of 30 to 100℃, preferably. Manufactured by reaction at 40-70°C. Also, the general formula

It is also possible to mix the compound represented by the formula and R ₄ OH in advance and react with phosphoric anhydride. Furthermore, in order to prevent polymerization during the reaction, a polymerization inhibitor may be added if necessary. Also,

The mixing ratio of [Formula] and R ₄ OH is

[Formula] and To,

It is preferable to select so that the production ratio of [Formula] is 1/1 or more. Furthermore, there is no problem in separately synthesizing and blending these phosphoric acid esters. Specific examples of alcohols used in the production of these phosphoric acid esters include the following. First, the general formula

[Formula] includes ethylene oxide adducts of acrylic acid, propylene oxide and butylene oxide adducts, random or block co-adducts of these alkylene oxides, ethylene oxide adducts of methacrylic acid, propylene oxide and butylene oxide adducts, and these. Examples include random or block coadducts of alkylene oxide. In addition, R ₄ O (R ₁ O) _n H includes butyl alcohol, lauryl alcohol, dova 2.3 alcohol,
Examples include oleyl alcohol, ethylene oxide, propylene oxide, and butylene oxide adducts thereof, and ethylene oxide, propylene oxide, and butylene oxide adducts of t-butylphenol, menylphenol, and octylphenol. Further, examples of the inorganic substances used in the present invention include calcium carbonate, clay, talc, gypsum, calcium sulfite, aluminum hydroxide, magnesium hydroxide, zinc oxide, mica, and quartz powder. In addition, the polyolefin resin mentioned here is
Examples include polyethylene, ethylene vinyl acetate resin, polypropylene, polyvinyl chloride, polystyrene, styrene-acrylic resin, and the like. In the present invention, by blending phosphoric acid esters with inorganic compounds, it is possible to increase the filling of polyolefin resins and improve the physical properties of the resin. The impact strength and melt strength that are said to be
It has the surprising feature of actually improving index, elongation, tensile strength, etc. The reason why various physical properties are improved by blending the phosphoric acid esters of the present invention with an inorganic compound is that the inorganic compound improves the filling properties and dispersibility of the inorganic compound into the polyolefin resin based on the fact that it is a phosphoric acid ester. The reason for this is presumed to be an improvement in the adhesive strength between the inorganic compound and the polyolefin resin due to its reactivity. When blending with an inorganic compound, it is preferable to perform high-speed fluid mixing using a Henschel mixer. Further, the inorganic compound thus mixed is heated and kneaded with the polyolefin resin, and at this time, a general heating kneading device such as an extruder, kneader, Banbury mixer, or mixing roll is used. The heating temperature is selected taking into consideration the polyolefin resin, the functions of the kneading equipment, etc., but generally the temperature
A temperature range of 130°C to 300°C, more preferably 150°C to 280°C is suitable. In addition to the above, the polyolefin composition of the present invention also includes stabilizers, plasticizers, lubricants, radical initiators, pigments,
An antistatic agent, a flame retardant, a foaming agent, and other additives may also be included. Furthermore, when aluminum hydroxide or magnesium hydroxide is used as the inorganic material, flame retardance can be imparted in addition to mechanical strength. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the Examples. Example 1 Phosphate esters (A to E) to be used in the composition of the present invention were synthesized using the blending ratios of raw materials shown in Table 1.

【table】

[Table] For both A to E, all raw materials except phosphoric anhydride were prepared in advance, and phosphoric anhydride was gradually added dropwise at a temperature of 40℃.
The preparation is completed in 1 hour at 70°C, and then the reaction is carried out at 70°C for 3 hours. Example 2 Various inorganic compounds and phosphoric acid esters were blended in the following various blends. All formulations were made in a Henschel mixer at room temperature.
High speed flow mixing was performed for minutes. Examples of formulations are shown in Table 2.

[Table] Example 3 10 to 40 parts of polypropylene (same as Showa Yuka Showa Aroma MA410 and below) of 1.0 kg was blended into compound G, kneaded for 5 minutes at 180 to 190°C in a Banbury mixer, and pelletized. A test piece was prepared by extrusion molding, and the Izod impact strength was measured. For comparison, a polypropylene blended with an unblended inorganic substance (comparative product) was also measured, and the relationship between the Izot impact strength and the filling concentration of the product of the present invention and the comparative product is shown in FIG. As is clear from FIG. 1, it can be confirmed that the product of the present invention greatly increases the impact strength of the resin. Example 4 100 parts by weight of medium density polyethylene (Neozex 2006H manufactured by Mitsui Petrochemicals) was kneaded with 150 parts by weight of blended product J using a mixing roll, a 1 mm test piece was prepared using a hot press, and the test piece was tested using a Tensilon type tester. The tensile properties were investigated. Similarly, combination products
M150 parts by weight were similarly tested. The results are shown in Table 3.

[Table] Example 5 Compound H1Kg, polypropylene 1Kg, 1,2 polybutadiene (RB820 made by Japan Synthetic Rubber) 0.02Kg,
0.4 g of dicumyl peroxide was blended and heated and kneaded for 5 minutes at 180°C to 190°C in a Banbury mixer. A test piece was prepared by pelletizing and injection molding, and the bending strength, bending modulus, tensile strength, and impact strength were measured. Similarly, formulations I and M as well as untreated calcium carbonate were tested at similar consumption rates. The results are shown in Table 4. As is clear from Table 4, good results are shown in terms of tensile strength and impact strength.

【table】 [Brief explanation of the drawing]

FIG. 1 is a graph showing the relationship between the Izot impact strength and the filling concentration of the inventive product and the comparative product in Example 3.

Claims (1)

[Claims] 1. Based on 100 parts by weight of polyolefin resin,
In a polyolefin resin composition comprising 10 to 300 parts by weight of a powdered inorganic compound and, if necessary, various additives in desired amounts, 1 to 50 parts by weight per 100 parts by weight of the inorganic compound. The general formula for (However, in the formula, R is H or a methyl group, R ₁ is a -CH ₂ CH ₂ group, [Formula] group, or [Formula] group, or a mixture thereof, and R ₂ is an OH group. ,
[Formula] or indicates OR ₃ . Note that R ₃ is represented by the general formula (R ₁ O)mOR ₄ , and R ₄
is a residue of a saturated or unsaturated alkyl phenol having 3 to 18 carbon atoms, or a saturated or unsaturated alkylphenol having 1 to 12 carbon atoms. Further, n is an integer of 1 to 50, and m is 0 or an integer of 1 to 50. ) An inorganic-filled polyolefin resin composition characterized in that it contains a phosphoric ester having the following phosphoric ester as a main component.