JPS6189239A - Polyolefin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition with improved plysical properties such as impact strength and enhanced surface processability such as coatability, by incorporating polyolefin with a specific amount of a graft copolymer prepared by grafting unsaturated dicarboxylic acid 9anhydride) to specific ethylene- propylene copolymer. CONSTITUTION:The objective composition can be obtained by incorporating (A) 99.9-80 (pref. 99-50) pts.wt. of a polyolefin (e.g., polyethylene) with (B) 0.1-70 (pref. 1-50) pts.wt. of a modified polymer prepared by grafting 1) 0.1-10wt% of an unsaturated carboxylic acid (anhydride) [e.g., maleic acid (anhydride)] to 2) crystalline and/or rubbery copolymer with an ethylene content 10-80wt% from ethylene and propylene (plus >=4C olefin), followed by kneading.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a polyolefin composition that improves the physical properties of polyolefin resin molded articles, such as high impact pressure, and also facilitates surface treatments such as painting, adhesion, flocking, printing, hot stamping, and plating. Regarding.

More specifically, the present invention relates to a polyolefin composition obtained by kneading a modified polymer obtained by graft copolymerizing an unsaturated dicarboxylic acid or its anhydride to a specific ethylene-propylene copolymer with a polyolefin.

Polyolefins have excellent mechanical properties such as rigidity and tensile strength, as well as excellent chemical resistance and processability, so they are used in a wide range of applications. Surface treatments such as flocking, printing, hot stamping, and plating are difficult, and various techniques have been devised. In particular, it has been studied and applied to modify the surface layer of molded polyolefin products by physical or chemical methods to modify the surface, but these methods require complicated processes and are difficult to process due to etching. Depending on the method, the molded product may be deformed or the effect may be insufficient, and the current situation is that satisfactory results cannot be obtained despite the high cost.

As a result of intensive studies by the present inventors to solve these problems, we have found that a modified polymer obtained by graft copolymerizing a specific ethylene-brobylene material has a remarkable effect of improving these surface treatments and also improves impact strength. We discovered this surprising result and arrived at the present invention.

That is, the present invention provides (1) 99.9 to 80 parts by weight of polyolefin, preferably 99 to 50 parts by weight, more preferably 95 to 60 parts by weight, and (2) ethylene and propylene with an ethylene content of 10 to 80 parts by weight. Alternatively, an unsaturated dicarboxylic acid or its anhydride is added to a crystalline and/or rubbery copolymer of these and an olefin having 4 or more carbon atoms (hereinafter referred to as ethylene-propylene copolymer). - A polyolefin composition comprising 0.1 to 70 fi, preferably 41 parts, preferably 1 to 50 parts by weight, and more preferably 5 to 40 parts by weight of a graft copolymerized modified polymer.

Typical polyolefins used in the present invention include polyethylene, polypropylene, ethylene-propylene copolymer, propylene-ethylene-butene terpolymer, ethylene-butene copolymer, polybutene-1, etc., and combinations thereof. can be mentioned.

In the present invention, these polyolefins are further mixed with a modified polymer obtained by graft copolymerizing ethylene-propylene copolymerized unsaturated dicarbonate or its anhydride to obtain a composition.

In this case, the ethylene content of the ethylene-propylene copolymer is preferably 10 to 80% by weight, preferably 12X, 10M amount $
If it is less than 7 parts by weight, the impact resistance will be poor, and if it is more than 800 parts by weight, the rigidity will decrease. Ethylene-propylene copolymers include block PP and ethylene-propylene rubber (El' rubber). Furthermore, BP rubber' includes ethylene-propylene rubber and ethylene-propylene-nonconjugated diene copolymer (EPDM). Further, olefins having 4 or more carbon atoms to be used together with ethylene and propylene resin include butene-1, pentene-1,4-methylhexene-1, etc., and these are effective in imparting viscosity.

The modified polymer used in the present invention can be prepared by dissolving an ethylene-propylene copolymer in an organic solvent, adding an unsaturated carboxylic acid or anhydride thereof, and a radical generator, stirring and heating, or adding each of the above components. It can be obtained by known methods such as feeding it into an extruder and performing graft copolymerization.

Examples of unsaturated dicarboxylic acids or anhydrides thereof that can be graft copolymerized with ethylene-propylene copolymers to obtain modified polymers include maleic acid, hymic acid, itaconic acid, maleic anhydride, himic anhydride, and itaconic anhydride. At least 1 a of a compound selected from the following is used.

The weight of this unsaturated dicarboxylic acid or its anhydride is 0.1 to 10% by weight in the total modified polymer. Poor effect, 10 again! If the amount exceeds the amount, the polarity may be too strong and it may not be well compatible with the polyolefin, which is not preferable.

In the composition of the present invention, if the amount of the modified polymer is less than 0.1 part by weight, the effect of improving surface workability and bullet resistance is poor, while if it is more than 70 parts by weight, the characteristic of the polyolefin is This is undesirable as it may result in a decrease in rigidity, tensile strength, etc. We have also found the surprising result that the modified polymer of Nouki EP rubber is more effective in improving the strength of polyolefins than unmodified EP rubber.

The above composition can be further improved in surface workability and resistance by adding one or more compounds selected from polyhydric alcohols, trimethylolpropane, 1,6-hexanediol, pentaerythritol, dipentaerythritol, etc., as necessary. Impact resistance etc. may be improved.

In addition, if necessary, styrene elastomers such as styrene-butadiene random copolymer and styrene-butadiene block copolymer, various fillers such as glass fiber, talc, wood flour, and calcium carbonate, antioxidants, and weathering agents are added. It is also possible to add additives such as.

Methods for kneading a modified polymer obtained by graft copolymerizing an unsaturated dicarboxylic acid or its anhydride to a polyolefined or ethylene-propylene copolymer include Banbury kneading, kneading, roll kneading, and l-shaft or twin-screw scree. Examples include continuous kneading.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Contains ethylene 150:! ji! % ethylene-propylene rubber (hereinafter abbreviated as EI'R) in toluene solution in the presence of peroxide at 155 °C.

EPR containing 5 weight portions of maleic anhydride (hereinafter abbreviated as MAEI) was synthesized. (This compound is hereinafter referred to as MAEi-modified E
PR-1) The MAEI modified EPR-120 phoenix part and ethylene-containing t
Ethylene with a melt index of 8 at 7.4 fifi
80 parts by weight of propylene block copolymer (hereinafter referred to as block PP) from Ikegai Iron Works! i! Cross-wire and granulate using a twin-screw extruder.

Then, an injection molded plate of 150)c90 x 2ss$ was produced using an injection molding machine.

Either the molded plate is not pretreated or the following 3.
After performing various pre-treatments, spray painting the urethane paint Flexene◆101 manufactured by Nippon Bee Chemical Co., Ltd.
Baking was performed at 120° C. for 80 minutes to dry.

Pre-treatment - (1.1.1- at 974°C) Steam for 80 seconds with lychloroethane vapor.

(hereinafter abbreviated as chlorocene treatment) t-ti) pHIB, 5 ortho-sodium silicate (
After immersing in Na8i04) aqueous solution at 60°C for 8 minutes while stirring the solution, wash with water.

(hereinafter abbreviated as alkaline degreasing treatment) I-■ Wipe the surface of the molded product with isopropyl alcohol.

(Hereinafter, abbreviated as solvent wiping) The initial adhesion and water resistance of the coated plate were evaluated. The results are shown in Table-1.

Table-1 Paint film physical property evaluation results (Note) Initial adhesion Nichiban Co., Ltd. (Remaining rate (4) evaluation (90°
2) Water resistance Adhesion test after 240 hr immersion in 40°C warm water As a result, no peeling was observed in any pretreatment in the cellophane tape peeling test, and adhesion was achieved even without an undercoat Comparative Example 1 MAEI Coating evaluation was performed in the same manner as in Example 1 except that modified EPR-1 was not added. (Block P
As a result, as shown in Table 2, there was no adhesion at all.

Comparative Example 2 MAH unmodified (unmodified) ethylene-propylene rubber (ethylene content f150M amount -0 or less, unmodified E
Coating evaluation was performed in the same manner as in Example-1, except that PR) was used.

The results are shown in Table-8.

As a result, there is almost no close contact.

Example 2 MAH double-layered EPR was synthesized from ethylene-containing EPR of 150% by weight at 155° C. in a toluene solution under a peroxide catalyst. (This compound is hereinafter referred to as MA 1ifi
The MAEIi EPIL-
2BON'lk part and PP70 heavy ff used in Example 1
Part i was cross-wired, granulated, and injection molded in the same manner as in Example 1, resulting in 150 x 90 x 2 vm* injection molding.
t. A shape plate was created.

After the molded plate was subjected to low-temperature plasma treatment as described below, it was spray-coated with urethane-based paint Flexene 101 manufactured by Nippon Bee Chemical Co., Ltd. in the same manner as in Example 1, and heated at 120°C.
, Baking for 80 minutes was followed by drying.

Low-temperature plasma treatment: Using a microwave plasma generator, treatment was performed so that the surface wetting tension of the molded plate surface was 48 to 50 tines/-.

(Hereinafter, abbreviated as plasma treatment) The initial adhesion and water resistance of the naval plate were evaluated in the same manner as in Example 1, and no peeling was observed.

Example 8 A propylene-ethylene block copolymer with an ethylene content of 14 times ns and a melt index of 2 was heated at 166°C in the presence of an AM compound in a toluene solution MA EI 2
7! A ts-containing PP was synthesized. (This compound is referred to as M
(referred to as Atl-modified PP) The above MAEI-modified PPgQii part and ethylene content 7.4
In the same manner as in Example 1, 70 parts by weight of PP with an upper index of 8 was mixed in an amount of 1.

Granulation, pretreatment, painting, and evaluation were performed.

As a result, no peeling was observed.

Cold Example 4 The composition of Example 1 was bonded to a polyvinyl chloride sheet using Hard Lenna 15L (chlorinated PP) manufactured by Toyo Kasei Co., Ltd. as an undercoat and 546N (NBR type) manufactured by Cemedine ■ as an adhesive. Then, the 180'' peel strength was measured.

Comparative Example 8 The procedure was the same as that of Example 4 except that only block PP was used.

Example 5 Without any surface treatment of the injection molded plate of the composition used in Example 1, a stroke of 5 strips in width was made using a gold-deposited hot stamping foil manufactured by Klug Japan. The temperature of the mold in which the letters were engraved in a convex manner was set to 170.
℃ and hot stamped the letters onto the injection plate. The adhesion of the foil was examined by applying a 24-meter cellophane tape made by Nichiban Co., Ltd. to the top of the foil with a fingertip, and then peeling it off rapidly.

The hot-stamped foil was not removed by the sellotape at all, and the residual rate was 100%.

Comparative Example 4 Hot stamping was performed in the same manner as in Example 5, except that only block PP was used, and a cellophane tape peeling test was conducted.

As a result, the residual rate was 70 vomit.

Example 6 From EPR with 50% ethylene content in toluene solution,
MAHO at 165°C in the presence of peroxide, containing 5g% E
PR was synthesized (hereinafter referred to as MAR-modified EPR-
9).

Said MAH-modified EPR-840fflff 1 part and ethylene content y, 47! One part of block PP60 weight with f1% and melt index 8 was mixed, granulated, and molded in the same manner as in Example 1 to produce an injection molded plate of 150:90×2 wa t.

The molded plate was coated in the same process as in Example 1, baked and dried, and initial adhesion and water resistance were evaluated.

As a result, no peeling was observed.

Example 7 MAl1fi EPR-1, -2, -80) 020 parts by weight each and the pro-I resin PP80 shown in Example 1! Izot [70 strength (Mu8TM D256) of the composition with the amount part
As a result of measurement at 28°C (with notch), the zero value was 4.
4.2.51.1゜46, Ji h ・cm/'611
Met.

Comparative Example 5 Composition of unmodified KPR and pro-drop PP shown in Example 2 (20 parts by weight of unmodified EPR, 3011 parts of block PF)
Izot impact strength (Mu8TM Dg56.28℃
, Notsuchi Yu) was 20.9-.37 countries.

Example 8 Izod impact strength (Mu8T) of the composition shown in Example 8
M Dg56.28℃, with notch) is 8.8-cm
/ 511.

Comparative Example 6 The Izot impact strength of the single block PP shown in Example 1 (Mu8TM D256.28°C, with notches) was 6.4.
It was 9.3151.

Claims (1)

[Claims] (1) Polyolefin 99.9 to 80 parts by weight (2) Crystalline and/or rubbery copolymer of ethylene and propylene with an ethylene content of 10 to 80% by weight, or a crystalline and/or rubbery copolymer of these and an olefin having 4 or more carbon atoms. A polyolefin composition comprising 0.1 to 70 parts by weight of a modified polymer obtained by graft copolymerizing 0.1 to 10% by weight of dicarboxylic acid or its anhydride.