JPS6253357A - Stabilized polyethylene composition - Google Patents

Abstract

PURPOSE:To provide a stabilized polyethylene composition having remarkably improved thermal deterioration resistance, by compounding a polyethylene with an inorganic filler, a metal, a metal oxide or a pigment, and adding a compound having cyanato group to the obtained polyethylene composition. CONSTITUTION:A polyethylene is compounded with a inorganic filler (e.g. calcium carbonate, magnesium hydroxide, etc.), a metal (e.g. copper, iron, cobalt, etc.), a metal oxide (e.g. copper oxide, antimony trioxide, etc.) or a pigment (e.g. copper phthalocyanine, chrome yellow, etc.) and if necessary other additive. The obtained composition is added with monofunctional or polyfunctional cyanic acid ester compound having one or more cyanato groups in the molecule [e.g. monocyanatobenzene, 2,2-bis(4-cyanatophenyl)propane, etc.]. The amount of the cyanato compound is 0.1-10wt% based on the polyethylene.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel stabilized polyethylene composition containing inorganic fillers, metals, metal oxides or pigments.

[Conventional technology and its problems]

Polyethylene is used as a general-purpose plastic for a variety of purposes, from general consumption materials to industrial materials. However, it is susceptible to deterioration due to ultraviolet rays and heat, and this deterioration is caused by the presence of inorganic fillers, metals, metal oxides, or pigments. There were issues promoted below.

Conventionally, as a method for this stabilization, a method of blending organic phosphoric acid or phosphite compounds or antioxidants such as sterically hindered phenols has been known.

The present invention provides a novel stabilized polyethylene composition that can significantly prevent the decomposition and oxidative deterioration of polyethylene even when additives such as inorganic fillers, metals, metal oxides, or pigments are added. This is what we discovered.

[Means for solving problems]

As a result of various studies on the utilization of the unique properties of cyanato groups in compounds having cyanato groups <-0-, miN), the present invention has developed a polyethylene film containing inorganic fillers, metals, metal oxides, or pigments. This work was completed based on the discovery that the thermal deterioration properties of polyethylene compositions can be significantly improved by adding a compound having a cyanato group to the compositions.

That is, the present invention provides a polyethylene composition containing an inorganic filler, a metal, a metal oxide, or a pigment, and a monofunctional or polyfunctional cyanate ester compound containing one or more cyanato groups in the molecule. It is a stabilized polyethylene composition formed by mixing 0.1 to 10% by weight.

The present invention will be explained below.

The polyethylene of the present invention (hereinafter referred to as rPEl) is a mixture of various additives explained in the next section, and includes low density PE, medium density PE, high density PE, and LLPE (linear
low-density PE), etc. Furthermore, these PEs are combined with polypropylene,
Other polyolefins such as polyisobutylene, polyacetal resins, HIPs, AS, ABS, etc.
Aromatic vinyl copolymers represented by MAS, MBS, MABS, etc., polyphenylene ether resins and mixtures of these and aromatic vinyl copolymers, polysulfone resins, polytetrafluoroethylene, coumaroindene These are resin compositions containing resins and the like; and compositions containing plasticizers, flame retardants, ultraviolet absorbers, stabilizers, etc. other than the additives described in the next section.

The inorganic fillers added to the PE of the present invention include calcium carbonate, magnesium hydroxide, aluminum hydroxide,
Calcium hydroxide, talc, clay, mica, wollastonite, etc. Metals include copper, iron, cobal l-,
Powders, fibers, flakes, etc. of nickel, chromium, manganese, aluminum, manganese, or alloys of these metals.Metal oxides include powders, fibers, etc. of copper oxide, iron oxide, antimony trioxide, lead oxide, etc. , flakes, etc., and examples of pigments include organic compounds such as copper phthalocyanine (phthalocyanine blue), yellow lead, mineral violet, carbon blank, red iron, ultramarine blue, cobalt blue, cobalt violet, and titanium white. These include metal oxides and metal composite oxides. PE of these additives
The amount added is the usual amount, which is about 5 to 70% for inorganic fillers and 0.01 to 5% for pigments.
used in moderate amounts. Incidentally, the PE composition of the present invention naturally includes compositions in which fillers other than those similar to the fillers exemplified above, which are appropriately added to conventional PE, are used in combination.

Suitable monofunctional or polyfunctional cyanate ester compounds containing one or more cyanato groups in the molecule of the present invention to be added as a stabilizer to the PE composition consisting of the above components are of the following general formula (11 General formula (1): R(OCN)m -----=(1) (m in the formula is 1
The above is usually an integer of 5 or less, R2 is an aromatic organic group, and the cyanato group is bonded to the aromatic ring of the organic group. Specific examples include monocyanatobenzene, alkylcyanatobenzene such as P-tert-butylcyanatobenzene, monocyanatonaphthalene, 1,3- or 1,4-dicyanatobenzene, 1,
3.5-) lycyanatobenzene, 1.3-. 1.4-
.

1.6-, L8-. 2.6- or 2.7-dicyanatonaphthalene, 1.3.6-1-dicyanatonaphthalene, 4
, 4'-dicyanatobiphenyl, bis(4-dicyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)pronogne, 2,2-bis(3,5-dichloro-4
-cyanatophenyl)propane, 2,2-bis(3,5
-dibromo-4-cyanatophenyl)propane, bis(
4-cyanatophenyl) ether, bis(4-cyanatophenyl) thioether, bis(4-cyanatophenyl) sulfone, tris(4-cyanatophenyl) phosphite, tris(4-cyanatophenyl) phosphate,
and cyanate esters obtained by the reaction of novolak with cyanogen halides. In addition to these, Tokuko Sho 41-1928, Sho 43-18468, Sho 44-
4791, 45-11712, 46-/11112
, 47-26853 and JP-A-51-63149 may also be used.

In addition, in the molecule obtained by polymerizing the above-mentioned polyfunctional cyanate ester in the presence of mineral acids, Lewis acids, salts such as sodium carbonate or lithium chloride, phosphate esters such as tributylphosphine, organic metal salts, etc. It can be used as a prepolymer having a cyanato group, and it can also be used as a prepolymer with an amine.

The amount of the cyanate ester compound of the present invention explained above in PE is not particularly limited, but from the viewpoint of effectiveness, it is 0.
It is in the range of 1 to 10% by weight, and monomers are more effective because they have a larger number of functional groups (-0CN groups) per unit weight.

If the amount added is less than 0.1%, the stabilizing effect is insufficient, and if it is used in an amount exceeding 10%, it shows a remarkable effect in preventing deterioration, but other properties such as a decrease in the elongation of PE are This is not desirable as it will damage it.

Furthermore, as explained above, it is presumed that a cyanato group is necessary for the effect of the present invention to be expressed, and additives that react with this functional group, such as -011, -COOH, -N
When it is necessary to add a compound having l2, -COOM, -3t1, etc. (former metal atom), it is preferable to avoid mixing the cyanate ester compound and these compounds in advance before adding them.

The method of mixing the cyanate ester compound into the PE composition of the present invention is generally not particularly limited as long as the cyanate ester compound is uniformly dispersed. for example,
A method in which the above components are mixed in a blender or other means and made into pellets with an extruder, a method in which they are mixed with PE as a solution and dried, a method in which they are mixed in a kneader, a Henschel mixer, etc. and made into pellets as is or by extrusion, and addition. The additives of the present invention and the cyanate ester compound are mixed in advance, heat treated as necessary to form a semi-cured or cured film of the cyanate ester compound on the surface of the additive component, and this and PE are mixed together. Methods such as mixing and extruding, and methods such as the masterbatch method in which a high concentration masterbatch is produced and mixed are also suitable, and as for the mixing conditions, in the case of an extruder, the extrusion conditions for PE can be used as they are. In other cases, it is sufficient to mix at room temperature or under heating, and the mixing time depends on the relationship with the temperature, but at 170 to 250"C.
The effect of the present invention can be maintained even by mixing for about 2 to 3 hours at a temperature of about 100 to 100 mL, so there is no particular limitation, but a method that causes less reaction of the cyanato groups in the cyanate ester compound is more preferable. However, under conditions that allow uniform mixing, it is preferable to use a shorter time.

〔Example〕

The present invention will be explained below with reference to Examples.

Example-1 Low-density PE (manufactured by Mitsubishi Yuka Okiku, product name: MS 30) was added with the filler listed in Table 1 and 2,2-bis(4-cyanatophenyl)propane (hereinafter referred to as rBP^-CNJ). written as)
was added in the amount shown in Table 1 and kneaded in a kneader for 13 minutes at a temperature of 170"C. This mixture was press-molded to make a flat plate with a thickness of 2. The results are shown in Table 1. Example 2 The same PE as in Example 1 was coated with the pigments listed in Table 2 and 1
．． A flat plate was prepared and the physical properties were measured in the same manner as in Example 1, except that 4-dicyanatohenzene (hereinafter referred to as rHQ-CN J) was added.

The results are shown in Table 2.

Table 2 Example-3 High-density PE (Mitsubishi Yuka A Nursing Co., Ltd., product name 1JXI "c. After kneading in a kneader for 3 minutes, this mixture was press-molded to a thickness of 21".
A flat plate of the seal was prepared, and its strength and elongation were measured under normal conditions and after a 120°C deterioration test.

The results are shown in Table 3.

[Operation and effects of the invention]

As is clear from the above detailed description and Examples 1 to 3, the composition of the present invention has an effect of preventing thermal decomposition, an original color tone of the pigment seen in pigmented compositions, an effect of preventing thermal decomposition, etc. It can be seen that the composition significantly improves thermal deterioration and is extremely excellent in practical use.

Claims (1)

[Claims] 0.1 to 10 weight of a monofunctional or polyfunctional cyanate ester compound containing one or more cyanato groups in the molecule is added to a polyethylene composition containing an inorganic filler, a metal, a metal oxide, or a pigment. % stabilized polyethylene composition.