JP2588325B2 - Inorganic highly filled resin composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly inorganic-filled composition, and more particularly, to a highly-inorganic polyolefin resin composition suitable for a building material field represented by a folded plate and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, it is a known technique to use a composition in which a polyolefin-based resin is filled with an inorganic powder in a field requiring flame retardancy such as a building material (Japanese Patent Publication No. 62-16217). JP-B-56-51181, JP-A-59-81345, JP-A-1-126346.
issue). In these prior arts, there is an example in which a polyolefin resin is highly filled with an inorganic powder to obtain flame retardancy, and a flame retardant is further added to improve the flame retardant effect.
In addition, a foaming agent may be added to these inorganic filling compositions to form a crosslinked foam.

By the way, if a low crystalline resin such as ethylene-vinyl acetate copolymer (EVA) or the like is used as the polyolefin resin in order to highly fill the inorganic powder, processing is difficult because the polymer has adhesiveness. is there. Even when ultra-low-density polyethylene (VLDPE) or the like is used, the processing is still not easy because the filled composition having high lubricity is relatively inferior. In addition, the highly filled composition imposes a large torque load during kneading due to the oil absorption of the filled material. Therefore, when silicone oil is added to reduce the tackiness and torque during kneading, the silicone oil bleeds out to the surface of the resin composition in a short time, as if the silicone oil was applied to the surface. A silicone oil film occurs. The bleed-out silicone oil film adheres and contaminates when it comes into contact with other substances. In addition, the bleed out of the silicone oil impairs the appearance of the molded product.

On the other hand, it has been proposed to add an organopolysiloxane polymer to a polyolefin resin composition highly filled with inorganic powder (Japanese Patent Publication No. 59-301).
No. 78). Addition of the organopolysiloxane polymer is expected to improve the lubrication properties at the interface between the inorganic powder and the polyolefin resin and the lubricity of the molded product. There is difficulty in sex. Organopolysiloxane polymers have poor compatibility with polyolefin-based resins, and require a long time for kneading in order to be highly dispersed.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to improve the lubricity at the interface between a highly filled inorganic powder and a polyolefin resin and the tackiness of a polymer, thereby improving the processability and the lubricity imparting component. And to provide a modified inorganic highly-filled resin composition.

The present inventors have conducted intensive studies to overcome the problems of the prior art, and as a result,
One end or both ends, methacryl group, carbinol
Group, amino group, carboxyl group, epoxy group, mercap
It has been found that by using a silicone oil having a functional group selected from the group consisting of a phenol group and a phenol group , the torque during kneading can be reduced and the dispersibility of the filler and the resin can be improved. Moreover, by performing chemical crosslinking or irradiation crosslinking with ionizing radiation, bleed-out of the silicone oil can be prevented, and the physical properties of the resin composition can be improved. The present invention has been completed based on these findings.

[0007]

According to the present invention, (a)
100 parts by weight of a polyolefin resin, (b) 50 to 500 parts by weight of an inorganic powder, and (c) one or both ends,
Methacrylic group, carbinol group, amino group, carboxy
From phenol, epoxy, mercapto and phenol groups
The present invention provides an inorganic high-fill composition containing 0.1 to 15 parts by weight of a silicone oil having a functional group selected from the group consisting of:

Further, according to the present invention, (a) 100 parts by weight of a polyolefin resin, (b) inorganic powders 50 to 5
00 parts by weight and (c) methacrylic acid on one or both ends.
Groups, carbinol groups, amino groups, carboxyl groups,
A group consisting of a oxy group, a mercapto group and a phenol group
Silicone oil having a functional group selected from 0.1 to 1
The present invention provides a method for producing an inorganic highly-filled composition, characterized in that after 5 parts by weight, the composition is crosslinked by irradiation with chemical crosslinking or ionizing radiation.

Hereinafter, the present invention will be described in detail. The silicone oil used in the present invention is a dimethylpolysiloxane having a reactive functional group at one or both terminals represented by the following general formula [1] or [2].

[0010]

[0011]

[0012] In the above general formula [1] and [2], R is main
Tacryl group, carbinol group, amino group, carboxyl
Group, epoxy group, mercapto group and phenol group.
Represents a functional group selected from the group Among these functional groups, a methacryl group is preferable.

When a silicone oil having a functional group is added to a resin composition, a part functions as an external lubricant, and the other part exists at an interface between the inorganic powder and the resin to provide lubricity. And, compared with the case where an organopolysiloxane polymer is added, it is advantageous in terms of torque and dispersion, and a lubricating effect can be obtained.

When the resin composition is chemically cross-linked or cross-linked by irradiation with ionizing radiation (electron beam, α-ray, β-ray, γ-ray, etc.), it is possible to prevent the bleed out of silicone oil, which has been a conventional problem. Not only can be obtained, but also the functions (impact resistance, flexibility, water repellency, etc.) of the resin composition can be improved. It is presumed that the bleed-out is prevented because the functional group of the silicone oil having a functional group is bonded to, for example, the main chain or side chain of the polymer in these crosslinking steps.

The silicone oil having a functional group is added in the range of 0.1 to 15 parts by weight based on 100 parts by weight of the polyolefin resin. If the amount is less than 0.1 part by weight, the effect of imparting lubricity is small, and if it exceeds 15 parts by weight, the physical properties of the resin composition deteriorate.

As the polyolefin resin used in the present invention, for example, polyethylene (low density, medium to high density, linear low density, VLDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-acryl Ethyl acid copolymer, ethylene-acrylic acid copolymer, ethylene-α
-Olefin copolymer, polypropylene, propylene-
Butene copolymers, ethylene-propylene copolymers, and mixtures thereof.

Examples of the inorganic powder include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, tin oxide hydrate, basic magnesium carbonate, hydrotalcite, heart crew, talc, mica and the like. Examples thereof include hydrated metal oxides and mixtures thereof. The mixing ratio of the inorganic powder is 50 to 500 parts by weight, preferably 50 to 350 parts by weight, based on 100 parts by weight of the polyolefin resin. If the amount is less than 50 parts by weight, the flame retarding effect due to the addition of the inorganic powder is small, and if it exceeds 500 parts by weight, the moldability and physical properties are reduced.

A higher flame retardancy can be imparted to the composition of the present invention by appropriately adding a flame retardant and a flame retardant auxiliary.
Examples of the flame retardant include decabromodiphenyl ether, pentabromochlorocyclohexane, hexabromocyclododecane, 2,3,5,6-pentabromoethylbenzene, 1,2-bis (2,4,5-tribromophenoxy) ethane And halogenated flame retardants such as chlorinated paraffin, hexachloropentacyclodecane, hexabromobenzene, and tetrabromobisphenol A / derivative. Examples of the flame retardant aid include antimony trioxide, sodium antimonate, tin oxide, and red phosphorus. When these flame retardants are used, the amount is usually 3 to 30 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the polyolefin resin. When a flame retardant aid is used, it is usually 1 to 20 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the polyolefin resin.

The composition of the present invention may be added with a foaming agent, subjected to chemical crosslinking or crosslinking by irradiation with ionizing radiation, and foamed by heating to form a foam.

[0020]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples.

Example 1 5 parts by weight of trimethylpolysiloxane having a methacrylic group at one end per 100 parts by weight of commercially available polyethylene (density 0.923, MI = 2.0) and 100 parts by weight of magnesium hydroxide Was added.
This composition was sufficiently kneaded with two rolls heated to 130 ° C., and then pressed into a plate having a thickness of 3 mm. On the other hand, for comparison, a plate-like molded product was prepared in the same manner as described above except that the silicone oil having a functional group was not added.

Observation of the surfaces of the obtained two types of plate-like molded products showed that the one to which silicone oil having a functional group was added was more beautiful.

[Example 2] Polyethylene (density 0.92)
3, MI = 2.0) 100 parts by weight of magnesium hydroxide and 100 parts by weight of magnesium hydroxide were added with 5 parts by weight of trimethylpolysiloxane having a methacryl group at one end, and roll-mixed, followed by hot pressing to form a plate. Created things. This plate-like molded product was irradiated with an electron beam at a dose of 5 Mrad. On the other hand, for comparison, a plate-like molded product was obtained in the same manner as described above, except that trimethylpolysiloxane having no functional group was added, and was similarly irradiated with an electron beam.

In the plate-like molded product to which trimethylpolysiloxane having no functional group was added, a silicone oil layer as if silicone oil was applied was clearly observed on the surface after 48 hours. No such bleed-out was observed in the plate-like molded product to which trimethylpolysiloxane having the following was added.

Example 3 Ethylene-vinyl acetate copolymer (density 0.94, vinyl acetate content 25% by weight) 10
0 parts by weight and 100 parts by weight of magnesium hydroxide,
5 parts by weight of trimethylpolysiloxane having a methacryl group at one end was added and kneaded with two rolls heated to 130 ° C. On the other hand, for comparison, the mixture was kneaded with two rolls in the same manner as above except that the silicone oil having a functional group was not added.

The composition to which the silicone oil having a functional group was added could be easily kneaded, but the composition to which no silicone oil had been added adhered to the roll during kneading and was difficult to mold.

When the kneading operation was carried out with a 3 liter kneader-mixer instead of the two rolls, the composition containing the silicone oil having a functional group could be easily kneaded. The composition which was not present was difficult to discharge due to adhesion to the casing during kneading.

[0028]

According to the present invention, it is possible to provide a resin composition in which the interface characteristics between the inorganic powder and the resin are improved and the lubricity of the molded product is improved. In addition, by crosslinking, bleed-out of silicone oil can be prevented and the resin composition can be modified.

Claims (2)

(57) [Claims] (1) 100 parts by weight of a polyolefin resin, (b) 50 to 500 parts by weight of an inorganic powder, and (c) a methacrylic group, a carbinol group,
Amino group, carboxyl group, epoxy group, mercapto group
And an inorganic high-filling composition containing 0.1 to 15 parts by weight of a silicone oil having a functional group selected from the group consisting of phenol groups . 2. (a) 100 parts by weight of a polyolefin resin, (b) 50 to 500 parts by weight of an inorganic powder, and (c)
One end or both ends, methacryl group, carbinol
Group, amino group, carboxyl group, epoxy group, mercap
A high-inorganic composition, comprising 0.1 to 15 parts by weight of a silicone oil having a functional group selected from the group consisting of a thiol group and a phenol group , followed by chemical crosslinking or irradiation crosslinking with ionizing radiation. Method of manufacturing a product.