JPH07108590A - Plastic blow molded product for automobile - Google Patents

Plastic blow molded product for automobile

Info

Publication number
JPH07108590A
JPH07108590A JP27773593A JP27773593A JPH07108590A JP H07108590 A JPH07108590 A JP H07108590A JP 27773593 A JP27773593 A JP 27773593A JP 27773593 A JP27773593 A JP 27773593A JP H07108590 A JPH07108590 A JP H07108590A
Authority
JP
Japan
Prior art keywords
polypropylene
weight
nylon
carboxylic acid
modified polypropylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP27773593A
Other languages
Japanese (ja)
Inventor
Nobuo Arai
Koji Egashira
Fumio Kato
Kazuhiro Maekawa
Tadashi Sezume
和弘 前川
文夫 加藤
孝治 江頭
忠司 瀬詰
伸夫 荒井
Original Assignee
Nippondenso Co Ltd
Tonen Chem Corp
日本電装株式会社
東燃化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippondenso Co Ltd, Tonen Chem Corp, 日本電装株式会社, 東燃化学株式会社 filed Critical Nippondenso Co Ltd
Priority to JP27773593A priority Critical patent/JPH07108590A/en
Publication of JPH07108590A publication Critical patent/JPH07108590A/en
Pending legal-status Critical Current

Links

Abstract

(57) [Summary] [Objective] To provide a plastic blow-molded product for automobiles, which is excellent in heat resistance, calcium chloride resistance, impact resistance, antifreeze resistance, moldability, mechanical strength and the like. [Structure] (a) Nylon 66 30 to 90% by weight and (b) modified polypropylene with an unsaturated carboxylic acid or its anhydride, or a total of 10 to 70% by weight of polypropylene and the modified polypropylene is contained. Blow molding comprising a composition in which the ratio of the number of moles of terminal amine of 66 to the number of moles of carboxylic acid group in the modified polypropylene is 10 to 1000 and the melt flow rate is 0.1 to 10 g / 10 minutes. Goods.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an automobile plastic blow molded product comprising a composition containing nylon 66 and polypropylene, and particularly to heat resistance, calcium chloride resistance, impact resistance, antifreeze resistance and moldability. The present invention also relates to a plastic blow-molded article for automobiles, which is made of a composition containing nylon 66 and polypropylene having excellent mechanical strength and the like.

[0002]

2. Description of the Related Art Recently, plastic blow molded products have been used for various automobile parts such as fuel tanks, heaters for automobiles, tubes for connecting radiators, pipes, etc. for the purpose of reducing the weight of automobiles and improving the space utilization ratio. It has started to be done. Conventionally, such tubes and pipes are manufactured by bending a straight metal pipe, and there is a problem that it takes time to form a complicated shape.

For this reason, the merits of easy workability and weight reduction of plastics have been attracting more attention, and various automobile parts are manufactured by blow molding plastics. When a molded product of such a complicated shape is manufactured by blow molding, molding is easy when a resin having a relatively low melting point such as polyolefin is used as a material resin, but the heat resistance of the resulting molded product is There is a problem that heat resistance strength characteristics are not sufficient. In applications such as automobiles, heat resistance and heat strength characteristics are important requirements. Therefore, it is conceivable to use a high melting point engineering plastic such as polyamide to which an inorganic filler such as glass fiber is blended, if necessary. Then, the content of the inorganic filler such as glass fiber is particularly large. At times, the temperature of the resin drops during extrusion of the parison, and it tends to solidify. Therefore, there is a problem that the parison does not reach the end, or even if the parison reaches the end, the parison does not grow sufficiently and it is difficult to blow.

Therefore, an object of the present invention is to provide a plastic blow-molded article for automobiles which is excellent in heat resistance, calcium chloride resistance, impact resistance, antifreeze resistance, moldability, mechanical strength and the like.

[0005]

As a result of earnest research in view of the above objects, the present inventors have found that nylon 66 and a polypropylene resin containing a polypropylene modified with an unsaturated carboxylic acid or an anhydride thereof in a predetermined ratio. If a tube, a pipe or the like is molded by blow molding from a composition containing and having a predetermined melt viscosity, the moldability is good, and the resulting molded article has heat resistance, calcium chloride resistance, impact resistance, The inventors have found that they are excellent in antifreeze resistance, mechanical strength, etc., and have conceived the present invention.

That is, the plastic blow molded article for automobiles of the present invention comprises (a) nylon 6630 to 90% by weight, and (b)
A modified polypropylene with an unsaturated carboxylic acid or an anhydride thereof, or a total of 10 to 70% by weight of polypropylene and the modified polypropylene is contained, and the number of moles of the terminal amine of the nylon 66 and the moles of the carboxylic acid group in the modified polypropylene. It is characterized by comprising a composition having a ratio to the number of 10 to 1000 and a melt flow rate of 0.1 to 10 g / 10 min.

The present invention is described in detail below. First, each constituent component of the resin composition forming the plastic blow-molded article for automobiles of the present invention will be described.

[1] Resin Composition (1) Composition Component (a) Nylon 66 In the present invention, nylon 66 is used as the polyamide resin from the viewpoint of heat resistance and blow moldability. Nylon 66 is a polyamide produced by using hexamethylenediamine and adipic acid as main components, and may contain 5 mol% or less of another polyamide structural unit.

Although the molecular weight of the above nylon 66 is not particularly limited, those having a relative viscosity η r (measured in JIS K6810, 98% sulfuric acid) of 0.5 or more are generally used, and those having a relative viscosity of 2.0 or more are excellent in mechanical strength. It is preferable in that

(B) Modified polypropylene The modified polypropylene used in the present invention is a polypropylene modified with an unsaturated carboxylic acid or an anhydride thereof. As the unsaturated carboxylic acid or its anhydride, acrylic acid, monocarboxylic acid such as methacrylic acid, maleic acid, fumaric acid, dicarboxylic acid such as itaconic acid, maleic anhydride, dicarboxylic acid anhydride such as itaconic anhydride and the like. Among them, dicarboxylic acid and its anhydride are particularly preferable.

The polypropylene modified with an unsaturated carboxylic acid or its anhydride is not limited to a homopolymer of propylene, and contains 50% by mole or more of a propylene component.
It is also possible to use a random or block copolymer with another α-olefin, which is preferably contained in an amount of 80 mol% or more. Examples of the comonomer copolymerized with propylene include ethylene and other α-olefins, and ethylene is particularly preferable. Therefore, the term "polypropylene" as used herein should be understood to include not only propylene homopolymers but also copolymers. Melt flow rate of the above polypropylene (MFR, 230 ℃, 2.16kg
Load) is preferably 0.01 to 50 g / 10 minutes, especially 0.1 to 5
g / 10 minutes is preferred.

The content of unsaturated carboxylic acid or its anhydride in the modified polypropylene is such that the molar ratio of amine (derived from nylon 66) / carboxylic acid in the composition is in the range of 10 to 1000. Is. Specifically, the content of unsaturated carboxylic acid or its anhydride in the modified polypropylene is preferably 0.01 to 10% by weight. If the amount of modification is less than 0.01% by weight, the effect of improving the compatibility between nylon 66 and polypropylene by the addition of modified polypropylene is not sufficient, and if it exceeds 10% by weight, the compatibility with polypropylene decreases.

The modified polypropylene can be produced by either the melt kneading method or the solution method. In the case of the melt kneading method, polypropylene, modifying unsaturated carboxylic acid (or acid anhydride) and a catalyst are charged into an extruder or a twin-screw kneader,
Knead while heating to a temperature of 180-250 ℃.
In the case of the solution method, the above-mentioned starting materials are dissolved in an organic solvent such as xylene and the stirring is performed. In any case, a usual radical polymerization catalyst can be used as a catalyst, for example, benzoyl peroxide, lauroyl peroxide, ditert-butyl peroxide, acetyl peroxide, tert-butyl peroxybenzoic acid, dicumyl peroxide, Peroxides such as peroxybenzoic acid, peroxyacetic acid and tertiary butyl peroxypivalate, and diazo compounds such as azobisisobutyronitrile are preferable. The amount of the catalyst added is about 1 to 100 parts by weight per 100 parts by weight of the unsaturated carboxylic acid for modification or its anhydride.

The melt flow rate (MFR, 230 ° C., 2.16 kg load) of the modified polypropylene obtained as described above is preferably 0.1 to 500 g / 10 minutes, particularly preferably 1 to 100 g / 10 minutes. If the melt flow rate is less than 0.1 g / 10 minutes, the moldability, especially the blow moldability, is not sufficient, and it becomes difficult to form a complicated shape such as a tube for connecting a heater for an automobile, a radiator or the like, or a pipe. On the other hand, 500 g /
If it exceeds 10 minutes, the mechanical strength decreases, which is not preferable.

In the present invention, it is also possible to use a mixture of the above-mentioned modified polypropylene and unmodified polypropylene. As the unmodified polypropylene, the same polypropylene as the above-mentioned polypropylene to be modified can be used.

In the case of a mixture of modified polypropylene and unmodified polypropylene, the mixing ratio of both is the sum of them.
As 100% by weight, the modified polypropylene is preferably 1% by weight or more, particularly preferably 5% by weight or more.

However, even in the case of a mixture of modified polypropylene and unmodified polypropylene, the content of unsaturated carboxylic acid or its anhydride in the modified polypropylene is such that the amine / carboxylic acid molar ratio is within the range of 10 to 1000. It is like Specifically, the content of unsaturated carboxylic acid or its anhydride in the modified polypropylene is 0.01-10% by weight.
Is preferred.

In the case of the mixture, the melt flow rate (MFR, 230 ° C., 2.16 kg load) is 0.1 to 500 g / 10 min, especially 1 to 10 as in the case of the modified polypropylene alone.
It is preferably 0 g / 10 minutes.

(2) Blending ratio In the composition used in the present invention, the blending ratio of the resin component (nylon 66 + modified polypropylene (added polypropylene as necessary)) is 10 in total.
Nylon 66 is 30 to 90% by weight as 0% by weight, and modified polypropylene (added polypropylene if necessary)
Is 10 to 70% by weight. If nylon 66 is less than 30% by weight (modified polypropylene is more than 70% by weight), heat resistance and mechanical strength are insufficient, and nylon 66 is
When it exceeds 90% by weight (when the modified polypropylene is less than 10% by weight), moldability, calcium chloride resistance and antifreeze resistance are insufficient, and the cost is increased. In particular, nylon 66 is 40 to 80 when it is used as a bend blow molded product such as a tube or a pipe for connecting a heater for an automobile or a radiator.
%, Especially 50 to 70% by weight, preferably 20 to 60% by weight, in particular 30 to 50% by weight, of modified polypropylene (added polypropylene if necessary).

However, as mentioned above, the amount of modified polypropylene and the amount of its carboxylic acid groups are correlated with the amount of terminal amine in nylon 66. The reason is that when the carboxylic acid in the modified polypropylene is melt-blended, nylon 66
Modified polypropylene produced by reaction with the terminal amine of
It is considered that the polyamide graft copolymer serves as a compatibilizer for polypropylene and polyamide, and it is assumed that the amount of the graft copolymer produced is related to the molar ratio of carboxylic acid group / polyamide terminal amine. Is. Therefore, it is necessary to adjust the content of the modified polypropylene so that the ratio of the number of moles of the terminal amine to the number of moles of the carboxylic acid group in the modified polypropylene is 10 to 1000. If the amine / carboxylic acid molar ratio is less than 10, the compatibilization proceeds too much, the properties of nylon 66 and polypropylene are averaged, and the heat resistance decreases. On the other hand, when the amine / carboxylic acid molar ratio exceeds 1000, the compatibilizing effect of the modified polypropylene is insufficient and the mechanical strength of the resulting composition becomes low. The preferred molar ratio is 20-800.

(3) Other Components Inorganic Filler For the purpose of reinforcing the resin composition used in the present invention, an inorganic filler such as glass fiber, talc, calcium carbonate, mica, and whisker may be added. it can. Of these, glass fiber is particularly preferable.

As the glass fiber, either chopped strand or roving can be used, but it is preferable that the average fiber diameter is 6 to 20 μm and the aspect ratio is 100 to 500. In addition, it is preferable to use those which have been surface-treated with a silane coupling agent and / or a binding agent made of a polymer having a carboxyl group or an acid anhydride group. Such surface treatment improves the adhesion between the glass fiber and the polyamide resin.

The compounding amount of the above-mentioned inorganic filler is 50 parts by weight or less, particularly 5 parts by weight, based on 100 parts by weight of the total resin components.
It is preferably about 40 parts by weight. The amount of inorganic filler compounded
If it exceeds 50 parts by weight, moldability, particularly blow moldability, is deteriorated and it becomes difficult to form a tube or pipe having a complicated shape.

Others In the composition used in the present invention, other additives such as a heat stabilizer, an antioxidant, a light stabilizer, a flame retardant, a plasticizer, and an antistatic agent may be added for the purpose of modifying the composition. , A release agent and a foaming agent can be added.

(4) Manufacturing method The composition comprising the above components is heated at 250 to 320 ° C. by using a kneading device such as an extruder such as a single screw extruder or a twin screw extruder. It can be obtained by kneading in a molten state. At that time, for example, JP-A 1-2405
It is also possible to use a twin-screw extruder as shown in No. 61. When glass fibers are mixed, the glass fibers may be added from the beginning together with the polyamide resin, polypropylene and modified polypropylene, or may be added halfway after the resin components are melt-kneaded to some extent.

Melt viscosity The composition used in the present invention is obtained as described above, but has a melt flow rate (275 ° C, 2.16 kg load) of 0.1 to 10 g in view of blow moldability.
/ 10 minutes, preferably 1 to 7 g /
10 minutes. If the melt flow rate is less than 0.1 g / 10 minutes, the resin will flow insufficiently, especially in the mold, and the resin will solidify during extrusion of the parison, resulting in a decrease in moldability. If it exceeds the range, the drawdown property becomes large, and uneven thickness occurs, which causes problems such as cracks in the molded product.

[2] Plastic blow-molded product for automobiles The plastic blow-molded product for automobiles of the present invention comprises the resin composition obtained as described above. The method of molding the plastic blow-molded product for automobiles is not limited to ordinary blow molding, and a three-dimensional bending blow molding method (for example, IHI method or Placo method) can be applied.

A method for producing an automobile plastic blow-molded article (for example, a pipe) of the present invention by blow molding from a composition comprising, for example, nylon 66 / modified polypropylene (polypropylene is added if necessary) / glass fiber will be described.

First, the resin component is melted and extruded into a cylindrical shape from an extrusion blow molding machine at a resin temperature of 250 to 320 ° C., particularly 260 to 290 ° C. As the extrusion blow molding machine, an ordinary accumulator type machine, screw type machine or the like can be used. At this time, in order to delay the solidification of the parison, it is preferable to heat the mold to 80 to 200 ° C., particularly 100 to 180 ° C.

Then, the cylindrical parison is lowered from the upper opening of the mold to guide the parison. On this occasion,
By supplying heated air from the upper opening of the mold as needed and sucking this heated air from the lower opening, the parison can be smoothly guided even in a complicatedly bent shape. .

After that, when the front end of the cylindrical parison protrudes from the lower end opening by a required amount, the front end of the parison is sealed by a punch plate or the like, and then air is blown to blow the plastic blow-molded article for automobiles of the present invention. Can be manufactured.

[0032]

The plastic blow-molded article for automobiles of the present invention comprises a composition containing nylon 66 and a polypropylene resin containing polypropylene modified with an unsaturated carboxylic acid or an anhydride thereof in a predetermined ratio. It can be easily formed into a tube or pipe having a complicated shape by molding, and is excellent in heat resistance, calcium chloride resistance, impact resistance, antifreeze resistance, mechanical strength and the like.

The reason why such an effect is obtained is not necessarily clear, but it is considered as follows. That is, although nylon 66 and polypropylene generally have poor compatibility, by interposing an unsaturated carboxylic acid-modified polypropylene in the ratio of the present invention, the terminal amine of nylon 66, the carboxyl group-containing compound, and the carboxylic acid in the modified polypropylene are mixed. The acid groups react with each other to form a copolymer, and nylon 66 and polypropylene are compatibilized. For this reason, it is considered that both the good blow moldability of polypropylene and the heat resistance of nylon 66 are ideally exhibited, and the physical properties suitable as a plastic blow molded article for automobiles are exhibited.

[0034]

The present invention will be described in more detail by the following examples. The following resin components were used as raw materials. [1] Nylon 66 and Ny66: [M300, T300, Korshak-Za
0.051 m of terminal amino group measured by the method of myationa (reverse titration method) (Chem.Abs.40,4665, '46, ibid. 42,6152, '48)
Equivalent / g] [2] Polypropylene-PP-1: [Melt flow rate (MFR, 230 ° C, 2.
16 kg load) 0.5 g / 10 minutes] PP-2: [Melt flow rate (MFR, 230 ° C, 2.
16kg load) 15g / 10 minutes] [3] Modified polypropylene with unsaturated carboxylic acid or its anhydride-Maleic anhydride modified polypropylene CMPP [Addition amount of maleic anhydride 0.14% by weight, melt flow rate (MFR, 230 ° C, 2.16) kg load) 3g / 10
Min] [4] Glass fiber GF: [MAFT2A, manufactured by Asahi Fiber Glass Co., Ltd., average fiber diameter 13 μm, aspect ratio 230, surface treated with maleic anhydride]

Examples 1 to 3 and Comparative Examples 1 and 2 Nylon (Ny66), polypropylene (PP) and polypropylene modified with maleic anhydride (CMPP) were mixed in the proportions shown in Table 1 and dry blended with a high speed mixer. Then, it was put into the main hopper of a 45 mmφ twin-screw extruder. In addition, the glass fiber (G
F) was charged from the middle of the twin-screw extruder and kneaded at 280 ° C,
A pellet of the composition was obtained.

Table 1 also shows the molar ratio of the amine in nylon 66 to the unsaturated carboxylic acid or its anhydride in the modified polypropylene in each composition.

Using an extrusion blow molding device (IPB-10, manufactured by Ishikawajima Harima Heavy Industries Co., Ltd.), pellets of the obtained composition were set to a resin temperature of 280 ° C. at the time of extrusion, a mold temperature of 150 ° C., and a length of 1000 mm, A plastic pipe having an outer diameter of 20 mm and an average wall thickness of 2 mm was manufactured.

Formability of the pipe thus obtained,
The antifreeze resistance and calcium chloride resistance were evaluated, and the maximum bending load and product weight were measured. The results are also shown in Table 1.

Comparative Examples 3 and 4 Using brass (Comparative Example 3) and stainless steel (Comparative Example 4), a pipe having a length of 1000 mm, an outer diameter of 20 mmφ and an average wall thickness of 0.6 mm was manufactured, and the pipe was manufactured. In the same manner as in Example 1, antifreeze resistance and calcium chloride resistance were evaluated, and maximum bending load and product weight were measured. The results are also shown in Table 1.

Table 1Composition (parts by weight) Example 1 Example 2 Example 3 Example 4 Ny66 60 60 60 60 PP-1 35 35 30 15 PP-2 --- 20 CMPP 5 5 10 5 GF 15 35-15Amine / acid molar ratio * 1 44 44 22 44 MFR* 2 4 3 4 10 Physical property Formability(1) ◎ ◎ ◎ ○ Antifreeze resistance(2) ○ ○ ○ ○ Calcium chloride resistance(3) ○ ○ ○ ○ Maximum bending load(Four) 75 60 45 65 Product weight(Five) 128 147 116 128

Table 1 (continued)Composition (parts by weight) Comparative Example 1 Comparative example 2 Comparative example 2 Comparative Example 3 Ny66 100 60-* 3 −*Four PP-2-35 --- CMPP-5 --- GF-15 ---Amine / acid molar ratio * 1 − 44 − − MFR* 2 14 − − Physical property Formability(1) × × − − Antifreeze resistance(2) −*Five −*Five ○ ○ Calcium chloride resistance(3) −*Five −*Five ○ ○ Maximum bending load(Four) −*Five −*Five 45  Product weight(Five) −*Five −*Five 245 245 Note) * 1: Amine in nylon 66 and modified polypropy
Molar ratio with maleic anhydride in ren. * 2: The melt flow rate of the composition complies with JIS K7210.
Measured at 275 ℃ and 2.16 kg load (Unit: g / 10
Minutes). * 3: Brass pipe. * 4: Stainless steel pipe. * 5: Not evaluated because of poor moldability.

(1) Formability: x indicates cracks or cracks on the surface of the obtained pipe, x indicates slight uneven thickness, and no cracks, cracks, uneven thickness, etc. Was evaluated as ⊚. (2) Antifreeze resistance: Cut a pipe to 100 mm and put it into a 50% aqueous solution of a commercial automobile long life coolant at 120 ° C for 10
After soaking for 00 hours, x was evaluated when cracks and cracks were found on the surface of the pipe, and o when not. (3) Calcium chloride resistance: After wiping the pipe surface with gauze containing a 5% calcium chloride aqueous solution, leaving it in an air oven at 120 ° C for 1 hour and then taking it out 5 times, the pipe surface Cracks, cracks, etc. were evaluated as x, and those not recognized were evaluated as o. (4) Maximum bending load: A pipe was cut into 100 mm and a 3-point bending test was performed with a span distance of 70 mm, and the maximum bending strength was measured (unit: kgf). (5) Product weight: The total weight of the pipe was measured (the unit is g).

As is clear from Table 1, Examples 1 to 4
The plastic pipe of No. 1 had good moldability, antifreeze resistance and calcium chloride resistance, had a large maximum bending load, and was sufficiently lightweight, and was suitable for automobiles. .

[0044]

As described above in detail, the plastic blow-molded article for automobiles of the present invention comprises nylon 66 and a polypropylene resin containing a polypropylene modified with an unsaturated carboxylic acid or an anhydride thereof in a predetermined ratio. Since it is composed of the composition contained in 1., it is easy to form a tube or pipe having a complicated shape by blow molding, and further, in heat resistance, calcium chloride resistance, impact resistance, antifreeze resistance, mechanical strength, etc. Are better.

The plastic blow-molded article for automobiles of the present invention is suitable for various automobile parts such as fuel tanks, heaters for automobiles, tubes and pipes for connecting radiators and the like, especially automobile parts having a complicated curved shape. is there.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Reference number within the agency FI Technical indication location B29L 23:22 31:30 (72) Inventor Koji Egashira 1-chome, Showa-cho, Kariya city, Aichi Japan Within Denso Co., Ltd. (72) Inventor Fumio Kato 1-1, Showa-cho, Kariya city, Aichi Prefecture In-house Denso Co., Ltd. (72) Innovator Nobuo Arai 1-1-cho, Showa-machi, Kariya city, Aichi Nippondenso Co., Ltd. Within

Claims (1)

[Claims]
1. (a) Nylon 66 30 to 90% by weight,
(b) Polypropylene modified with unsaturated carboxylic acid or its anhydride, or containing 10 to 70% by weight of polypropylene and the modified polypropylene, and containing nylon 6
The ratio of the number of moles of the terminal amine of 6 and the number of moles of the carboxylic acid group in the modified polypropylene is 10 to 1000,
A plastic blow-molded article for automobiles, which is characterized by comprising a composition having a melt flow rate of 0.1 to 10 g / 10 minutes.
JP27773593A 1993-10-08 1993-10-08 Plastic blow molded product for automobile Pending JPH07108590A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP27773593A JPH07108590A (en) 1993-10-08 1993-10-08 Plastic blow molded product for automobile

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP27773593A JPH07108590A (en) 1993-10-08 1993-10-08 Plastic blow molded product for automobile

Publications (1)

Publication Number Publication Date
JPH07108590A true JPH07108590A (en) 1995-04-25

Family

ID=17587601

Family Applications (1)

Application Number Title Priority Date Filing Date
JP27773593A Pending JPH07108590A (en) 1993-10-08 1993-10-08 Plastic blow molded product for automobile

Country Status (1)

Country Link
JP (1) JPH07108590A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1066949A1 (en) * 1999-07-08 2001-01-10 Itib S.P.A. Hollow polyamide body obtained by extrusion and blow moulding
JP2006241466A (en) * 2000-10-06 2006-09-14 Arkema France Mixture of polyamide-block-grafted copolymer and flexible polyolefin
CN104072862A (en) * 2014-05-29 2014-10-01 安徽海纳川塑业科技有限公司 Nylon corrugated pipe

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1066949A1 (en) * 1999-07-08 2001-01-10 Itib S.P.A. Hollow polyamide body obtained by extrusion and blow moulding
JP2006241466A (en) * 2000-10-06 2006-09-14 Arkema France Mixture of polyamide-block-grafted copolymer and flexible polyolefin
CN104072862A (en) * 2014-05-29 2014-10-01 安徽海纳川塑业科技有限公司 Nylon corrugated pipe

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