JPH07156351A - Multilayer molding - Google Patents

Abstract

PURPOSE:To obtain a multilayer molding having excellent rigidity, heat resistance, weather resistance, adhesive properties, durability and recyclability by laminating a cyclic olefin resin layer on an outer surface of a core layer made of a polyolefin resin as a core material through an adhesive layer. CONSTITUTION:A cyclic polyolefin resin, a styrene copolymer elastomer of an adhesive layer and a polypropylene resin are separately extruded by three extruders. The melted resins are poured in multilayer molds, and coextruded to obtain a rain gutter 8 made of three type-five layer-molded form of a cyclic polyolefin resin layer 3, an adhesive layer 4, a polypropylene resin layer 5, an adhesive layer 6 and a cyclic polyolefin resin layer 7 in which the cyclic polyolefin resin is laminated on a rain gutter visible surface 1 and a rain gutter water receiver 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multi-layer molded product such as a rain gutter and deck material, which has excellent weather resistance, durability and recyclability.

[0002]

BACKGROUND OF THE INVENTION Conventionally, rain gutters, deck materials, etc. are generally made of polyvinyl chloride (hereinafter abbreviated as "PVC"), but PVC products have poor weather resistance, and therefore weather resistance. Various means for improving the above have been proposed.

For example, in a rain gutter, Japanese Patent Laid-Open No. 56-1 is used.
As described in Japanese Patent No. 46554, a rain gutter in which an acrylic resin is coated with a polystyrene or polyacrylonitrile-styrene copolymer resin layer on the outer peripheral surface of a PVC tubular core material has been proposed, and has weather resistance and As for durability, it had weather resistance and durability sufficient for outdoor use. However, since PVC is flame-retardant, it has a problem in waste treatment, and since it has poor thermal stability, it has been difficult to recycle it. Further, since PVC rain gutters have low heat resistance, there is a problem that the rain gutter surface and inner surface temperature rises with temperature rise in the summer, causing bending and expansion and contraction.

In the deck material, for example, a surface protective layer made of a transparent acrylic resin or the like is formed on the surface, or an acrylic resin is used to protect the printed layer by directly printing a wood pattern on the surface. Deck materials such as those having a surface protective layer formed thereon, or those having a colored acrylic resin coating layer formed on the surface and a surface layer made of an ultraviolet curable resin (see Japanese Patent Publication No. 5-5017) have been proposed. ing. However, the method of forming a transparent acrylic resin layer on the surface is inferior in the ability to block sunlight, resulting in discoloration of PVC products, and the method of coating a colored acrylic resin coating has a coating-drying step. The cost was high. Moreover, similar to rain gutters, there are problems in waste disposal, difficult to recycle, and problems such as bending and stretching due to temperature rise in the summer.

Therefore, in order to solve the above problems, a polyolefin resin having excellent heat resistance and recyclability is used.
Although it can be considered to be used as a material for rain gutters or deck materials, polyolefin resins do not have weather resistance that can withstand outdoor use.

Conventionally, as a method for improving the weather resistance of a polyolefin resin, there is a method of adding an ultraviolet absorber or an antioxidant to the polyolefin resin. As a method of laminating an acrylic resin and improving weather resistance, a method of using a block copolymer of a monovinyl-substituted aromatic compound polymer and a conjugated diolefin polymer as an adhesive layer of a polyolefin resin and an acrylic resin is used. Japanese Patent Examination Sho 60-4
No. 2029 discloses a method of laminating and bonding an ethylene-vinyl acetate graft polymer-containing acrylic resin film and a polyolefin-based resin film.
It is disclosed in the issue.

[0007]

However, in the method of adding the polyolefin resin ultraviolet absorber or the antioxidant, the change in the color tone and the deterioration of the mechanical properties were insufficient in the long-term outdoor use. Further, a method of laminating an acrylic resin on a polyolefin resin and improving the weather resistance has a sufficient effect of improving the weather resistance, but the adhesiveness in the initial and long-term use is insufficient, and the laminated product is peeled off. There was a problem in adhesion. The method of laminating the ethylene-vinyl acetate graft polymer-containing acrylic resin on the polyolefin resin is inferior in heat resistance of the ethylene-vinyl acetate graft polymer, resulting in poor thermal stability during molding and discoloration when used outdoors for a long time. However, there is a problem in that the physical properties tend to deteriorate. Further, there is a problem that peeling of each layer is difficult at the time of recycling and the compatibility of each layer is insufficient, so that the physical properties after recycling are significantly reduced.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a multilayer molded article having excellent rigidity, heat resistance, weather resistance, adhesiveness, durability and recyclability.

[0009]

The multilayer molded article of the present invention comprises a core layer made of a polyolefin resin as a core material and at least one cyclic olefin resin layer laminated on the outer surface via an adhesive layer. .

The polyolefin resin used in the present invention refers to a homopolymer of α-olefin and a copolymer with a monomer having an unsaturated group copolymerizable with α-olefin, such as polyethylene and polypropylene. , Polybutene, polyisoprene, polypentene, polymethylpentene, chlorinated polyethylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-1-butene copolymer, 4-ethylene-2
-Methylpentene copolymer, ethylene-butadiene copolymer, ethylene-acrylate copolymer, ethylene-vinyl acetate copolymer and the like can be mentioned. Further, glass fibers, an inorganic filler, an ultraviolet absorber, a flame retardant, etc. can be added to the above polyolefin resin.

As the adhesive layer, a resin exhibiting properties of a rubber region at room temperature, for example, a styrene copolymer elastomer,
Examples include olefin elastomers. They are,
They may be used alone or in combination of two or more.

The styrene copolymer elastomer is a block copolymer of styrene and an ethylene / diene copolymer, and the diene component is, for example,
1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene and the like can be mentioned. These may be hydrogenated at the time of copolymerization, or the double bond may remain. When the amount of ethylene / diene component is too small, the rubber resin layer obtained becomes too hard, and when it is too large, the strength becomes low.In either case, the adhesive strength of the finally obtained laminate becomes low. 30 to 90% by weight is preferable in all the constituent components of the united body. The ethylene / diene-styrene block copolymer is apt to cause resin leakage from a mold or the like when the rubber-like resin layer is formed by extrusion molding and when the weight average molecular weight is small. However, when it is large, the moldability becomes poor, so 40,000 to 150,000 is preferable.

The above-mentioned olefin elastomer is an α-olefin resin having rubber-like elasticity at around room temperature, such as ethylene-propylene rubber and ethylene-1.
Examples include butene rubber, propylene-1-butene rubber, ethylene-propylene-diene rubber, and polyisobutylene.

The cyclic olefin resin used in the present invention is a resin excellent in rigidity, heat resistance and the like, specifically, a random copolymer of ethylene and cyclic olefin (ethylene content 40 to 90 mol%). And a modified copolymer obtained by graft-polymerizing an ethylene-α-olefin copolymer (ethylene content 30 to 95 mol%) with a polycyclic (meth) acrylate monomer, if necessary, to improve impact resistance. And ethylene-α-olefin copolymer (ethylene content 30 to 95 mol%) can be added (JP-A-3-95243).
(See the official gazette).

Further, known methods can be used for producing these multilayer molded bodies. That is, the conventional multi-layer molding manufacturing method can be used, and the polyolefin resin, the adhesive layer, and the cyclic olefin resin are melted by separate extruders, respectively, and injected into the same mold (mold temperature 200 to 250 ° C.) to form each layer. Bond and then solidify by cooling. The molding temperature of each layer is 140 to 230 ° C. for the polyolefin resin, 220 to 250 ° C. for the adhesive layer, and 220 to 250 for the cyclic olefin resin layer.
Molded at 250 ° C. The thickness of each layer should be designed to satisfy the quality of the multi-layer molded product such as rain gutter and deck material.
The cyclic olefin resin layer is 50 μm or more so as to exert the effect of improving rigidity, and the adhesive layer is 30 μm from the viewpoint of adhesive strength.
The above is preferable.

In the multilayer molded product of the present invention, the outer surface means a surface exposed to sunlight, that is, the cyclic olefin resin needs to be laminated on at least one surface exposed to sunlight. At least one layer must be laminated on the visible surface of the rain gutter and on the surface of the deck material in the case of deck material. If necessary, for example, it can be laminated on the water receiving part of the rain gutter, the inner surface of the deck material, etc. can do.

[0017]

Since the multi-layer molded article of the present invention is constructed as described above, the adhesion of the multi-layer molded article such as rain gutter and deck material having a surface exposed to sunlight, which has not been sufficiently improved by the prior art. Performance, weather resistance, etc. are improved.

[0018]

EXAMPLES The details of the present invention will be described below with reference to examples, but the present invention is not limited to these examples as long as they are within the scope of the claims.

Examples 1 to 2 Cyclic polyolefin resin, styrene copolymer elastomer as an adhesive layer, and polypropylene resin were extruded separately by three extruders, and the melted resin was placed in a multi-layer mold. Injection and co-extrusion, as shown in FIGS. 1 and 2,
Cylindrical polyolefin resin layer 3 / adhesive layer 4 / polypropylene resin layer 5 / adhesive layer 6 / cyclic polyolefin resin layer 7 in which cyclic polyolefin resin is laminated on the rain gutter visible surface 1 and the rain gutter water receiving part 2 5 layers A rain gutter 8 composed of a molded body was obtained.

The manufacturer names and grades of the resins used for the resin layers 3, 5, 7 and the adhesive layers 4, 6 and the thickness of each resin layer are as follows. Cyclic polyolefin resin: Mitsui Petrochemical Co., Apel 130R, MI = 5 at 260 ° C Polypropylene resin: Mitsubishi Petrochemical Co., EC-
8, PP-PE block, MI = 1.5 at 230 ° C. Adhesive layer Example 1: Styrene-Ethylene / Butadiene / Styrene Copolymer, H1041, Styrene / Ethylene / Butadiene = 30/70 Example 2: Kuraray Manufactured by Styrene-Ethylene / Isopropylene-Styrene
Copolymer, Cefton 2043, Styrene / Ethylene / isoprene = 13/87 Thickness of each resin layer: Cyclic olefin resin layer 100 μ
m Adhesive layer 50 μm Polypropylene resin layer 1.3 mm

Test method 1) Adhesive strength: The sample obtained above is immersed in warm water at 60 ° C. for 2 weeks and immersed (evaluation of durability). The adhesive strength of the adhesive layer 4 before and after immersion is shown in FIG. As described above, the polypropylene resin layer 5, the adhesive layer 4, and the cyclic polyolefin layer 3 are in the arrow X direction, and the cyclic polyolefin resin layer 7 is in the arrow Y direction at a pulling speed of 5 mm / min and a test temperature of 23 ° C. Measured by pulling at an angle of degrees. 2) Weather resistance: Accelerated evaluation was performed using a sunshine weatherometer, and Charpy impact strength (JISK 7111) after irradiation for 2000 hours and before irradiation was measured. 3) Recyclability: After crushing the 3 types and 5 layers of rain gutter molded under the above-mentioned molding conditions, the crushed product was put into the extruder again, and the Charpy impact strength of the obtained molded product was measured.

Examples 3 to 4 The same procedure as in Examples 1 and 2 was carried out except that the following olefinic elastomer was used as the adhesive layer instead of the styrene elastomer. Example 3: Mitsui Petrochemical Co., Ltd., ethylene-propylene glycol,
Toughmer P0280 Example 4: Mitsui Petrochemical Co., Ltd., ethylene-1-butene, Tuffmer A4085

Examples 5 to 6 The same procedure as in Examples 1 to 2 was carried out except that the following polyolefin resin was used in place of the polypropylene resin. Example 5: Mitsubishi Petrochemical, LLDPE resin, UE320 Vi 95 Example 6: Mitsubishi Petrochemical, ethylene-vinyl acetate copolymer,
V223H be 82

Comparative Example 1 Using the above polypropylene resin as the core material, H 1041 which is a styrene / ethylene / butadiene / styrene copolymer manufactured by Asahi Kasei Co., Ltd. was used for the adhesive layer, and PMMA resin (HFI- 10, MI
= 4 at 230 ℃) was evaluated.

Comparative Example 2 A rain gutter obtained in the same manner as in Comparative Example 1 was evaluated, except that the adhesive layer was changed to Kuraray Co., Ltd. styrene-ethylene / isoprene-styrene copolymer, Septone 2043.

The results of Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 1.

[0027]

[Table 1]

In Table 1, strength change rate = strength reduction amount /
The strength before acceleration evaluation is shown.

Examples 7 to 8 Resins of cyclic polyolefin resin, styrene copolymer elastomer as an adhesive layer, and polypropylene resin were extruded separately by three extruders, and the melted resin was placed in a multi-layer mold. Injected and co-extruded, as shown in FIGS. 3 and 4,
A deck material 23 composed of a cyclic polyolefin resin layer 20 / adhesive layer 21 / polypropylene resin layer 22 in which a cyclic polyolefin resin was laminated on the outer periphery of a core material was obtained.

The names and grades of manufacturers of the resins used for the resin layers 20 and 22 and the adhesive layer 21 and the thickness of each resin layer are as follows.

Cyclic polyolefin resin: Mitsui Petrochemical Co., Ltd., Apel 130R, MI = 5 at 260 ° C. Polypropylene resin: Mitsubishi Petrochemical Co., EC-
8, PP-PE block, MI = 1.5 at 230 ° C. Adhesive layer Example 7: Asahi Kasei Corp. styrene-ethylene / butadiene / styrene copolymer, H1041, styrene / ethylene / butadiene = 30/70 Example 8: Kuraray Manufactured by Styrene-Ethylene / Isopropylene-Styrene
Copolymer, Cefton 2043, Styrene / Ethylene / isoprene = 13/87 Thickness of each resin layer: Cyclic olefin resin layer 100 μ
m Adhesive layer 50 μm Polypropylene resin layer 2.0 mm

Test Method 1) Adhesive Strength: The sample obtained above was immersed in warm water at 60 ° C. for 2 weeks, and immersed (durability evaluation). The peeling condition after immersion was observed. 2) Weather resistance: Accelerated evaluation was performed using a sunshine weatherometer, and Charpy impact strength (JISK 7111) after irradiation for 2000 hours and before irradiation was measured. 3) Recyclability: After crushing the three-layer deck material molded under the above-mentioned molding conditions, the crushed product was put into the extruder again, and the Charpy impact strength of the obtained molded product was measured. 4) Heat resistance: The heat distortion temperature was measured according to JIS K7207. (Load 18.5 kg / cm ² )

Examples 9 to 10 The same procedures as in Examples 8 to 9 were carried out except that the following olefin elastomer was used as the adhesive layer instead of the styrene elastomer. Example 9: Mitsui Petrochemical Co., Ltd., ethylene-propylene glycol, Tuffmer P0280 Example 10: Mitsui Petrochemical Co., Ltd., ethylene-1-butene,
Toughmer A4085

Examples 11 to 12 The same procedure as in Examples 8 to 9 was carried out except that the following polyolefin resin was used in place of the above polypropylene resin. Example 5: Mitsubishi Petrochemical, LLDPE resin, UE32 be 95 Example 6: Mitsubishi Petrochemical, ethylene-vinyl acetate copolymer,
V223H be 82

Comparative Example 3 Using the above polypropylene resin as a core material, a styrene-ethylene / butadiene-styrene copolymer, H1041, manufactured by Asahi Kasei Corporation was used for the adhesive layer, and PMMA resin (HFI- 10, MI
= 4 at 230 ° C) was evaluated.

Comparative Example 4 The deck material obtained in the same manner as in Comparative Example 3 was evaluated except that the adhesive layer was changed to Kuraray Co., Ltd. styrene-ethylene / isoprene-styrene copolymer, Septone 2043.

Comparative Example 5 PVC (manufactured by Tokuyama Sekisui Kogyo Co., Ltd., TS-800E, degree of polymerization = 800) was used as the core material, and the same PMMA as in Comparative Example 3 was used for the surface layer.
The deck material in which the resin was laminated was evaluated.

The results of Examples 7 to 12 and Comparative Examples 3 to 5 are shown in Table 2.

[0039]

[Table 2]

In Table 2, ○ indicates no peeling after immersion in warm water,
X indicates peeling after immersion in warm water, and strength change rate = amount of strength reduction / strength before acceleration evaluation.

[0041]

EFFECTS OF THE INVENTION Since the multilayer molded article of the present invention is constructed as described above, it has a rigidity, heat resistance, weather resistance, adhesiveness, durability and recyclability, and is a multilayer molding of rain gutters, deck materials and the like. You can get the body.

[Brief description of drawings]

FIG. 1 is a perspective view showing an example of a multilayer molded body of the present invention.

FIG. 2 is a sectional view taken along line AA of FIG.

FIG. 3 is a front view showing another example of the multilayer molded body of the present invention.

FIG. 4 is a sectional view taken along line BB of FIG.

[Explanation of symbols]

 1 visible surface 2 water receiving part 3, 7, 20 cyclic polyolefin resin layer 4, 6, 21 adhesive layer 5, 22 polypropylene resin layer 8 rain gutter 23 deck material

Claims (1)

[Claims] 1. A multi-layered molded product comprising a core layer made of a polyolefin resin as a core material, and a cyclic olefin resin layer laminated on at least one outer surface via an adhesive layer.