JPS63277253A - Polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition, containing a polyolefin resin, styrene- butadiene copolymer and styrene based polymer in a specific proportion and capable of exhibiting excellent adhesive properties to expanded polyurethane in casting and expanding polyurethane. CONSTITUTION:The aimed composition obtained by blending (A) 100pts.wt. polyolefin resin (e.g. PE, PP or ethylene-propylene copolymer) with (B) >=5pts. wt., preferably 10-60pts.wt. styrene-butadiene copolymer [preferably copolymer of 50-70wt.% butadiene and 50-30wt.% styrene] and (C) 30-150pts.wt., preferably 60-100pts.wt. styrene based polymer [e.g. (copolymer of styrene or methylstyrene].

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a polyolefin resin composition that exhibits good adhesion to foamed polyurethane when the polyurethane is cast and foamed.

(Conventional technology) Polyolefin resin has excellent moldability, mechanical strength,
It has excellent heat resistance and chemical resistance, is non-hygroscopic, and is cheaper and lighter than other resins, so it is widely used in home appliances, plastics, automobile parts, miscellaneous goods, etc.

In these applications, it is conceivable to use a heat insulating material or a cushioning material in which a polyolefin resin and a polyurethane foam are bonded together, the surface is made of a polyolefin resin with an excellent appearance, and the inner surface is made of polyurethane foam. Such a laminate can be manufactured by forming a hollow body with continuous polyolefin resin and then injecting and foaming polyurethane.

However, since polyolefin resin does not have a polar group in its molecule, has high crystallinity, and is chemically extremely inert, its adhesion to polyurethane is extremely small. Therefore, at present, the applications in which polyolefin resin is used as a surface base material and polyurethane foam is directly laminated are extremely limited.

The surface of polyolefin resin is coated with potassium dichromate-concentrated i
Treatments such as acid mixture immersion, gas flame treatment, and corona discharge treatment have been considered to improve the adhesion between polyolefin resin and cast-poured polyurethane, but the effects vary and the treatment methods are complicated. However, there were problems such as being expensive.

There is a method of improving the adhesive strength with polyurethane by applying a polyolefin resin primer containing chlorinated polyolefin or acrylic resin as a main component to the polyolefin resin surface in advance (Utility Model Application Publication No. 60-83734, Utility Model Application No. 60-83881, and Utility Model Application No. 60-83881) Jitsukai Sho 60-69087).

However, this method increases the number of manufacturing steps and increases costs, so it cannot be said to be practical.

There is a method of graft polymerizing droxyethyl acrylate or hydroxyethyl methacrylate to polyolefin resin to change the surface condition and improve adhesion (
JP-A-58-154732, JP-A-58-185244
, JP-A-58-191706, JP-A-58-16762
6 and Japanese Unexamined Patent Publication No. 58-219244). However, the acrylic-modified polyolefin resin obtained by this method lacks safety due to residual acrylic monomer, has a strong odor, and does not have sufficient adhesion.

Good adhesion with cast-foamed polyurethane.
There is also a method of blending acrylonitrile-butadiene-styrene copolymer (ABS) with a polyolefin resin;
Butadiene-styrene copolymers have poor compatibility, and good molded products cannot be obtained from blends thereof.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a polyolefin resin composition that has good adhesion to polyurethane.

[Means for solving problems]

The present inventors blended a styrene polymer with a polyolefin resin, and added a predetermined amount of a specific component to make the polyolefin resin and styrene polymer compatible, thereby making the polyolefin resin and cast-foamed polyurethane strong. It has been found that an even better molded product can be obtained, and the drawbacks of the above methods for improving adhesion can be overcome.

That is, the polyolefin resin composition of the present invention is characterized by comprising (A) 100 parts by weight of a polyolefin resin, (B) 5 parts by weight or more of a styrene-butadiene copolymer, and (C) 30 to 150 parts by weight of a styrene polymer. That is.

Typical polyolefin resins used in the present invention include polyethylene, polypropylene, ethylene-propylene copolymer, propylene-ethylene-butene copolymer, ethylene-pentene copolymer, polybutene, etc. It may also be used.

The styrene-butadiene copolymer used in the present invention is a generally commercially available unvulcanized plastic elastomer, and the copolymerization ratio of butadiene and styrene is 20 to 80 parts/f.
fi%, styrene is 80 to 20% by weight, particularly preferably butadiene is 50 to 70% by weight, and styrene is 50 to 30% by weight.
Weight%.

The blending ratio of the styrene-butadiene copolymer is 5 parts by weight or more, preferably 10 to 60 parts by weight, per 100 parts by weight of the polyolefin resin.

If the amount of 1 in the coelectric material is less than 5 parts by weight, the compatibility between the polyolefin resin and the styrene polymer will not be improved and a good molded product will not be obtained. Furthermore, the effects of improvement are extremely poor.

If the amount of this co-electric material exceeds 60 parts by weight, there will be no further increase in effectiveness, but only increased costs.

The styrenic polymer used in the present invention is a homopolymer or copolymer of a styrene polymer such as styrene or methylstyrene, a copolymer of a styrenic polymer and a non-styrenic polymer, such as acrylonitrile. -styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), or a mixture thereof.

The blending ratio of the styrene polymer is 30 to 150 parts by weight, preferably 60 to 100 parts by weight, per 100 parts by weight of the polyolefin resin. The amount of this polymer is 3
If the overlapped part is less than 0, the effect of modification is insufficient, and if the overlapped part is less than 15
If the amount exceeds 0 parts by weight, the compatibility with the polyolefin resin will be poor even if a butadiene-styrene copolymer is added, making it impossible to obtain a good molded product.

The composition of the present invention includes, to the extent that the effects of the present invention are not impaired,
It may also contain other thermoplastic resins, rubbers, and inorganic fillers. Furthermore, if necessary, additives such as heat stabilizers, lubricants, neutralizing agents, ultraviolet stabilizers/absorbers, antistatic agents, crystal nucleating agents, and pigments commonly used in polyolefin resins may be added to the composition of the present invention. May be added.

The composition of the present invention can be manufactured using common methods for granulating polyolefin resins.

That is, it can be produced by mixing predetermined amounts of each component using a Henschel mixer, ribbon blender, drum blender, etc., and then melt-kneading using a screw extruder or the like. This melt kneading is generally performed at 170 to 30
Performed at 0°C.

Products can be obtained using the composition of the present invention by known molding methods such as injection molding, blow molding, sheet molding, and film molding.

It can also be laminated with a polyolefin resin and used as a hot melt adhesive.

〔Example〕

The present invention will be explained in more detail by showing Examples and Comparative Examples below. These Examples are only for illustrating the present invention and should not be construed as limiting.

Example 1 Ethylene-brobylene block copolymer “BF, Il
” (manufactured by Mitsui Toatsu Chemical ■, MI = 0.5 g/10 minutes) 100 parts by weight, styrene-butadiene copolymer "Toughblen A" (Asahi Kasei ■! 8-ri 40 weight L 1 part, ABS
Resin “JSR-8BS 15” (made by Japan Synthetic Rubber ■,
Specific gravity 1.05) 100 parts by weight, 0.1 parts by weight of 2.6-di-butyl-p-cresol, tetrakis(methylene-3-(3°, 5°-di-t-butyl-4-hydroxyphenyl) Propionate) Methane (0.1 parts by weight) and calcium stearate (0.11 parts by weight) were mixed in a Henschel mixer, and then mixed in a screw extruder for 2 hours.
The mixture was melt-kneaded at a resin temperature of 40° C. and then granulated. The resulting pellets were molded into sheets with a width of 300 m using a sheet forming machine with a T-die at the tip of an extruder with a diameter of 40III+.
A 0.5 mm sheet was manufactured using J5. The resin temperature at this time was 240°C, and the roll temperature of each of the three rolls used was 90°C. Table 1 shows the appearance of the obtained sheet.

Furthermore, the sheet is a 30011IIg square sample,
This is 300m1+ in length, 300mm in width, and 30m in height.
Mitsui Nisso Polyurethane Co., Ltd. is pasted on both sides of a wooden frame to form a hollow body, and this hollow body contains MDI and polyol as main components, and various chain extenders, crosslinking agents, foaming agents, etc. A polyurethane composition for integral skin was injected and foamed.

A sample with a width of 10 mm and a length of 200 mm was prepared from the obtained laminate of polyolefin resin and polyurethane foam, and a peel test was conducted to measure the adhesion strength.

The adhesion strength was expressed as the strength when peeled off using a spring balance. The results are shown in Table-1.

Comparative Example 1 In Example 1, the amount of styrene-butadiene copolymer was reduced to 4 parts by weight, and sheet molding was carried out in the same manner. The sheet was torn when rolled and could not be molded.

Example 2 In Example 1, 1 of the styrene-butadiene copolymer
11 was increased to 70 parts by weight, sheet molding was performed in the same manner, and polyurethane was cast and foamed.
Adhesion strength was measured. The results are shown in Table-1.

Example 3 In Example 1, high-density polyethylene (manufactured by Nippon Petrochemicals, MI = 17 g/10 minutes) was used as the polyolefin resin, sheet molding was performed in the same manner as in Example 1, and polyurethane was cast and foamed. Adhesion strength was measured. The results are shown in Table-1.

Comparative Example 2 In Example 1, the amount of ABS was reduced to 20 parts by weight and 14 parts, sheet molding was carried out in the same manner as above, polyurethane was cast and foamed, and the adhesion strength was measured. The results are shown in Table-1.

Comparative Example 3 In Example 1, the amount of ABS was increased to 160 parts by weight,
Thereafter, sheet molding was performed using the same procedure. The surface of the sheet molded product became rough, making it impossible to obtain a good sheet.

Example 4 In Example 1, the styrene polymer was AS “Lightac-^100Pc” (manufactured by Mitsui Toatsu Chemical Co., Ltd., MI
= 1.4 g/10 minutes), sheet molding was carried out in the same manner as above, and polyurethane was cast and foamed, and the adhesion strength was measured. Table 1 shows the results.
Shown below.

Example 5 In Example 1, polyskelene "Tobolex 550-01" (manufactured by Mitsui Toatsu Chemical Co., Ltd., MI = 24 g/10 minutes) was used as the styrene and fS polymer, and sheet forming was performed in the same manner as in Example 1. Then, polyurethane was cast and foamed, and the adhesion strength was measured. The results are shown in Table-1.

Comparative Example 4 Ethylene-propylene block copolymer “BIEB”
Sheet molding was carried out in the same manner as in Example 1 using only polyurethane, followed by casting and foaming of polyurethane, and the adhesion strength was measured. The results are shown in Table-1.

Comparative Example 5 A sheet was formed in the same manner as in Example 1 without using the styrene polymer, and then polyurethane was cast and foamed, and the adhesion strength was measured. The results are shown in Table-1.

Comparative Example 6 Molding was carried out in the same manner as in Example 1 without using the styrene-butadiene co-ITc combination.

The sheet broke when rolled and could not be molded to 1".

Example 6 An extruder with a diameter of 65 mm and an extruder with a diameter of 40 mm are connected by a foot block, and the molten resin flowing out from the extruder with a diameter of 65+nm and the molten resin flowing out from the extruder with a diameter of 40 ml form two layers. Using an extruder with a diameter of 65 va to extrude this through a T-die, a composition (M
I = 0.5 g/10 min) to a thickness of 1.8 mm, and a skin layer with a thickness of 0.2+++n using a pellet obtained by the procedure of Example 1 from an extruder with a diameter of 40 mm.
Thickness 2 with a two-layer structure extruded from a T-die so that it becomes +
A sheet of mm was obtained.

The resin temperature at this time was 240°C, and the temperature of the three wood rolls was 90°C.

Width 10mm and length 20III11 from the obtained sheet
A sample was prepared, the core layer and skin layer were peeled off, and the adhesion strength was measured. The adhesion strength was measured by peeling at a speed of 30 mm/min using an Instron type Tensilon. The results are shown in Table 2.Furthermore, a two-layer sheet was used as a 300 mm square sample, and as in Example 1, it was placed in a wooden frame with a length and width of 300 mm square and a height of 30 mm so that the skin layer was on the inner surface (1 ), to form a hollow body, and then polyurethane was cast and foamed in the same manner as in Example 1, and the adhesion strength was measured. The results are shown in Table-2.

Comparative Example 7 In Example 6, the amount of ABS was reduced to 20%, and sheet molding was carried out in the same manner as in Example 6. Furthermore, polyurethane was cast and foamed, and the adhesion strength was measured.

The results are shown in Table-2.

Comparative Example 8 In Example 6, the amount of ABS was increased to 160 parts, and sheet molding was carried out in the same manner as in Example 6. Polyurethane was roughly cast and foamed, and the adhesion strength was measured.

The results are shown in Table-2.

Comparative Example 9 A sheet was formed in the same manner as in Example 6 without using the styrene-butadiene copolymer, and polyurethane was cast and foamed to measure the adhesion strength. The results are shown in Table 2.

Table 2: Effects of the Invention The composition of the present invention has extremely good adhesion to polyurethane, and can be favorably used in the production of laminated structures with polyurethane foam.

Claims (1)

[Claims] 1, consisting of (A) a polyolefin resin, (B) a styrene-butadiene copolymer, and (C) a styrene-based polymer, with 5 parts by weight or more of (B) per 100 parts by weight of (A), (C)
) is 30-150 parts by weight.