JP2000073501A - Laminated molded rain gutter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated molded rain gutter light in weight and excellent in heat resistance, impact resistance and weather durability without causing troubles in incineration of end materials. SOLUTION: A laminated molded rain gutter includes a core layer 1 formed of ABS resin and a coating layer 2 of a thermoplastic resin composition coated to the outer surface of the core layer 1 and containing 60-95% by weight of a resin composition (I) shown below and 5-40% by weight of a modified polyolefin based polymer (II). The resin composition (I) is a composition of copolymer (A) containing aromatic vinyl monomeric units, vinyl cyanide monomeric units and vinyl monomeric units having epoxy groups, the vinyl monomeric units having epoxy groups having an amount of 0.1-10% by weight based on 100% by weight of the composition containing the copolymer (A). The modified polyolefin polymer (II) is modified by 0.1-10% by weight of unsaturated dicarboxylic acid anhydride monomeric units and/or unsaturated carboxylic acid monomeric units.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a new rain gutter, e.g., a gutter, a water collector, a stamp, etc., which is conventionally made of a hard PVC resin, and uses ABS resin as a core layer. The present invention relates to a rain gutter made of a laminated molded product in which a thermoplastic resin composition has a coating layer on the outer surface.

[0002]

2. Description of the Related Art Conventionally, hard PVC resin has been used almost all for rain gutters. However, PVC resin has high specific gravity and heat resistance,
It has the disadvantage of low impact strength. Furthermore, the environmental hygiene problem that has recently been taken up is that molding manufacturers and field construction contractors cannot incinerate due to concerns about the generation of dioxins, and are currently very troubled with the disposal of waste materials such as offcuts. Therefore, there has been a demand for the development of a resin which is improved in physical properties and which is not troublesome for disposal of scrap materials or the like, in place of the conventional hard PVC resin.

For the purpose of improving the disadvantages of these hard PVC resins, rain gutters formed in two layers have been reported (JP-A-56-146554, JP-A-59-1112).
No. 19, Japanese Patent Publication No. 63-23339,
-299665, JP-A-9-228577, etc.). However, in these publications, the improvement was not satisfactory, such as the use of a hard PVC resin for the outer layer and the use of an adhesive at the interface between the inner layer and the outer layer.

[0004]

Accordingly, what is needed at present is to improve the disadvantages of such rigid PVC resin, and is light in weight, excellent in heat resistance and impact resistance, and incinerated offcuts and the like. An object of the present invention is to provide a gutter having no processing problem.

[0005] That is, it is possible to some extent to improve the drawbacks of hard PVC resin by using ABS resin, but ordinary ABS resin is excellent in heat resistance and impact resistance, but poor in weather resistance, so that it can be used outdoors. In such a case, it is difficult to substitute a hard PVC resin as a single resin.

Therefore, an object of the present invention is to provide a rain gutter which is made of ordinary ABS having good weather resistance but good heat resistance and impact resistance.
The resin is used as a core layer, and a new thermoplastic resin composition having good weather resistance and affinity for ABS resin is laminated and molded as a coating layer on its outer surface, so that it is lightweight, heat resistant, impact resistant, and weather resistant. An object of the present invention is to provide a laminated rain gutter which is excellent in heat resistance and which has no problem of incineration treatment of scraps and the like.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned problems, and as a result, laminated a novel thermoplastic resin composition having good weather resistance as a coating layer with a normal ABS resin as a core layer. By molding, heat resistance, impact resistance,
The present invention has been completed by finding that the above-mentioned problems can be solved by forming a laminated rain gutter having excellent weather resistance and having no problem of incineration of offcuts or the like.

That is, the present invention provides a core layer made of an ABS resin, a resin composition (I) 60 to 95% by weight coated on the outer surface of the core layer and a modified polyolefin polymer (II) A laminated rain gutter comprising a coating layer of a thermoplastic resin composition containing 5 to 40% by weight. (I) a copolymer (A) containing an aromatic vinyl monomer unit, a vinyl cyanide monomer unit and a vinyl monomer unit having an epoxy group, or the copolymer (A) and an aromatic vinyl A copolymer (B) containing a monomer unit and a vinyl cyanide monomer unit, wherein the amount of the vinyl monomer having an epoxy group in the copolymer (A) is When the polymer (B) is not contained, the total amount of the copolymer (A) and the copolymer (B) is contained with respect to 100 parts by weight of the copolymer (A). Resin compositions (I) and (II) containing 0.1 to 10% by weight with respect to 100 parts by weight, respectively, of an unsaturated dicarboxylic acid anhydride monomer unit and / or an unsaturated carboxylic acid monomer unit 0.1 Modified polyolefin-based polymer (I)
I).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The laminated rain gutter of the present invention is made of ABS.
A laminated molded article comprising a core layer made of a resin and a coating layer of the following thermoplastic resin composition coated on the outer surface of the core layer, wherein the thermoplastic resin composition comprises (I) an aromatic vinyl A copolymer (A) containing a monomer unit, a vinyl cyanide monomer unit and a vinyl monomer unit having an epoxy group,
Or a composition of the copolymer (A) and a copolymer (B) containing an aromatic vinyl monomer unit and a vinyl cyanide monomer unit, wherein the epoxy in the copolymer (A) is The amount of the vinyl monomer having a group is based on 100 parts by weight of the copolymer (A) when the copolymer (B) is not contained, and the amount of the copolymer (B) when the copolymer (B) is contained. (I) 60 to 95% by weight of the resin composition (I) containing 0.1 to 10% by weight based on 100 parts by weight of the total amount of the copolymer (A) and the copolymer (B);
I) Heat consisting of 5 to 40% by weight of a modified polyolefin polymer (II) modified with 0.1 to 10% by weight of an unsaturated dicarboxylic acid anhydride monomer unit and / or an unsaturated carboxylic acid monomer unit It is a plastic resin composition.

Hereinafter, the present invention will be described in detail. The ABS resin used as the core layer in the present invention is not particularly limited, and a commercially available ABS resin is used. That is, in the presence of a butadiene rubber and / or a styrene-butadiene rubber-like polymer, a graft copolymer obtained by polymerizing styrene and acrylonitrile (hereinafter referred to as an ABS graft copolymer) is polymerized with styrene and acrylonitrile. This is a resin comprising a copolymer (hereinafter, referred to as an AS copolymer) obtained by the above method. In some cases,
It is made of ABS graft copolymer, and is not necessarily
In some cases, no copolymer is added. Also, preferably,
An ABS resin suitable for extrusion molding is used. Specifically, in accordance with JIS K 6874, a temperature of 220 ° C. and a load of 1
Melt low rate measured at 0 kg is 0.3 to 10 g
/ 10 min ABS resin.

Next, the thermoplastic resin composition used as a coating layer on the outer surface in the present invention will be described. The thermoplastic resin composition contains a resin composition (I) and a modified polyolefin-based polymer (II).

First, the copolymer constituting the resin composition (I) will be described. The resin composition (I) comprises the copolymer (A) or the copolymer (A) and the copolymer (B). Specific examples of the aromatic vinyl monomer used for the copolymer (A) and the copolymer (B) include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and the like. α-Methylstyrene is particularly preferred. Further, specific examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is preferable. Further, specific examples of the vinyl monomer having an epoxy group include glycidyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether and the like, and glycidyl methacrylate is particularly preferred.

Further, the graft copolymer (A) and the copolymer (B) of the present invention may be optionally copolymerized with other acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate, and methyl methacrylate. And a monomer unit such as methacrylic acid ester such as ethyl methacrylate.

The proportion of each monomer unit of the copolymer (A) is not particularly limited as long as it is within a copolymerizable range, but preferably, an aromatic vinyl monomer unit and a vinyl cyanide monomer are used. The total amount of the monomer units is 99.9 to 70% by weight, more preferably 99.9 to 90% by weight, and the vinyl monomer unit having an epoxy group is preferably 0.1 to 30%.
%, More preferably 0.1 to 10% by weight.

The proportion of the aromatic vinyl monomer unit in 100% by weight of the aromatic vinyl monomer unit and the vinyl cyanide monomer unit is preferably 50 to 90% by weight,
Particularly preferably, it is 65 to 85% by weight. If the proportion of the aromatic vinyl monomer unit is out of this range, the chemical resistance and the fluidity of the thermoplastic resin composition decrease, which is not preferable.

Next, the ratio of the aromatic vinyl monomer unit to the vinyl cyanide monomer unit in the copolymer (B) is not particularly limited, but preferably the total of both is 100%.
The proportion of the aromatic vinyl monomer unit in the weight% is 50 to 90.
% By weight, more preferably 65 to 85% by weight. If the proportion of the aromatic vinyl monomer unit is less than this, the fluidity of the thermoplastic resin composition is low, and if it is more than this, the chemical resistance is undesirably reduced.

The amount of the vinyl monomer unit having an epoxy group copolymerized in the copolymer (A) in the resin composition (I) of the present invention is determined by the amount of the copolymer (A) in the resin composition (I). When used alone, a copolymer (A) containing 0.1 to 10% by weight of a vinyl monomer unit having an epoxy group is used. When the copolymer (B) is contained, 0.1 to 30% by weight of an epoxy group-containing vinyl monomer unit
Can be used, but the total amount of the copolymer (A) and the copolymer (B) in 100 parts by weight of the vinyl monomer unit having an epoxy group is 0.1
-10% by weight. The ratio of the copolymer (A) to the copolymer (B) is not limited as long as the amount of the vinyl monomer unit having an epoxy group is within the above range. When the amount of the vinyl monomer unit having an epoxy group is 0.
If the amount is less than 1% by weight, the impact resistance of the thermoplastic resin composition is inferior, and if it exceeds 10% by weight, the fluidity becomes extremely low, and the impact strength also decreases.

Next, the modified polyolefin polymer (II) in the present invention will be described. The modified polyolefin polymer (II) of the present invention refers to a polymer of an olefin monomer or a modified product of a copolymer thereof, and specific examples of the olefin monomer used include ethylene, propylene, 1- Butene, isobutylene, 2-butene, cyclobutene, 3-methyl-1-butene, 4-methyl-1-butene, 4-methyl-1-pentene, cyclopentene, 1-
Hexene, cyclohexene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned.

If the preferred composition range is exemplified, ethylene is 20 to 90 mol% and α-olefin monomer unit 10
To 80 mol% and other monomer units of 0 to 10 mol%, preferably the ethylene monomer content is 50 to 85 mol%, particularly preferably 50 to 80 mol%.
Further, the glass transition temperature of these modified polyolefin-based polymers (II) is -10C or less, particularly preferably -30C or less.

Specific examples of the unsaturated dicarboxylic anhydride monomer that modifies the polyolefin polymer or copolymer include maleic anhydride, methylmaleic anhydride,
Examples thereof include 2-dimethylmaleic acid, ethylmaleic anhydride, and phenylmaleic anhydride, with maleic anhydride being particularly preferred. Specific examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, and maleic acid.

The modified polyolefin polymer (II) in the present invention is a polymer modified with 0.1 to 10% by weight of an unsaturated dicarboxylic anhydride monomer unit and / or an unsaturated carboxylic acid monomer unit. Yes, modified amount is 0.1% by weight
If it is less than 10%, the impact strength of the thermoplastic resin composition will be poor. If it exceeds 10% by weight, the impact resistance of the composition will be poor and the fluidity will be low.

The term "modified" as used in the present invention means that a monomer unit used for modifying the main chain or side chain of the polyolefin polymer, for example, a maleic anhydride monomer unit is present. Modification can be performed by a known technique such as random copolymerization or Guchft polymerization. The denaturation method is not particularly limited. For example, Japanese Patent Publication No.
JP-A-43677, JP-A-53-5716, and JP-A-56
Modification can be performed according to the methods disclosed in JP-A-9925 and JP-A-58-445.

In the modification, those modified as grafts are more preferable than those introduced into the main chain in view of the low-temperature impact value of the thermoplastic resin composition, and the unreacted monomer residue The amount is preferably 0.5% by weight or less from the viewpoint of physical properties.

The weight average molecular weight of the modified polyolefin polymer (II) is not particularly limited, but is preferably 50,000 to 500,000, particularly preferably 100,000 to 100, from the balance of impact resistance and moldability.
300,000 is preferred. Examples of these modified polyolefin-based polymers (II) include commercially available Tuffmer M
P-0620 (trade name, manufactured by Mitsui Chemicals, Inc.).

The thermoplastic resin composition of the present invention comprises 60 to 95% by weight, preferably 65 to 90% by weight of the resin composition (I) and 5 to 40% by weight, preferably 5 to 40% by weight of the modified polyolefin polymer (II). It is a thermoplastic resin composition comprising 10 to 35% by weight. Modified polyolefin polymer (II)
If it is less than 5% by weight, the impact strength of the thermoplastic resin composition is poor, and if it exceeds 40% by weight, heat resistance and rigidity are undesirably reduced. The thermoplastic resin composition is not particularly limited, but a composition suitable for extrusion molding is preferably used. Specifically, JIS K
This is a composition having a Melt-Roll rate of 1 to 20 g / 10 min measured at 220 ° C. under a load of 10 kg according to 6874.

The thermoplastic resin composition of the present invention can further improve the weather resistance by adding a weather agent. As the weathering agent, an ultraviolet absorber, a light stabilizer, an antioxidant, and a combination thereof are used.

Further, the thermoplastic resin composition of the present invention can be made into a composition by adding other additives or modifiers depending on the application. Specifically, glass fiber, carbon fiber And fillers such as talc, silica, clay, mica, and calcium carbonate, flame retardants, lubricants, coloring agents, and the like.

Next, the mixing for obtaining the thermoplastic resin composition of the present invention can be performed using a usual melt-kneading apparatus. Suitable melt kneading devices include a screw extruder, a Banbury mixer, a co-kneader, and a mixing roll.

A method of forming a laminated rain gutter by coating a thermoplastic resin composition as a coating layer on an ABS resin serving as a core layer is performed by extruding the core layer material with a twin-screw extruder, and forming the coating material simply. A method of coating at the tip of an extrusion die with a screw extruder is generally used. The coated product is cooled by a cooling device after extrusion and cut into a predetermined length through a take-off machine.

In particular, in the present invention, the ABS resin and the thermoplastic resin composition are composed of the same or very similar monomer units except for the rubber component of both resins. The adhesion between the layer and the coating layer is good and there is no need to use an adhesive.

[0031]

The present invention will be described in more detail with reference to the following examples. These are all examples and do not limit the content of the present invention. The ratios are shown on a weight basis unless otherwise specified.

The following were used as the ABS resin, the resin composition (I) and the modified polyolefin-based polymer (II) used in the test of the present invention.

(1) ABS resin [S-1] (a) ABS graft copolymer A graft copolymer having a ratio of polybutadiene, styrene and acrylonitrile of 50: 37.5: 12.5, and (b) AS Copolymer After mixing styrene and an AS copolymer having a ratio of acrylonitrile of 75:25 with a Henschel mixer at a ratio of 50:50, a TEM-35B extruder (a twin screw extruder manufactured by Toshiba Machine Co., Ltd.) And extruded at 220 ° C. into pellets. The pellets had a melt flow rate of 3 g / 10 minutes measured at a temperature of 220 ° C. and a load of 10 kg in accordance with JIS K 6874.

(2) Thermoplastic resin composition (2) -1: resin composition (I) (a) copolymer (A) The copolymerization ratio of styrene, acrylonitrile and glycidyl methacrylate is 74/25/1. Using a copolymer,
This is defined as (a-1).

(B) Copolymer (B) A standard commercially available styrene-acrylonitrile copolymer having a copolymerization ratio of styrene and acrylonitrile of 75:25 is used, and is referred to as (b-1). .

(2) -2: Modified polyolefin-based copolymer (II) Maleic anhydride is added to an ethylene / propylene copolymer having an ethylene content of 80 mol%, and the added amount of maleic anhydride is 1.3. % By weight, and this is (c-
1).

The thermoplastic resin composition [H-1] comprises a copolymer (a-1), a copolymer (b-1) and a modified polyolefin-based copolymer (c-1) in a ratio of 28:57:15. The mixture was mixed with a Henschel mixer at a ratio of 1 and then extruded into a pellet at a resin temperature of 230 ° C. using a TEM-35B extruder.

Further, the thermoplastic resin compositions [H-2] and [H-3] were similarly prepared at the mixing ratios shown in Table 3. In addition, JIS K687 of these pellets
H-1 was 11.8 g / 10, as measured in accordance with No. 4 and at a temperature of 220 ° C. and a load of 10 kg.
Min, H-2 9.5 g / 10 min, H-3 5.9 g / 1
It was 0 minutes.

Example 1 Using the above raw materials, ABS [S-1] for a core layer was 65 mm
In a φ2 screw extruder, a thermoplastic resin composition for a coating layer [H-
1] was co-extruded using a 50 mmφ single screw extruder under the extrusion conditions shown in Table 1 to produce a laminated molded gutter having the shape shown in FIG. In the figure, 1 indicates a core layer (about 1.6 mm in thickness), and 2 indicates a coating layer (about 0.3 mm in thickness).

Example 2 and Example 3 H used in Example 1 as the thermoplastic resin composition for the coating layer
Coextrusion was carried out in the same manner as in Example 1 except that H-2 was used in Example 2 and H-3 was used in Example 3 instead of -1. Created.

Comparative Example 1 In order to obtain a rain gutter having the same shape as in Example 1, both co-extrusion extruders were fed with ABS resin [S-1], molded under the same conditions, and formed into the same shape. I got a gutter. Example 1
Table 1 shows the extrusion conditions of Comparative Examples 1 to 3.

[0042]

[Table 1]

COMPARATIVE EXAMPLE 2 In order to obtain a rain gutter having the same shape as in Example 1, both co-extrusion extruders were fed with a hard PVC resin compound (polymerization degree 1100, lead stabilizer compound) under the same conditions. To obtain a rain gutter of the same shape. Table 2 shows the extrusion conditions of Comparative Example 2.

[0044]

[Table 2]

Table 3 shows the physical property evaluations of the gutters obtained in the above Examples and Comparative Examples. In addition, the measuring method of various physical properties is as follows. (1) Weather resistance test Rain gutters (thickness of about 2.1) prepared in the above Examples and Comparative Examples
mm), a test piece of 10 mm × 20 mm was cut out from the bottom portion (extrusion direction: 20 mm), and the temperature was 83 ° C. with a sunshine weather meter, and the temperature was 10 ° C. with a shower.
Irradiation was performed for 00 hours, and the impact strength before and after the irradiation was measured.

(2) Impact resistance test The above test piece was subjected to an impact resistance test without a notch using a Dynestat impact tester manufactured by Toyo Seiki Seisaku-sho, Ltd. (3) Measurement of Specific Gravity A test piece was cut out from the bottom of the rain gutter produced in the above Examples and Comparative Examples, and was measured based on ASTM D-792.

(4) Measurement of heat resistance (Vicat softening point) A test piece was cut out from the bottom of the rain gutter prepared in the above Examples and Comparative Examples, and according to JIS K7206.
The Vicat softening point under a load of 5 kg was measured.

[0048]

[Table 3]

From the results of the Examples and Comparative Examples in Table 3, the impact strength before and after the irradiation with the sunshine weather meter can be seen from the comparative data. It can be seen that the subsequent drop in impact is very small and the weather resistance is very good.

The laminated gutter of this embodiment has a lower specific gravity, a higher heat resistance and a lower original impact strength before irradiation in a weather resistance test than the conventional hard PVC resin gutter. It is clear that the strength is high and the impact strength after irradiation is small.

[0051]

As described above, the laminated gutter of the present invention improves the weather resistance, which is a drawback of the conventional ABS, by lamination molding, and also improves the drawback of the hard PVC rain gutter to reduce the weight, It is excellent in heat resistance, impact resistance, and weather resistance, and can be usefully used as a rain gutter which is not troublesome for waste material disposal.

[Brief description of the drawings]

FIG. 1 is a sectional view showing the shape of a laminated molded gutter created in Example 1.

[Explanation of symbols]

 1 core layer 2 coating layer

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Koichi Shimizu 6 Goi-minamikaigan, Ichihara-shi, Chiba Electrochemical Industry Co., Ltd. Chiba Plant (72) Inventor Toshio Shimada 2-3-1-1, Kamakura-shi, Kanagawa Oriental chemical Co., Ltd. in the F-term (reference) 4F100 AH02B AH02C AH02J AK03B AK03C AK03J AK11B AK11C AK11J AK27B AK27C AK27J AK53B AK53C AK53J AK74A AL01B AL01C AL05B AL05C AL07B AL07C BA02 EH17 GB07 JB16B JB16C JJ03 JK10 JL03 JL09 YY00B YY00C 4J002 BB213 BC062 BG102 BN151 CD192 GF00 GL00

Claims (1)

[Claims] 1. A core layer made of an ABS resin, and the following resin compositions (I) 60 to 9 coated on the outer surface of the core layer.
5% by weight and modified polyolefin polymer (II) 5 to 4
A laminated rain gutter comprising a coating layer of a thermoplastic resin composition containing 0% by weight. (I) a copolymer (A) containing an aromatic vinyl monomer unit, a vinyl cyanide monomer unit and a vinyl monomer unit having an epoxy group, or the copolymer (A) and an aromatic vinyl A copolymer (B) containing a monomer unit and a vinyl cyanide monomer unit, wherein the amount of the vinyl monomer having an epoxy group in the copolymer (A) is When the polymer (B) is not contained, the total amount of the copolymer (A) and the copolymer (B) is contained with respect to 100 parts by weight of the copolymer (A). Resin compositions (I) and (II) containing 0.1 to 10% by weight with respect to 100 parts by weight, respectively, of an unsaturated dicarboxylic acid anhydride monomer unit and / or an unsaturated carboxylic acid monomer unit 0.1 Modified polyolefin-based polymer (I)
I).