JPS58118838A - Novel polyolefinic composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel polyolefin-based compositions and to the uses of these compositions.

Polyolein (polyethylene, polypropylene, etc.)
can be used advantageously in a large number of applications.

However, these polyolefins have limited properties such as shock resistance, dye affinity, paintability or antistatic properties.
*It is known that the desired type of use is not completely satisfactory.

Therefore, articles obtained by molding, extrusion or injection molding of polyolefins, such as chains,
There has been a long-standing desire to improve the shock resistance of materials intended for use in the automobile and electrical appliance manufacturing industries. Furthermore, attempts have been made to improve the dyeing affinity and paintability of these materials so that they can be used in industrial and decorative applications. Furthermore, for many years there has been a desire to dye certain polyolefins, which have not been dyed satisfactorily to date.

The aim of the invention is to overcome the above-mentioned drawbacks. Fact 1: The present invention can impart shock resistance to new polyolefin-based products, thereby expanding the scope of use of polyolefins. moreover.

The invention makes it possible to obtain polyolefin-based products having various coloring properties and improved antistatic properties.

The present invention provides compositions which are completely miscible with the specified compounds of which the polyolefins are comprised and which are comprised of mixtures of polyolefins and these compounds.

This is based on the present unexpected finding that they exhibit improved shock resistance at low temperatures, as well as improved staining affinity and antistatic properties.

The present invention relates to polyolefins of one kind or several S (herein, "one or more kinds" means @two or more kinds).

consisting of an intimate mixture of one or more polyetheresters, optionally containing organic or inorganic fillers, said mixture containing 1 to 99% by weight of polyolefin and 99-1% by weight of y. The present invention relates to a composition comprising polyether ester ide.

Polyether ester and here refers not only to random polyether ester eyed (i.e., formed by random chains of various monomer components) but also to polyether ester eyed (i.e., polyether ester eyed and block bodies formed by various components in a predetermined manner). V formed by a block with a chain length) is also meant.

As is well known, polyether ester asdo is a copolycondensation product of a polyamide block with one reactive end and a polyether with a reactive end, such as in particular: The product (by cyanoethylation and hydrogenation of the polyether diol) with either a polyether diol block or a polyether diamine block containing a polyether diol blocked α,ω-dihydroxyl polyoxyalkylene with a
Mention may be made of the products of polyamide blocks with non-chain ends and polyether blocks with carboxyl chain ends.

These products are described in French patents 74-18,913 and 77-261,678.

6.6.6.1 According to the 14-body example of the present invention, the boria ζ-doblock of polyetherester eyed
2.11 or 12 Borian denominated dollars (PA-6, PA-1
1% PA-6.6. Preferably, the molecular weight of these polyand blocks is 500-10,000. Particularly preferred tL< is 1,000 to 5,000.

According to another embodiment of the invention, the polyether block is polytetramethylene glycol (PTMG).

It is made of polypropylene glycol (PPG) or polyethylene glycol (PEG).

Preferably, the polyether has a molecular weight of 150 to 5.00.
0. % tL< is 400-3,000.

According to another variant of the invention, the polyether ester eyes described above are composed of polyether of 5-851 1c 3O-SOW and 95-15% of polyamide, preferably To-20*.

Examples of polyolefins used in the present invention include polypropylene (pp), polyethylene (PE), mixtures or copolymers thereof, or 8urlyn from DuPont.
An example is an ionomer resin sold under the name (registered trademark).

Preferably, the mixture of polyolefin and polyether ester Az-P is comprised of 70-97% polyolefin and 30-3x polyether ester Az-P.

Organic or inorganic fillers that the composition may contain include, for example, silica, titanium dioxide, talc, mica, kaolin,!
gnesia, glass fiber, carbon black, vermiculite,
Standard fillers used in conjunction with polymeric compositions can be used, such as glass beads, calcium oxide, carbon fibers, and the like.

Of course, the compositions may also contain standard additives such as UV inhibitors, light and heat stabilizers, mold release agents, and the like.

The method for obtaining these compositions is to process a mixture of the raw materials in dry powder or granular form and to process the resulting mixture in a single or double screw extruder or mixer, such as a Banbury® or in a pass (registered trademark) or even in a calendaring device such as, for example, a screw rolling machine. Additionally, before extrusion or injection.

Mechanical mixing operations can also be carried out in the hollow/Q-hole of an extruder injection press.

A further aspect of the invention relates to the use of said compositions for the manufacture of shock resistant and antistatic articles, particularly by in-mold molding, extrusion, injection molding and the like. Furthermore, the present invention relates to manufactured articles obtained from said compositions, such as tubes, films, casings, and further colored or painted manufactured articles obtained from these compositions.Other objects and advantages of the present invention are described below and It will become clear from the non-limiting examples.

Examples 1-4 Operation vCarried out in a double-screw W@rn@r Pfl*ld*r@r extruder with screw rotation speed of 50 rpm.

The flow rate of the extruder was 2019/h. The temperature gradient of the extruder is 225-230-240-2 from the inlet to the outlet t.
The temperature was 30°C.

In these examples, the polyolefin is ATOC
30208 manufactured and sold by HIMIE
N-tertiary homopolymer polypropylene was used, and its melt index (M, I,) was 8. (Load 5
Measured under boiling water at a temperature of 230°C).

The polyether ester ide used was made from 30% FA-12 having a molecular weight of about 850 and 70% PTMG having a molecular weight of about 2.000.

In each of the compositions of Examples 1 to 4, the weight ratio of polyolein/polyetheresteramide was 9515.
90/10.85/15-J3 and 80/20.

The physical properties of test samples obtained from these compositions were determined and the results are shown in Table 1.

Example 5 50 of PA-12 with a molecular weight of 2.000, which is the same polyolein as the polyolein used in Examples 1 to 4.
% and a molecular weight of 2.000 (D) was mixed with polyether ester amyl prepared from PTMG and 50y. This mixing was carried out according to the same procedure as in Examples 1-4.
and under the same conditions.

The weight ratio of polypropylene/polyether ester ζr was 90/10.

The physical properties of the compositions measured on test samples obtained from these compositions are shown in Table 1.

Examples 6-7 The same polyolefin (3
0208N-tertiary polypropylene) V was used and under the same mixing operating conditions.

60% of PA-6 with a molecular weight of about 1.300 and about 6
9 polypropylene/mixed with a polyether ester amide composed of 32% PPG with a molecular weight of 0.00
The weight ratio of polyether ester aodo is 90/90/
l O (!!Example 69) and 85/15 (Example 7
).

Physical properties measured on test samples obtained from these compositions are shown in Table Vllll1.

Example 8 The operating conditions were the same as those described in Example 5, except that the polyether ester and used had a molecular weight of 1,500
C) PA-goso* and PEG3 with a molecular weight of approximately 1,500
It was composed of 0%.

The physical properties measured on test samples obtained from these compositions are shown in Table 1.

Example 9 (Reference example) The operation was carried out under the same conditions as in Examples 1 to 4, but
This time no polyether ester was added to the olefin used, and the olefin used was a Pukupyre/monopolymer sold by ATOCHIMHC under the name 30208N-3.

Physical properties determined for the test samples are shown in Table V.

The operation was carried out in the same manner as in Examples 1 to 40 Hatai, but this time polyether ester and was not added and 3040
The 4111 table of the ATOC1 ("HINO-SHOCK" class, sold by IMIK under the name MN6, is shown in Examples 1 to 10).
1 shows the results of measurements carried out on test samples obtained from compositions according to the present invention.

Analysis of these results, taking into account experimental errors, shows that: e The Shore hardness of the test samples obtained from the composition according to the invention is, on average, the Shore hardness of the polypropylene homopolymer of Reference Example 9. and "High No Shock" of Reference Example 10
The Shore hardness is lower than that of polypropylene copolymer.

- Vinyl of the test sample composed of the composition according to the invention /
7-(VICAT)11 degrees is between the "VICAT temperature of the hypershock j copolymer of Reference Example 1O" and the VICAT temperature of the homopolymer of Reference Example 9.

- The bending warpage elongation of the test sample of the composition according to Examples 1-8 is a value between the bending warpage elongation of the test sample of the "Hi No Shock" copolymer of Reference Example 10 and the homopolymer of Reference Example 9. It is.

- The density of the compositions according to Examples 1 to 8 was higher than that of Reference Examples 9 and 100 density.

- The shock resistance at 23°C and 0°C in the samples of Examples 1-8 is clearly higher than that of the test sample of Reference Example 9 and most of the test samples of Reference Example 10.

Additionally, measurements of antistatic properties were carried out on molded articles obtained from the compositions according to Examples 1-1O.

Evaluation tests for antistatic properties are carried out under the same conditions under which electrostatic charges are generated by friction and the generated current is applied to a cigarette ash test (c).
The result was 0 when evaluated by igaret@ash test).

Considering experimental errors, the products of Examples 1-8 are:

It was observed that it exhibited significantly higher antistatic properties than the products of Reference Examples 9 and 10.

Furthermore, the compositions of Examples 1 to 10 were used to fabricate a cabinet (housing) for a radio receiver.

The cabinet of these receivers is 80℃ in the dyeing container.
into an acetic acid-containing water bath solution. This acetic acid-containing aqueous solution had the following composition: oAJL') Macid Plue... River... 3xa 7. f f )-
Le LT・・・・River・・・・・・・ 0.1*・
Add 8ox acetic acid at PE5.

After soaking for 1 hour, the cabinet was removed from the container and cleaned.

It was clearly shown below that the housings obtained from the compositions of Reference Example 9 and 1O were not dyed, that is, the dye was not fixed to the Yabinet constituent material. On the other hand, Examples 1 to 11
The housing obtained from composition No. 8 was colored deep blue.

Examples 11-15 The same procedure as in Examples 1-4 was followed, and the polyolefin-containing compositions were prepared using LACQTENE® 1055 MN-20 (high pressure, low density polyethylene manufactured by ATOCHIMIE) and Table 2. Table 2 also shows the weight ratio of PLACQTENE®/polyether ester amide.

measuring the physical properties of products obtained from these compositions;
Compared to LAQTINE (registered trademark) of Reference Example 15,
Products obtained from the compositions of Examples 11-14 t)
It was observed that the cookability, antistatic properties and dyeing affinity were clearly better.

Examples 16-19 The same mixtures as in Examples 2, 9, 11 and 15 respectively were prepared and to this was added a filler consisting of 30% (by weight) glass fibers having a length of about 1 m.

A cover for a radio set cabinet (housing) was made from these mixtures. These covers were coated with a coating layer V by spraying with a technical gray glycerophthalic acid lacquer. After drying.

Adhesive band test shows that the paint layer of Examples 16 and xs
It was observed that the paint layer adhered to the cover obtained from the oms product. In contrast, Reference Examples 17 and 19
(Each pure polypropylene filled with glass plate TMV (
Formed from Example 9) and pure polyethylene (Example 15)], the coating layer was
It lacked the property of being fixed.

Of course, the invention is not limited only to the embodiments described above, and many modifications can be made by those skilled in the art without departing from the spirit of the invention.

In this specification, for convenience, the common names polytetramethylene glycol, polyethylene glycol, and polypropylene glycol are used instead of the official names polyoxytetramethylene glycol, polyoxyethylene glycol, and polyoxyV-f' propylene glycol. It was used.

Sakurijin Benzorishi Imamura Moto

Claims (1)

Claims: (1) consisting of an intimate mixture of one or more polyolefins 6111 or more polyetheresteramides, said mixture comprising 1 to 99 weight y of polyolefin and 99-1 weight X of polyolefin; A novel composition comprising an ether ester amide. (2) The composition according to claim 1, wherein the polyether ester amide is a random polyether ester amide. (3) The terether ester amide is composed of a copolycondensation product composed of a block polyamide having one reactive end and a polyether block having a reactive end, for example, a boria having particularly at the end of the dicarboxyl chain 1111. d-blocked, polyether diol blocks or polyether cyan blocks (by cyanoethylation and hydrogenation of d?teriter diols);
2. The composition according to claim 1, comprising a copolycondensation product composed of a polyamide block having a diamino chain end and a polyether block having a carboxyl chain end. (4), 3? The polyamide blocks of riether ester and are preferably 6, 11, 6.6, 6.12 or 124 lyamide (PA-6, PA-11, FA-
6,6, FA-6, 12, PA-12) or produced from a copolyamide formed by copolycondensation of these monomers. The composition according to any one of the above. (5) The molecular weight of these polyamide blocks is 500
~10,000. 5. The composition according to claim 4, which has a molecular weight of 1,000 to 5,000. (6) Any one of claims 1 to 3, in which the polyether resin is polyoxyctetramethylene glycol (PTMG), polyoxypropylene glycol (PPG), or polyoxyethylene glycol (PEG). Compositions as described. (c) The composition according to claim 6, wherein the polyether has a molecular weight of 150 to 6%,000, particularly 400 to 3,000. ~80% polyether and 95-15X especially 70
7. A composition according to any one of claims 1 to 7, wherein the composition is formed from ~20% of boriad. (9) The polyolefin is polypropylene (pp), polyethylene (pg), a mixture or copolymer thereof, or an ionomer resin sold under the name 8URLYN (registered trademark) by Dain Co., Ltd. The composition according to any one of items 1 to 8. Q(I) A composition according to any one of claims 1 to 9, wherein the mixture is formed from 70 to 97% polyolefin and to 3x polyether ester. αυ For example, silica , titanium difluoride, talc, mica,
Kaolin! Organic or inorganic fillers such as gnesia, glass fibers, carbon black, vermiculite, glass beads, calcium carbonate, carbon fibers and optionally additives such as UV inhibitors, heat or light stabilizers, and release agents. The composition according to any one of claims 1 to 9, containing an additive. 4I Claim 1 for obtaining a processed article 1 exhibiting a high degree of shock resistance and improved antistatic properties.
Use of the composition according to any of Items 1 to 1O. Processed articles obtained from the compositions according to any of claims 1 to 1O, which exhibit high VWI resistance and improved antistatic properties! Take other products.