JPH02249644A - Multilayer vessel - Google Patents

Abstract

PURPOSE:To obtain the multilayer vessel having almost no deformation in circumferential direction due to the shrinkage in molding by a method in which the polyolefin resin layers wherein fiber reinforcing material is blended with high nitric resin layer are mutually laminated, and the adhesive layer with a specified shrinkage factor in molding is provided between the high nitrile layer and the polyolefin resin layer. CONSTITUTION:The polyolefin to be used is preferably the material wherein the fiber resin forcing material such as fiber glass or carbon fiber, etc., is blended with polyethylene or polypropylene, etc., in the ratio of 10-40%, and its shrinkage factor in molding is caused to be 0.2-0.5%. An adhesive layer is preferably the block copolymer of butadiene or isoprene and styrene. By using a high speed blow molding machine, the multilayer parison is coextruded so that the outer layer is made of fiber reinforced polyolefin, the intermediate layer is made of adhesive resin and the inner layer is made of high acrylonitrile resin, and then said parison is blow-molded, thereby obtaining a multilayer vessel.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides at least one barrier thermoplastic resin whose main raw material is a high nitride resin having a molding shrinkage rate of 0.2 to 0.5%. The present invention relates to a multilayer container made of plastic having one layer, and is related to a multilayer container that undergoes almost no deformation in the circumferential direction due to molding shrinkage.

[Conventional technology]

High nitrile resins have excellent transparency and barrier properties against not only oxygen and carbon dioxide gas, but also organic solvent gases such as esters, and liquefied gases such as Freon.They also have excellent chemical resistance against various chemicals, especially alcohols. , esters,
Excellent chemical stability against organic solvents such as gasoline. In addition, high nitrile resin has excellent fragrance retention properties against a wide range of aromatic components such as fragrances, spices, and essential oils, making it ideal for cosmetics, pharmaceuticals, toiletries, etc. I4 drug,
It has been widely used as a packaging material for seasonings, fragrances, edible oils, aerosol containers, etc.

[Problem to be solved by the invention]

For plastic containers using high nitrile resin, multilayer containers with polyolefin resin have been used to increase cost benefits and impact strength, but among the polyolefin resins, the most common The polyethylene and polypropylene used are crystalline thermoplastic resins with a high molding shrinkage rate (polyethylene: about 3
．． 2%, polypropylene: approx. 1.7%), is a non-grade thermoplastic resin with a low molding shrinkage rate (0.2 to 0.5%). When laminated and bonded with high nitrile resin, the molding shrinkage rate after molding will decrease. This difference causes the container to deform, and there is a problem in that the deformation in the circumferential direction of the body is particularly large, and the appearance of the container is significantly impaired.

A means to solve the deformation of a plastic multilayer container having at least one layer made of barrier thermoplastic resin whose main raw material is high nitrile resin is to shape the container by providing ribs on the body of the container. The current method is to make containers difficult to deform, and since this method results in a narrower design of the container, improvements have been desired.

The object of the present invention is to relate to a plastic multilayer container having at least one layer made of a barrier thermoplastic resin whose main raw material is a high nitrile resin having a molding shrinkage rate of 0.2 to 0.5%. The object of the present invention is to provide a multilayer container that is hardly deformed in the circumferential direction due to molding shrinkage.

[Means for solving the invention]

The multilayer container of the present invention has at least one layer made of a barrier thermoplastic resin whose main raw material is a high nitrile resin having a molding shrinkage rate of 0.2 to 0.5%, and the high nitrile resin layer A polyolefin resin layer blended with a fiber reinforcing material is laminated and bonded on one or both sides of the layer, and if necessary, an adhesive layer with a molding shrinkage rate of 0.3% is provided between the high nitrile layer and the polyolefin resin layer. Molded by laminating and bonding.

Methods for manufacturing a multilayer container include methods of manufacturing a multilayer container with an integrated body and bottom by injection molding, blow molding, or injection stretch blow molding, extruding the constituent laminate into a film or sheet shape, and melt laminating. This method can be applied.

In blow molding, a multilayer parison is obtained by coextruding each of the above-mentioned resins, and this is blow molded as it is or after being stretched to obtain a multilayer container.

Note that the thickness of each layer of the molded multilayer container is not particularly limited.

The high nitrile resin used in the present invention is a copolymer mainly composed of an unsaturated nitrile compound, and preferably contains 50% by weight or more of the unsaturated nitrile compound.

Examples of the comonomer include styrene, butadiene, isoprene, etc., and it is preferable to copolymerize one or more of these with an unsaturated nitrile compound, and if necessary, stabilizers, A lubricant, an antistatic agent, an ultraviolet inhibitor, and a coloring pigment may be added.

The polyolefin used in the present invention includes polyethylene,
A fiber reinforcing material such as fiber glass or carbon fiber is blended into polypropylene, ethylene-propylene copolymer, or a mixture thereof at a ratio of 10 to 40%,
It is preferable that the molding shrinkage rate is 0.2 to 0.5%,
If necessary, stabilizers, lubricants, antistatic agents, ultraviolet inhibitors, and coloring pigments may be added.

The adhesive layer used in the present invention is preferably, for example, butadiene or a block copolymer of isoprene and styrene.

〔Example〕

The present invention will be explained below with reference to Examples.

[Example 1] High acrylonitrile resin “Valex 101ON”
(Product name, manufactured by Mitsui Toatsu Chemicals) and high-density polyethylene
FF-1004” (Product name, manufactured by LNPCORP)
Using a butadiene-styrene copolymer "Tuffprene 200" (trade name, manufactured by Asahi Kasei Corporation) as an adhesive resin, a Bekum high-speed blow molding machine BA-2 was used. A multilayer parison was coextruded so that the outer layer was a fiber-reinforced polyolefin, the middle layer was an adhesive resin, and the inner layer was a high-power acrylonitrile resin, and this was blow molded to obtain a multilayer container.

For co-extrusion of the multilayer parison, extruders with a diameter of 25 mm are used for high acrylonitrile resin and adhesive resin, and extruders with a diameter of 50 mm are used for fiber-reinforced polyolefin.
The experiment was carried out using a 3N hard head and a 3N extruder.
The extrusion temperature is 170-210'C higher than the screw/feed zone for high acrylonitrile resin.A blower is used to prevent temperature rise due to shear heat generation, and 155-200'C higher than the screw/feed zone for adhesive resin.
.

The temperature was 170-220°C for the fiber-reinforced polyolefin, and 210-220°C for the Gui head. The mold temperature is 16
'C1 cooling time 12 seconds, blowing pressure 8kg/cI12
The molding was done with.

The shape of the obtained container was 70 mm in diameter and 185 mm in height.
It was a cylindrical container with an inner diameter of 19 mm and a capacity of 500 m1, and the thickness of each layer of the body was 540 μm for the outer layer, 125 μm for the middle layer, and 170 μm for the inner layer.

The circumferential shape of the body of the multilayer container obtained above was measured, and the difference between the maximum diameter and the minimum diameter was determined.

The results are shown in Table 1.

[Example 2] High acrylonitrile resin “Valex 101ON” (
Product name: Mitsui Toatsu Chemical Co., Ltd.) and high-density polyethylene'
RPE-7210″ (Product name, Ferro C0R
Using a butadiene-styrene copolymer ``Kufubrene 200'' (trade name, manufactured by Asahi Kasei Corporation) as an adhesive resin, a resin blended with 10% fiberglass blend) (manufactured by P. Using machine BA-2, a multilayer parison having an outer layer of fiber-reinforced polyolefin, an intermediate layer of adhesive resin, and an inner layer of high acrylonitrile resin was coextruded, and this was blow molded to obtain a multilayer container.

For co-extrusion of the multilayer parison, extruders with a diameter of 25 mm are used for high acrylonitrile resin and adhesive resin, and extruders with a diameter of 50 mm are used for fiber-reinforced polyolefin.
The experiment was carried out using a 3-layer Gouy head using a 3-layer extruder.
The extrusion temperature is 170-210°C higher than the screw/feed zone for high acrylonitrile resin, 155-200°C higher than the screw/feed zone for adhesive resin using a blower to prevent temperature rise due to shear heat generation.
The temperature was 170-220°C for the fiber-reinforced polyolefin, and 210-220°C for the Gui head. The mold temperature is 16
℃, cooling time 12 seconds, and blowing pressure 8 kg/C Peng 3.

The shape of the obtained container was 85 mm in diameter and 227 mm in height.
It was a cylindrical container with an inner diameter of 18 mm and a capacity of 10,100 O, and the thickness of each layer of the body was 800 μm for the outer layer, 125 μm for the middle layer, and 300 μm for the inner layer.

The same measurements as in Example 1 were performed on the obtained multilayer container.

The results are also shown in Table 1.

[Comparative Example 1] High acrylonitrile resin “Valex 101ON°°”
(Product name, manufactured by Mitsui Toatsu Chemical ■) and high-density polyethylene”
HIZEX 6200B” (Product name, Mikata Petrochemical ■
Using a butadiene-styrene copolymer "Toughblane 200'" (trade name, manufactured by Asahi Kasei Corporation) as an adhesive resin, the outer layer is polyolefin and the middle layer is bonded using a Bekum high-speed blow molding machine BA-2. A multilayer parison whose inner layer was made of a high acrylonitrile resin and a high acrylonitrile resin was coextruded and blow molded to obtain a multilayer container.

In addition, for coextrusion of multilayer parisons, high acrylonitrile resin and adhesive resin have a diameter of 25 mm, respectively.
For polyolefins, an extruder with a diameter of 50 mm was used, and a three-layer Gouy head made by our company was used. The extrusion temperature is 170-210°C above the screw/feed zone for high-acrylonitrile resin.2 A blower is used to prevent temperature rise due to shear heat generation, adhesive resin is 155-200°C above the screw/feed zone, and 170-210°C for polyolefin. 220°C, Gui head is 210
The temperature was ~220°C.

Mold temperature was 16°C, cooling time was 12 seconds, and blowing pressure was 8
Molding was carried out at kg/c-.

The multilayer container obtained above has the same container shape as Example 1, and the thickness of each layer of the body is 540 μm for the outer layer and 12 μm for the middle layer.
The inner layer was 170μ.

The same test as in Example 1 was conducted on the obtained multilayer container.

The results are also shown in Table 1.

[Comparative Example 21 High acrylonitrile resin “Valex 101ON” (
Product name: Mitsui Toatsu Chemical ■) and high-density polyethylene
Hyzex 6200B" (trade name, manufactured by Mitsui Petrochemical Corporation) and butadiene-styrene copolymer "Toughblen 200" (trade name, Asahi Kasei Corporation) as an adhesive resin.
A multilayer parison consisting of an outer layer of polyolefin, an intermediate layer of adhesive resin, and an inner layer of high acrylonitrile resin was coextruded using Bekum high-speed blow molding IBA-2, and this was blow molded to obtain a multilayer container. Ta.

The multilayer parison was coextruded using a 3-layer Gouy head made by our company, using an extruder with a diameter of 25 mm for high acrylonitrile resin and adhesive resin, and an extruder with a diameter of 50 mm for polyolefin. The extrusion temperature is 170-210'C above the screw feed zone for high acrylonitrile resin, a blower is used to prevent temperature rise due to shear heat generation, 155-200'C above the screw feed zone for adhesive resin, and 170-210'C for polyolefin. 220°C, Gui head is 21θ~2
It was 20°C.

Mold temperature: 16°C, cooling time: 12 seconds, blowing pressure: 8
Molding was performed at kg/cm.

The shape of the obtained container was 85 mm in diameter and 227 mm in height.
It was a cylindrical container with an inner diameter of 18 mm and a capacity of 10,100 O, and the thickness of each layer of the body was 800 μm for the outer layer, 125 μm for the middle layer, and 300 μm for the inner layer.

The same measurements as in Example 1 were performed on the obtained multilayer container.

The results are also shown in Table 1.

Table 1: Dimensional measurement results [Effects of the invention] As shown in Table 1, the multilayer container of the present invention has a smaller diameter at the container body than the conventional multilayer container made of high nitrile resin and polyolefin resin. Considering that the mold cavity is a perfect circle with a small difference between the maximum circumferential diameter and the minimum circumferential diameter, it is assumed that there is almost no deformation of the container in the circumferential direction. No, it's a multi-layered container that maintains an excellent shape.

Claims (2)

[Claims] (1) A multilayer container characterized by laminating and bonding a polyolefin resin layer blended with a fiber reinforcing material on one or both sides of a high nitrile resin layer. (2) A multilayer container characterized in that an adhesive layer having a mold shrinkage rate of 0.3% is laminated and bonded between the high nitrile layer and the polyolefin resin layer according to claim (1).