JP2008164131A - Pressure container and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pressure container excellent in air tight sealing performance, in which the adhesive strength between the inside wall of a hollow container to be made of synthetic resin liner material and a mouth ring member is improved, and further to provide its manufacturing method by which the pressure container can be economically manufactured by a simple process. <P>SOLUTION: The pressure container is composed of: a hollow container to be made of the synthetic resin liner material, and a reinforcing material layer to be made of reinforcing material by covering the outer layer of the hollow container; and at least one mouth ring member, and is manufactured by bonding or depositting the hollow container and the mouth ring member via an adhesive layer provided on the outer layer of the hollow container. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a pressure vessel and a method for producing the same, and more specifically, by preventing winding slippage of a reinforcing yarn forming a reinforcing material on the outer surface of a hollow vessel formed of a synthetic resin liner material. In addition, by strengthening the adhesive force between the inner surface of the hollow container and the base member, the adhesive force is improved and the airtight seal performance is dramatically improved and the pressure container can be obtained in a simple process. Further, the present invention relates to a manufacturing method that can be manufactured economically.

  In pressure vessels such as natural gas, compressed natural gas, oxygen, nitrogen, and hydrogen tanks, the filling pressure is as high as 20 MPa to 100 MPa. Conventionally, metal high-pressure vessels made of cast iron or steel are generally used. However, in order to improve fuel economy, automobile parts have become more popular, such as the spread of fuel cell electric vehicles that use hydrogen to reduce the amount of carbon dioxide that causes global warming. Due to environmental changes such as weight reduction, automobile fuel diversification and recycling, these pressure vessels are also rapidly becoming plastic.

  For example, fuel cells using LPG and hydrogen as fuel for automobiles are used, and weight reduction of the pressure vessel to be mounted is desired. For example, as an alternative to steel containers, aluminum liners reinforced with carbon fiber are used, but resin containers using plastic liners have also been developed to further reduce weight. ing. For example, the container described in Patent Document 1 is a pressure container in which a resin-made liner having gas barrier properties is covered with an outer shell made of pressure-resistant fiber reinforced plastic (FRP), and is essentially made of resin. It is lighter than metal ones and can be expected to improve fuel efficiency.

  In such a pressure vessel, as shown in Patent Document 1, the outer surface of a synthetic resin liner material is made of fiber reinforced plastic (FRP) or fiber reinforced metal composite (FRM). Reinforcing yarn is wound and laminated in a helical winding layer, hoop winding layer, label winding layer, etc. by filament winding method or tape winding method, etc., and a reinforcing material layer is formed by melting or curing an adhesive such as thermosetting resin. Although it is generally formed, there is a problem that when these fiber yarns are wound around the liner material, the surface is slippery, and the reinforcing yarn is displaced and cannot be wound well.

  On the other hand, such a pressure vessel is provided with a nozzle mounting base in order to mount a nozzle for filling a gas into the container or taking out the gas from the container. Normally, the base member is integrally coupled with the inner liner material of the container, but the base member for screwing the nozzle is usually made of metal, and the inner liner material is used in terms of weight reduction or simplification of the manufacturing process. Since the base member is made of a different plastic material, the sealing property of the joint portion or interface portion between the inner liner material and the base member is required.

  In particular, since the pressure vessel is filled with a high-pressure gas of 25 MPa to 100 MPa, extremely high gas sealing properties are required. In these resin pressure vessels, as a technique for improving the gas sealability of the cap member, for example, in the pressure vessel described in Patent Document 2, the disc-shaped flange portion of the cap member is received by the upper and lower lips of the inner shell end portion. By adopting a structure, the gas sealability of the base member is enhanced, but the end of the base member is exposed on the inner wall surface of the inner shell, and the gas internal pressure is directly applied to the end of the base member. Even if there is no gas leakage immediately after manufacturing, the resin of the inner shell will creep and shrink while using the product container for a long time, and a gap will occur at the interface between the inner shell and the base member, There is a risk of gas leakage from gaps in the interface.

Moreover, in patent document 3, in the pressure vessel comprised by the outer shell which wound the filament, and the non-metallic inner liner, the locking groove provided in the annular flange so as to engage with the complementary tab on the liner; A pressure vessel is proposed, and a locking groove is provided on the upper and lower surfaces of the disc-shaped flange portion of the base, and a tab that matches the upper and lower locking grooves is formed at the end of the inner liner and joined. The risk of causing leakage between the outer shell and the liner is reduced.
However, since the end of the base member is exposed on the inner wall surface of the inner shell and the internal pressure of the gas is directly applied to the end of the base member, gas leakage occurs for the same reason as described above. There is a fear.

  Further, in Patent Document 4, a gas cylinder having an inner shell having a gas barrier property, a pressure outer shell provided so as to cover the inner shell, and a nozzle mounting cap built in a neck portion of the inner shell, A seal ring is fitted to the base and the seal ring is pressed to suppress gas leakage. However, when the pressure is high, there is a possibility that sufficient sealing performance may not be exerted and the gas is pressed. Therefore, the deterioration of the sealing material is remarkable, and not only is the replacement of the sealing (such as an O-ring) complicated and uneconomical, but also the inconvenience that the product container needs to be disassembled when the replacement is performed. . Similarly, pressure vessels having a sealing mechanism using lip packing (Patent Literature 5, Patent Literature 6 and the like) or pressure vessels having a self-sealing portion (Patent Literature 7) have been proposed. Have the same inherent problems.

Further, in Patent Document 8, in a pressure vessel having a gas barrier inner shell and a pressure-resistant outer shell, and a cap member attached to at least one end, the shoulder of the liner material of the inner shell and one end There has been proposed a pressure vessel in which a base member having a disk shape on the side is bonded via an adhesive resin layer and the sealing property at the interface between the liner material of the inner shell and the base member is excellent.
The adhesive resin layer in Patent Document 5 is preferably an unsaturated carboxylic acid-modified polyethylene resin, and has a density of 0.88 to 0.945 g / cm ³ and an MFR of 0.05 to 50 g / 10 min. It has been shown that polymers are used (see Patent Document 5, paragraph [0010]).
However, in these patent documents, an adhesive resin powder is attached to the base member in advance and pressed and adhered with a fluororesin, or the base member is heated to increase the melting temperature of the adhesive resin and the adhesive resin is placed on the surface. A complicated process is required, such as pressing and adhering the film to provide an adhesive resin layer. In addition, there are problems such as the property of the adhesive resin and the specific description thereof are not shown at all.

Furthermore, in Patent Document 9, when the insert member is mounted by blow molding, the parison is closed, and the parison and the insert member are integrated, the pressure applied via the thermoplastic adhesive between the parison and the insert member A method for manufacturing a container is disclosed.
However, in the above-mentioned patent document, the properties of the adhesive and the specific description thereof are not shown in the examples.

  Hydrogen gas with a low molecular weight, although it is airtight for natural gas with a relatively high molecular weight, especially in conventional pressure vessels, although demands for quality control of recent products, demand for higher-pressure gas filling, and particularly in conventional pressure vessels However, it is difficult to say that sufficient hydrogen gas permeation resistance is maintained, and there is a demand for producing a higher-performance adhesive performance and a high-quality product at a lower cost and with a simple manufacturing process.

Japanese Patent Laid-Open No. 7-305798 JP-A-6-42698 JP-A-6-137433 JP-A-8-219387 JP 2000-265138 A JP 2005-9591 A JP 2004-211763 A Japanese Patent Laid-Open No. 10-332082 JP 2006-161978 A

  An object of the present invention is to prevent the displacement of the reinforcing yarn that forms the reinforcing material of the outer surface of the hollow container formed of the synthetic resin liner material during winding, and the inner surface of the hollow container A pressure vessel with improved adhesive strength and dramatically improved hermetic sealing by strengthening the adhesive strength with the base member, and a manufacturing method capable of manufacturing the pressure vessel in a simple process and economically It is to provide.

  As a result of intensive studies in order to solve the above problems, the present inventors have determined that a hollow container formed of a synthetic resin liner material and a reinforcement formed by covering the outer peripheral surface of the hollow container with a reinforcing material. A pressure vessel having at least one base member, wherein the hollow container and the reinforcing material layer are bonded or welded via an adhesive layer provided on the outer layer of the hollow container. The pressure vessel and its manufacturing method can solve the above problems all at once, can form a uniform film in a simpler process, and reinforces the reinforcing material on the outer surface of the hollow container formed of a synthetic resin liner material By preventing unwinding during winding of the yarn, and by strengthening the adhesive force between the inner surface of the hollow container and the base member, the adhesive force is improved and the airtight sealing performance is dramatically improved. Pressure vessel and pressure vessel thereof It found that can be provided, which resulted in the completion of the present invention.

  That is, according to the first invention of the present invention, it has a hollow container formed of a synthetic resin liner, and a reinforcing material layer formed of a reinforcing material provided on the outer layer of the hollow container, and There is provided a pressure vessel having at least one base member, wherein the hollow vessel and the reinforcing material layer are bonded or welded via an adhesive layer provided on an outer layer of the hollow vessel.

  According to a second invention of the present invention, in the first invention, the hollow container is provided with a pressure container in which an adhesive layer is formed on the innermost layer.

  According to the third invention of the present invention, in the second invention, the hollow container and the base member are bonded or welded via an adhesive layer formed in the innermost layer of the hollow container. A pressure vessel is provided.

  According to a fourth aspect of the present invention, there is provided the pressure vessel according to any one of the first to third aspects, wherein the adhesive layer has a thickness in the range of 10 μm to 5 mm.

According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the adhesive forming the adhesive layer is at least one of the following (a) to (e): There is provided a pressure vessel which is an adhesive made of a polyolefin-based resin containing a functional group or a composition thereof.
[Functional group]
(A) Carboxylic acid group or carboxylic acid anhydride group (b) Epoxy group (c) Hydroxyl group (d) Amino group (e) Silyl group is provided.

According to a sixth invention of the present invention, in the fifth invention, the adhesive comprises the following (A) to (D) containing at least one functional group of the above (a) to (e): At least one polyethylene resin (X) selected from 0.5 to 100% by weight and at least one unmodified polyethylene resin (Y) selected from the following (A) to (E) 0 to 99. A pressure vessel comprising (z1) an adhesive resin (Z) having a density of 0.86 to 0.97 g / cm ³ and (z2) a melt flow rate of 0.01 to 100 g / 10 min is provided.
(A): (a1) density 0.94 to 0.97 g / cm ³ , (a2) high density polyethylene resin having a melt flow rate 0.01 to 100 g / 10 min (B): (b1) density 0.90 Less than 0.94 g / cm ³ , (b2) linear low density polyethylene resin (C) having a melt flow rate of 0.01 to 100 g / 10 min: (c1) high pressure radical method having a melt flow rate of 0.01 to 100 g / 10 min Polyethylene resin (D): (d1) Ultra low density polyethylene resin (E) having a density of 0.86 to less than 0.90 g / cm ³ and (d2) melt flow rate of 0.01 to 100 g / 10 min (E): thermoplastic elastomer

  According to a seventh aspect of the present invention, there is provided a pressure vessel according to the sixth aspect, wherein the (A), (B) or (D) is a polyethylene resin produced with a single site catalyst. The

  According to the eighth invention of the present invention, in the sixth or seventh invention, the adhesive resin (Z) is a functional group-containing polyethylene resin (X) of 5 to 95% by weight, and an unmodified polyethylene resin. A pressure vessel comprising (Y) 5 to 95% by weight is provided.

  According to a ninth invention of the present invention, in any one of the sixth to eighth inventions, the adhesive has at least one functional group of (a) to (e) described above as a whole of the adhesive. A pressure vessel containing 0.001 to 30% by weight, based on weight, is provided.

According to a tenth aspect of the present invention, in any one of the first to ninth aspects, the synthetic resin liner material includes a polyethylene resin having a density of at least 0.92 to 0.97 g / cm ^3. A pressure vessel that is a synthetic resin material is provided.

  According to an eleventh invention of the present invention, in any one of the first to tenth inventions, the synthetic resin liner material is a polyethylene resin having a high load melt flow rate of 2 to 70 g / 10 min. A pressure vessel that is a synthetic resin material is provided.

  According to a twelfth aspect of the present invention, in any one of the first to eleventh aspects, the synthetic resin liner material includes at least one of an engineering plastic, a metal member, and an inorganic filler in the resin. A pressure vessel is provided that is a dispersed composite.

  According to a thirteenth aspect of the present invention, in any one of the first to twelfth aspects, the synthetic resin liner material comprises a laminate including at least a thermoplastic resin layer / adhesive layer / barrier layer. A container is provided.

  According to a fourteenth aspect of the present invention, there is provided a pressure vessel according to any one of the first to twelfth aspects, wherein the reinforcing material is a fiber reinforcing material.

  According to the fifteenth aspect of the present invention, there is provided a hollow container formed of a synthetic resin liner material, and a reinforcing material layer formed of a reinforcing material provided on the outer layer of the hollow container, and A method of manufacturing a pressure vessel having at least one cap member, wherein an adhesive layer is provided on an outer layer of the hollow vessel, and the hollow vessel and the reinforcing material layer are bonded or welded via the adhesive layer. A manufacturing method is provided.

  According to a sixteenth aspect of the present invention, in the fifteenth aspect, an adhesive layer is further provided on the innermost layer of the hollow container, and the hollow container and the base member are bonded or welded via the adhesive layer. A pressure vessel manufacturing method is provided.

  According to the seventeenth aspect of the present invention, in the fifteenth aspect, the pressure for simultaneously forming the hollow container, the hollow container, and the adhesive layer of the outer layer of the hollow container by multilayer blow molding A method for manufacturing a container is provided.

  According to an eighteenth aspect of the present invention, in the sixteenth aspect, a pressure vessel according to the sixteenth aspect, wherein the hollow vessel and the outer and innermost adhesive layers of the hollow vessel are simultaneously formed by multilayer blow molding. A method is provided.

  According to a nineteenth aspect of the present invention, there is provided a method for manufacturing a pressure vessel according to any one of the fifteenth to eighteenth aspects, wherein the base member has been previously treated with a surface treatment agent.

According to the present invention, by providing an adhesive layer on the outer layer of a hollow container formed of a synthetic resin liner material, carbon fiber, glass fiber, or the like is wound around the outer surface of a conventional synthetic resin liner material. The reinforcing yarn is not misaligned when the reinforcing layer provided is formed, and a beautiful and strong reinforcing layer can be created. Further, by providing the adhesive layer in the innermost layer of the hollow container, it is not necessary to perform coating coating or sheeting processing like powder coating on the disk part of the base member in advance, and the liner material can be formed by multilayer blow molding or the like. The innermost adhesive layer can be extruded at the same time, and it is possible to manufacture the inner surface of the synthetic resin liner material and the base member in a single process, which greatly increases the manufacturing cost. Not only is it reduced and economical, but also the production speed and work efficiency are improved.
Moreover, by using a specific adhesive, the adhesive force can be dramatically improved, and the hermetic sealability can be enhanced.
In addition, by applying a metal base treatment agent to the base member in advance, the adhesive on the innermost layer of the synthetic resin liner and a strong adhesive force can be obtained. Therefore, it can be suitably used as a high pressure vessel such as hydrogen gas as well as a low pressure vessel such as natural gas.

  As described above, the present invention includes a hollow container formed of a synthetic resin liner material, and a reinforcing material layer formed of a reinforcing material provided on an outer layer of the hollow container, and at least one base. A pressure vessel having a member, wherein the hollow vessel and the reinforcing material layer are bonded or welded via an adhesive layer provided on the outer layer of the hollow vessel.

In addition, as described above, the present invention has a hollow container formed of a synthetic resin liner material, and a reinforcing material layer formed of a reinforcing material provided on the outer layer of the hollow container, and at least 1 A method of manufacturing a pressure vessel having two cap members, wherein an adhesive layer is provided on the outer layer of the hollow vessel, and the hollow vessel and the reinforcing material layer are bonded or welded via the adhesive layer It is.
Below, this invention is demonstrated in detail for every item.

1. Structure of Pressure Vessel Hereinafter, the pressure vessel of the present invention will be described in detail based on the drawings.
FIG. 1 shows a partially cutaway sectional view of an example of the pressure vessel of the present invention.
As shown in FIG. 1, the pressure vessel according to the present invention includes a hollow container 1 (inner wall) formed of a synthetic resin liner material, and a reinforcement formed of a reinforcing material on an outer layer outside the hollow container 1. A pressure vessel comprising a material layer 2 (outer wall) and having a base member 3 for attaching a nozzle for filling and discharging a high-pressure gas at at least one end of the hollow vessel 1, An adhesive layer 4 is provided on the outer layer of the hollow container 1 formed of a resin liner material. If desired, an adhesive layer 4 ′ is provided on the innermost layer of the hollow container 1, and the hollow container is interposed via the outer adhesive layer 4. 1 is a pressure vessel 10 formed by bonding or welding 1 and the reinforcing material 2 together.

2. Materials for Pressure Vessel Constituent Materials The raw materials used in the present invention are specifically described in detail below.
(1) Synthetic Resin Liner Material The synthetic resin liner material forming the hollow container 1 is required to contain a high-pressure gas filled in the pressure vessel 10 and have a gas barrier property that does not leak. As polyolefin resin such as high density polyethylene resin, cross-linked polyethylene, polypropylene resin, and cyclic olefin resin, polyamide resin such as nylon 6, nylon 6,6, nylon 11 and nylon 12, polyethylene terephthalate, polybutylene terephthalate, etc. Engineering plus for polyester resin, acrylonitrile-butadiene-styrene copolymer resin (ABS) resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyimide resin, etc. Such as ticks. The synthetic resin liner material may be composed of any of a single layer material, a laminated material, and a composite material. Among these, polyethylene resins are most preferable from the viewpoints of gas barrier properties, processability, workability, economy, and the like.

In the case where the polyethylene resin is used as a synthetic resin liner, the density is 0.920 to 0.970 g / cm ³ , preferably 0.930 to 0.960 g / cm ³ , and more preferably 0.8. A range of 940 to 0.950 g / cm ³ is desirable.
When the density is less than 0.920 g / cm ³ , the rigidity is insufficient and the rigidity of the tank mouth portion is insufficient, and when the density exceeds 0.970 g / cm ³ , the durability may be lowered.
In the polyethylene resin, the high load melt flow rate: HLMFR (JIS K6922-1 (1997), condition D (measured at a temperature of 190 ° C. and a load of 211.8 N)) is 2 to 70 g / 10 minutes, preferably 3 to 60 g / 10 min, more preferably 4 to 50 g / 10 min is desirable, and within such a range, the synthetic resin liner material and the adhesive may be pressed simultaneously, particularly by multilayer blow molding. It is preferable because there is no layer disturbance when taking out and the surface layer is improved.
When the HLMFR is less than 2 g / 10 minutes, the resin pressure increases and the extrusion characteristics deteriorate, and when it exceeds 70 g / 10 minutes, there is a possibility that the impact properties and durability are insufficient.

  These synthetic resin liner materials may be composed of a single layer body, a multilayer body, and a composite material of the thermoplastic resin. Examples of composite materials and laminated materials include composite materials in which engineering plastics, metal members, inorganic fillers, and the like are dispersed in the polyethylene-based resin. The laminated material may be a laminated body having a multilayer structure including at least a thermoplastic resin layer / adhesive layer / barrier layer.

  The engineering plastics include various polyamide (PA) resins such as nylon 6, nylon 6,6, nylon 11 and nylon 12, various hydroxyl group-containing resins such as ethylene-vinyl alcohol copolymer (EVOH) and polyvinyl alcohol (PVA). , Various polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-styrene copolymer resin (AS), polycarbonate (PC) resin, polyacetal (POM) resin, polyphenylene ether (PPE) resin, polyphenylene sulfide (PPS) resin, aromatic polyester resin (liquid crystal resin), and the like.

  Moreover, as said metal member, metals, such as iron, aluminum, copper, tin, zinc, nickel, titanium, and various alloys containing these are mentioned.

  In addition, examples of the inorganic filler include talc, silica, calcium carbonate, mica, and the like. When ensuring rigidity, fine powder talc having a plate-like crystal structure with an average particle size of 0.5 to 10 μm Fine powder mica is preferred.

Further, as a synthetic resin liner material having a laminated structure, a thermoplastic resin layer / adhesive layer / barrier layer, such as the above-mentioned polyethylene resin, has a three-layer structure, a thermoplastic resin layer / adhesive layer / barrier layer / Adhesive layer / thermoplastic resin layer 3 type 5 layer structure, thermoplastic resin layer / regrind layer / adhesive layer / barrier layer / adhesive layer / thermoplastic resin layer 4 type 6 layer structure, etc. In addition to a laminate of three or more layers, a laminate composed of two layers / two layers of a thermoplastic layer / adhesive layer or two layers / three layers of an adhesive layer / barrier layer / adhesive layer can be used.
Examples of the material suitably used for the barrier material layer include polyamide resin, polyester resin, ethylene-vinyl alcohol copolymer, polyvinyl alcohol resin, polyacrylonitrile resin, and the like.
As the adhesive layer used here, a general adhesive resin such as an adhesive resin (Z) of the present invention described later or a thermosetting resin such as an epoxy resin or a polyurethane resin can be used.
When these synthetic resin liner materials are used as containers, they can be produced by a molding method such as a blow molding method, an injection molding method, a rotational molding method, or a compression molding method. Of these, the blow molding method is preferred.

(2) Reinforcing material The reinforcing material forming the reinforcing material layer 2 covers the outer layer of the hollow container 1 formed from the synthetic resin liner material, and plays a role of improving the pressure resistance performance of the pressure container 10, aluminum, It may be made of a lightweight metal material such as titanium or light alloy. However, in consideration of molding processability, weight reduction, etc., fiber reinforced plastic (FRP) or fiber reinforced metal composite material (FRM) : Fiber reinforced metal). That is, in order to form the FRP outer wall so as to cover the outer peripheral wall of the cylindrical container formed by blow molding or the like of the synthetic resin liner material constituting the inner wall, the inner cylindrical container A winding layer of a reinforcing fiber bundle impregnated with a resin, such as a helical winding layer, a hoop winding layer, or a label winding layer, is formed on the outer peripheral wall by a filament winding method or a tape winding method, and then the resin is heated to melt or It can be used as a reinforcing material for the outer wall by curing and molding. The strength of the outer side wall can be reinforced within a suitable range according to the purpose by combining various types of reinforcing fibers that form the wound layer, winding form, winding thickness, resin type, resin thickness, etc. It can be a material. Further, it may be formed by other methods such as a prepreg method in which a continuous reinforcing material such as a fabric is impregnated with a thermosetting resin.

Examples of the reinforcing fiber for forming the wound layer include carbon fiber, glass fiber, organic high modulus fiber (for example, polyaramid fiber), inorganic fiber (metal fiber, whisker, boron fiber, Tyranno fiber), etc. One type or two or more types can be used in combination.
These reinforcing fibers are excellent in specific strength and specific elastic modulus, scarcely generate yarn breakage and fluff during winding, and carbon fibers are particularly preferable from the viewpoints of improving productivity and preventing reduction in impact resistance.

  Reinforcing material forming resins include epoxy resins, unsaturated polyester resins, urea resins, phenol resins, melamine resins, polyurethane resins, polyimide resins and other thermosetting resins, polyamide resins, polyethylene terephthalate, polybutylene terephthalate and other polyester resins Engineering plastics such as ABS resin, polyetherketone and polyphenylene sulfide, and thermoplastic resins such as polypropylene and poly-4-methyl-1-pentene resin. Among these, thermosetting resins are generally preferable from the viewpoints of performance such as heat resistance and strength, and economical efficiency.

(3) Base Member The base members 3 and 3 ′ of the present invention are installed for attaching a high-pressure gas filling and discharging nozzle, one end of which has a disk shape, and the pressure vessel 10. At least one end of a cylindrical container composed of an inner hollow container 1 and an outer pressure-resistant reinforcing material layer 2, a cap member 3 on a hemispherical shoulder 7 inside the hollow container 1 of the pressure container, 3 ′ disk portion 8 is embedded so as to be embedded, and preferably the base member 3, 3 ′ disk portion 8 and the innermost adhesive layer of the hollow container 1, which have been previously roughened or ground-treated. 4 'is contacted and adhered or welded.

  The material of the base members 3, 3 ′ may be either metal or resin. Examples of the metal include aluminum, copper, nickel, titanium alloys, composite materials thereof, and chromium / molybdenum alloys. As resins, nylon 6, nylon 66, nylon 12, polyethylene terephthalate, polybutylene terephthalate, polymethylpentene, polycarbonate, modified polyphenylene oxide, polyethersulfone, polyphenylene sulfide, polyarylate, polyetherimide, polyetheretherketone, polyimide , Polyamideimide, polyoxybenzylene, polysulfone and the like having high rigidity and excellent heat resistance. The material of the base member is not limited to those exemplified, but a metal material, particularly light weight, high mechanical strength, pressure resistance, relatively inexpensive aluminum, an alloy thereof, and the like are preferable.

  The disk portion 8 of the base member bonded to the shoulder portion 7 of the inner hollow container 1 is treated with a roughened surface or a surface treatment agent in order to increase the adhesive force with the adhesive 4. It is desirable. As a surface roughening method, a rough surface having an arbitrary shape such as a wave shape or a triangular wave shape can be obtained by a sand blast method, a shot blast method, a grid blast method, or the like. The surface roughness (conforming to JIS B0601: 2001) is desirably selected within a range of 1000 μm or less, preferably 560 μm or less, and more preferably 0.01 to 100 μm.

(4) Substrate treatment agent Further, as a base treatment agent for a die member, an anodizing method as disclosed in Japanese Patent Application Laid-Open No. 59-132777 or the like, and trivalent chromium as disclosed in Japanese Patent Application Laid-Open No. 5-9746. General treatment methods such as hydration oxidation treatment, chromate treatment, alternating current electrolytic treatment, application of resin paint, etc. disclosed in JP-A-5-51765 may be used, but in particular, JP-A-2006-40595. As disclosed in the Japanese Patent Publication No. 1, one or more chitosans selected from the group consisting of chitosan and chitosan derivatives, Ti, Hf, Mo, W, Se, Ce, Fe, Cu, Zn, V And a film formed by treating the surface of the die member with a base treatment agent containing a metal compound containing one or more metals selected from the group consisting of trivalent Cr. Is preferred.
In particular, a base treatment agent containing an organic compound having at least one carboxyl group in the molecule and a metal compound is preferable.

  The chitosan can be obtained, for example, by deacetylating 60 to 100 mol% of natural polymeric chitin extracted from crustaceans such as crabs and shrimps. The chitosan derivative is a compound obtained by, for example, carboxylation, glycolation, tosylation, sulfation, phosphorylation, etherification, alkylation, etc. with respect to the hydroxyl group or / and amino group present in chitosan. . Among these, as the chitosans, it is preferable to use one or more chitosans selected from the group consisting of chitosan, carboxymethyl chitosan, cationized chitosan, hydroxyalkyl chitosan, and salts with these acids.

  The organic compound having at least one carboxyl group in the molecule is not particularly limited. For example, acetic acid, succinic acid, malonic acid, malic acid, tartaric acid, melittic acid, adipic acid, succinic acid, maleic acid, phthalic acid, sebatin Examples include acid, citric acid, butanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, ethylenediaminetetracarboxylic acid, trimellitic acid and the like.

  As the metal compound, as a metal compound containing one or more metals selected from the group consisting of Ti, Hf, Mo, W, Se, Ce, Fe, Cu, Zn, V and trivalent Cr Although not particularly limited, for example, metal oxides, hydroxides, complex compounds, organic acid salts and inorganic acid salts of these metals can be mentioned. Among these, it is preferable to use a metal compound containing trivalent Cr. In this case, the resistance to electrolytic solution under high temperature conditions can be further improved, and the moldability can also be improved. Examples of the metal compound containing trivalent Cr include chromium sulfate, chromium nitrate, chromium fluoride, chromium oxalate, and chromium acetate.

(5) Adhesive As the adhesive forming the adhesive layers 4 and 4 ′ of the present invention, thermosetting resins such as epoxy resins, polyurethane resins, polyester resins, acrylic resins, or (a) carboxylic acid groups Or a thermoplastic resin such as a polyolefin resin containing at least one functional group such as a carboxylic acid anhydride group, (b) an epoxy group, (c) a hydroxyl group, (d) an amino group, (e) a silyl group, etc. Common adhesives can be used. Among these, a polyolefin resin containing a functional group is preferable.
The polyolefin-based resin containing a functional group of the present invention is a compound or monomer having the functional groups (a) to (e) (hereinafter also referred to as a functional group-containing compound) and an α-olefin having about 2 to 10 carbon atoms. And a modified polyolefin resin obtained by graft-modifying the functional group-containing compound on a polyolefin resin.
Hereinafter, the functional group-containing compounds (a) to (e) will be described in detail.

As the compound for introducing the functional group (a) carboxylic acid group or carboxylic acid anhydride group,
Α, β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, itaconic acid or their anhydrides, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, furanic acid, crotonic acid, vinylacetic acid, pentenoic acid An acid etc. are mentioned.

  Functional group (b) As the compound for introducing an epoxy group, glycidyl acrylate, glycidyl methacrylate, itaconic acid monoglycidyl ester, butenetricarboxylic acid monoglycidyl ester, butenetricarboxylic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester and α -Glycidyl esters such as chloroacrylic acid, maleic acid, crotonic acid, fumaric acid or the like, or vinyl glycidyl ether, allyl glycidyl ether, glycidyloxyethyl vinyl ether, glycidyl ethers such as styrene / p-glycidyl ether, p-glycidyl styrene, etc. Particularly preferable examples include glycidyl methacrylate and allyl glycidyl ether.

  As a compound which introduce | transduces a functional group (c) hydroxyl group, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, etc. are mentioned.

  Functional group (d) As the compound for introducing amino group, aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) Examples include acrylate, aminopropyl (meth) acrylate, phenylaminoethyl (meth) acrylate, and cyclohexylaminoethyl (meth) acrylate.

Functional group (e) The compound for introducing a silyl group is an organic silane compound, which is a compound represented by the general formula RR ′ _n SiY _n-3 . Here, R is, for example, an unsaturated aliphatic hydrocarbon such as a vinyl group, an allyl group, a butenyl group, or a cyclohexenyl group, or an unsaturated hydrocarbonoxy group, and preferably has a vinyl group at the terminal. Y is an arbitrary hydrolyzable organic group such as a methoxy group, an ethoxy group, a propoxy group, a methoxyethoxy group, an acetoxy group, and an alkylamino group. R ′ is an arbitrary organic group and may be the same as R or Y. Most preferred silane compounds include unsaturated silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetylsilane, and vinyltrichlorosilane.

As a specific method for introducing a functional group into a resin component of a polyolefin resin containing a functional group of the present invention, a modified polyolefin resin obtained by graft-modifying at least one functional group-containing monomer (functional group-containing polyolefin resin) Resin) and a random copolymer of a functional group-containing compound such as ethylene or propylene with a functional group-containing compound.
The content of the functional group is in the range of 0.001 to 30% by weight based on the weight of the entire adhesive, and in the case of the graft functional group-containing polyolefin resin, the range of 0.001 to 10% by weight. In the case of a random copolymer, it is appropriate to be in the range of 1 to 30% by weight.
If the content of the functional group is less than 0.001% by weight, the adhesive strength is low, the object of the present invention cannot be achieved, and a copolymer having a functional group content exceeding 30% by weight is available. It has drawbacks such as being difficult to perform, easy to deteriorate, poor handling and workability, and not economical.

As a method for producing a functional group-containing polyolefin resin obtained by graft-modifying at least one of the functional group-containing compounds (a) to (e) of the present invention, the compound having the functional group in the presence of a radical initiator is used. Examples thereof include a melting method in which at least one kind is reacted with a resin while being melted in an extruder, or a method in which a polymer is grafted to a polymer by a solution method in which the reaction is performed while being dissolved in a solution together with a resin.
Examples of the radical initiator include organic peroxides and dicumyl compounds.

  Examples of organic peroxides include hydroperoxide, dicumyl peroxide, t-butylcumyl peroxide, dialkyl (allyl) peroxide, diisopropylbenzene hydroperoxide, dipropionyl peroxide, dioctanoyl peroxide, and benzoyl. Peroxide, peroxysuccinic acid, peroxyketal, 2,5-dimethyl-2,5di (t-butylperoxy) hexane, t-butyloxyacetate, t-butylperoxyisobutyrate, etc. are preferably used. It is done.

The functional group-containing olefin random copolymer is generally produced by a high pressure radical polymerization method using a tubular reactor, an autoclave reactor or the like. Examples of the random copolymer of an olefin and the functional group-containing monomer include a copolymer of at least one olefin of an α-olefin such as ethylene and an unsaturated carboxylic acid.
Specifically, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-maleic anhydride copolymer, ethylene-acrylic acid-vinyl acetate copolymer, ethylene-methacrylic acid-vinyl acetate Examples include copolymers, ethylene-maleic anhydride-methyl acrylate copolymers, ethylene-maleic anhydride-ethyl acrylate copolymers, ethylene-maleic anhydride-vinyl acetate copolymers, and the like.

  Examples of the polyolefin-based resin used for the grafting include high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, and the like, which are produced by ion polymerization such as Ziegler catalyst, Phillips catalyst, metallocene catalyst, Polyethylene resins such as high-pressure radical polyethylene resins such as ethylene- (meth) acrylic acid copolymers and ethylene- (meth) alkyl acrylate copolymers, and polypropylene resins such as homopolypropylene and propylene-ethylene copolymers. Etc.

  The functional group-containing olefin random copolymer and the grafted functional group-containing polyolefin resin are used alone or mixed with an unmodified polyolefin resin. In particular, it is preferable to use the functional group-containing polyolefin resin as a mixture with the unmodified polyolefin resin because the functional group content, MFR, density and the like can be easily adjusted. Among these, a polyethylene resin is preferable.

Hereinafter, these adhesives will be described in more detail.
[adhesive]
(I) Materials of polyethylene-based resin (X) and unmodified polyethylene-based resin (Y) containing functional groups [high-density polyethylene resin (A)]
The high density polyethylene resin (A) according to the present invention is generally a high density polyethylene resin produced by ionic polymerization, and refers to an ethylene homopolymer or a copolymer of ethylene and an α-olefin. Yes, (a1) Density is 0.94 to 0.97 g / cm ³ , preferably 0.945 to 0.965 g / cm ³ , more preferably 0.95 to 0.96 g / cm ³ . (A2) The melt flow rate (MFR) is in the range of 0.01 to 100 g / 10 minutes, preferably 0.05 to 50 g / 10 minutes, more preferably 0.1 to 30 g / 10 minutes. Within such a range, the performance with excellent long-term life (durability) such as adhesive strength, rigidity and creep resistance is easily exhibited.
The density was measured based on the test method of JIS K6922-1 (1997).
Moreover, in this invention, melt flow rate (MFR) is measured on condition D (temperature 190 degreeC, load 21.18N) based on the test method of JISK6922-1 (1997).

[Linear low density polyethylene resin (B)]
The linear low density polyethylene resin (B) according to the present application is a linear low density polyethylene resin generally produced by ionic polymerization, and refers to a copolymer of ethylene and α-olefin. in and, (b1) density 0.90~0.94g / cm ^3, preferably a density 0.91~0.935g / cm ^3, more preferably from 0.92~0.93g / cm ^3. (B2) The melt flow rate (MFR) is in the range of 0.01 to 100 g / 10 minutes, preferably 0.05 to 50 g / 10 minutes, more preferably 0.1 to 30 g / 10 minutes. Within such a range, the performance with excellent long-term life (durability) such as adhesive strength, rigidity and creep resistance is easily exhibited.

  The α-olefin of the component (A) and the component (B) is preferably a linear or branched olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, Examples include 4-methyl-1-pentene, 1-octene, and 1-decene. Two or more of them may be used in combination. Among these copolymers, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, and ethylene / 1-octene copolymer are economical. It is preferable from the viewpoint.

  The high-density polyethylene resin (A) or linear low-density polyethylene (B) produced by the ionic polymerization is not particularly limited to the production catalyst, process and the like. Pp. 123-160, p. 163-196, etc. of "Yomihon" (edited by Kazuo Matsuura and Naotaka Mikami, published by Industrial Research Association, 2001). That is, it can be produced by various polymerization reactors, polymerization conditions, and catalysts in each polymerization mode of Ziegler catalyst, single site catalyst, etc., slurry method, solution method, gas phase method. As a single site catalyst resin, product name: Harmolex, product name: Kernel, product name of Evolue Co., Ltd., product name of Evolue Co., Ltd., product of Dow Chemical Co., Ltd. Name: Engage.

The density was measured based on the test method of JIS K6922-1 (1997).
Moreover, the melt flow rate (MFR) was measured on condition D (temperature 190 degreeC, load 21.18N) based on the test method of JISK6922-1 (1997).
The density of the above (a1) and (b1) can be controlled by the type and content of the α-olefin, and the density tends to decrease as the content increases, and the above (a2) or (b2) ) Melt flow rate (MFR) is controlled by a chain transfer agent such as hydrogen, a process or the like. These controls are conventional means well known to those skilled in the art.

[High pressure radical polyethylene resin (C)]
The high-pressure radical polyethylene resin (C) of the present invention is (c1) an ethylene homopolymer (low-density polyethylene resin) or ethylene vinyl ester by a high-pressure radical polymerization method having a melt flow rate of 0.01 to 100 g / 10 min. And copolymers of ethylene and α, β-unsaturated carboxylic acids or derivatives thereof. These low-density polyethylene resins and the like are produced by a known high-pressure radical polymerization method, tubular method, autoclave method. It may be produced by any of these methods.
The low density polyethylene resin preferably has a density of 0.91 to 0.935 g / cm ³ and a melt flow rate of 0.05 to 100 g / 10 minutes, preferably 0.1 to 50 g / 10 minutes. The

  The ethylene-vinyl ester copolymer is composed mainly of ethylene, and vinyl ester monomers such as vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate. It is a copolymer. Among these, vinyl acetate is particularly preferable. A copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of vinyl ester, and 0 to 49.5% by weight of other copolymerizable unsaturated monomers is preferred. Furthermore, the vinyl ester content is selected in the range of 3 to 20% by weight, particularly preferably 5 to 15% by weight.

Typical copolymers of ethylene and α, β-unsaturated carboxylic acid ester include ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate copolymer. Polymers, ethylene / (meth) acrylic acid such as ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer or alkyl ester copolymers thereof; ethylene / maleic anhydride / vinyl acetate copolymer, ethylene -A binary copolymer such as a maleic anhydride / methyl acrylate copolymer, an ethylene / maleic anhydride / ethyl acrylate copolymer, or a multi-component copolymer.
That is, as these comonomers, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, acrylic acid-n-butyl, methacrylic acid- Examples thereof include n-butyl, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, and lauryl methacrylate. Among these, alkyl esters such as methyl (meth) acrylate and ethyl (meth) acrylate are particularly preferable. In particular, the (meth) acrylic acid ester content is in the range of 3 to 30% by weight, preferably 5 to 20% by weight.

[Ultra low density polyethylene resin (D)]
The ultra-low density polyethylene resin (D) according to the present invention means (d1) a density of 0.86 to less than 0.90 g / cm ³ , preferably 0.87 to 0.89 g / cm ³ , (d2) MFR Is an α-olefin copolymer of ethylene and carbon 3-12 having a crystallinity in the range of 0.01 to 100 g / 10 min, preferably 0.1 to 50 g / 10 min. Examples thereof include a polymer and a microcrystalline ethylene / α-olefin copolymer.

[Thermoplastic elastomer (E)]
Examples of the thermoplastic elastomer of the present invention include polyolefin-based elastomers, polystyrene-based elastomers, polybutadiene-based elastomers, polyurethane-based elastomers, polyamide-based elastomers. Among these, polyolefin-based elastomers and polystyrene-based elastomers are used as liner materials. From the standpoint of compatibility, economy and the like.

  Examples of the polyolefin elastomer include ethylene / α-olefin copolymer rubbers such as ethylene-propylene copolymer rubber (EPR) and ethylene-propylene-diene copolymer rubber (EPDM). In addition, polypropylene resin and EPR, EPDM, if necessary, polyethylene resin such as ultra-low density polyethylene resin, linear low density polyethylene resin, or oil and a crosslinking agent can be dynamically partially crosslinked or completely crosslinked. The resulting polyolefin elastomer (TPO) is included.

  Examples of the polystyrene elastomer include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, vinyltoluene, One or more aromatic vinyl compounds from among p-tert-butylstyrene and the like, for example, from among butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc. 1 type (s) or 2 or more types are selected, and the block copolymer with a conjugated diene compound and / or its hydrogenated material are mentioned.

  Specific examples of the polystyrene elastomer include styrene-butadiene-styrene copolymer (SBS), styrene-isoprene copolymer, styrene-isoprene-styrene copolymer (SIS), and the like. A number of methods have been proposed as a method for producing the block copolymer. As a typical method, for example, a lithium catalyst or a Ziegler type catalyst is used by the method described in Japanese Patent Publication No. 40-23798. It can be obtained by block polymerization in an inert medium.

  Specific examples of the hydrogenated product include styrene-ethylene / butene copolymer (SEB), styrene-ethylene / propylene copolymer (SEP), styrene-ethylene / butene-styrene copolymer (SEBS), styrene- Ethylene / propylene / styrene copolymer (SEPS), styrene / ethylene / ethylene / propylene / styrene copolymer (SEEPS), styrene / butadiene / butylene / styrene copolymer (partially hydrogenated styrene / butadiene / styrene copolymer) , SBBS) and the like.

  Examples of other preferable thermoplastic elastomers include polybutadiene, butadiene-acrylonitrile rubber, acrylonitrile-butadiene-styrene copolymer rubber, isobutylene-isoprene rubber, chloroprene rubber and the like.

(Ii) Configuration of Functional Group-Containing Polyethylene Resin (X) The functional group-containing polyethylene resin (X) of the present invention includes the functional group-containing ethylene random copolymer and the grafted functional group-containing polyethylene resin. As the raw material of the grafted functional group-containing polyethylene resin, each of the component (A), component (B), component (C) and component (D) may be modified independently, (B), (B) + (C), (A) + (C), (A) + (D) or (A) + (B) + (C), (A) + (B) + (D ), (A) + (C) + (D), (B) + (C) + (D) and (A) + (B) + (C) + (D) It can also be modified as a product. These compositions may be dry blended at the time of modification, or may be modified by mixing them in advance with a known mixer such as a kneader or a Henschel mixer.
Moreover, when at least one of (A) to (D) does not satisfy the above-described conditions, the adhesive strength is lowered, and there is a concern that desired adhesive strength cannot be obtained.
In addition, it is preferable that at least one of (A), (B) and (D) is produced with a single site catalyst because of a good balance between adhesive strength and mechanical strength.
Moreover, as a structure of functional group containing polyethylene-type resin (X), it is preferable from economical efficiency, workability | operativity, etc. to use it as a mixture of 2 or more types rather than using (A)-(D) independently.
As a particularly preferred combination, a modified product produced with a single site catalyst of the component (A) and / or the component (B) is desirable.

(Iii) Functional group-containing monomer In the functional group-containing polyethylene resin (X) of the present invention, an unsaturated carboxylic acid or a derivative thereof containing the functional group (a) or the functional group (b) among the functional groups described above At least one monomer selected from the group consisting of Examples of the unsaturated carboxylic acid or derivative thereof include monobasic unsaturated carboxylic acids, dibasic unsaturated carboxylic acids, and metal salts, amides, imides, esters and anhydrides thereof. The number of carbon atoms of the monobasic unsaturated carboxylic acid is at most 20, preferably 15 or less. In addition, the carbon number of the dibasic unsaturated carboxylic acid is at most 30, preferably 25 or less, and the carbon number of this derivative is at most 30, preferably 25 or less. Among these unsaturated carboxylic acids and derivatives thereof, acrylic acid, methacrylic acid, maleic acid and anhydrides thereof, 5-norbornene-2,3-dicarboxylic acid and anhydrides thereof, and glycidyl methacrylate are preferable, and maleic anhydride is particularly preferable. , 5-norbornene acid anhydride is preferred because of the excellent adhesion performance of the polyethylene resin composition.
In the case of graft modification, the content is 0.001 to 30% by weight of at least one monomer selected from the group consisting of an unsaturated carboxylic acid or a derivative thereof with respect to the resin component. It is 0.001 to 10 weight%, Preferably it is 0.01 to 5 weight%, More preferably, it is 0.1 to 3 weight%. When the content is less than 0.001 part by weight, a sufficient adhesive performance which is the original purpose cannot be obtained, and when it is more than 10% by weight, unreacted monomers increase, which is not preferable. In the case of a random copolymer with ethylene or the like, the range of 1 to 30% by weight, preferably 2 to 28% by weight, more preferably 3 to 25% by weight is desirable.

(Iv) Radical initiator In the present invention, the radical initiator used for graft modification is dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t -Butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (t-butylperoxy) hexane, lauroyl Peroxide, t-butylperoxybenzoate, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, t-butylcumyl peroxide, α, α'-bis (t-butylperoxy -M-isopropyl) benzene, di-t-butyldiperoxyisophthalate, n-butyl-4 Examples of the organic peroxide include 4-bis (t-butylperoxy) valerate, t-butylperoxybenzoate, t-butylperoxyacetate, cyclohexanone peroxide, t-butylperoxylaurate, and acetyl peroxide. .
Among these, those having a decomposition temperature for obtaining a half-life of 1 minute are preferably 160 to 200 ° C. If the decomposition temperature is too low, the decomposition reaction will start before the raw polyethylene resin is sufficiently plasticized in the extruder, so the reaction rate will be low and more gels and fish eyes will be generated. Conversely, if the decomposition temperature is too high The reaction is not completed in the extruder or the like, and the amount of the unreacted unsaturated carboxylic acid and its derivative increases.
The blending amount of the radical initiator is usually 0.005 to 0.5 parts by weight, more preferably 0.01 with respect to 100 parts by weight of the total resin component including the polyethylene resin at the time of primary modification (containing functional groups). Used in the range of ~ 0.3 parts by weight. If it is less than 0.005 parts by weight, the grafting reaction is not sufficiently carried out and unreacted monomers increase, which is not preferable. On the other hand, when the amount is more than 0.5 parts by weight, gels and fish eyes frequently occur, which is not preferable.

  In the present invention, the ratio of the unsaturated carboxylic acid or its derivative monomer to the radical initiator is usually in the range of 60/1 to 10/1. If the amount of the radical initiator is too small, unreacted monomers increase, which is not preferable. Conversely, if the amount of radical initiator is excessive, gel and fish eyes are frequently generated, which is not preferable.

(V) Production method of functional group-containing polyethylene resin (X) The production method of functional group-containing polyethylene resin (X) is at least one of resins (A), (B), (C) and (D). At least one functional group-containing monomer selected from the group consisting of an unsaturated carboxylic acid or a derivative thereof in 100 parts by weight of a polyethylene-based resin or a composition thereof (hereinafter also referred to as a polyethylene-based resin) 0.05-2. 0 parts by weight and 0.005 to 0.5 parts by weight of a radical initiator are added and melt-kneaded or modified (functionalized) in a solvent using a single-screw extruder and / or twin-screw extruder or one or a plurality of reactors. Group).
Specific examples include a melt-kneading method using an extruder, a Banbury mixer, a kneader, a solution method in which the solution is dissolved in an appropriate solvent, a slurry method in which the suspension is suspended in an appropriate solvent, or a so-called gas phase grafting method.
The treatment temperature is appropriately selected in consideration of (A) to (D) deterioration of at least one polyethylene resin, decomposition of unsaturated carboxylic acid and derivatives thereof, decomposition temperature of peroxide used, and the like. However, taking the melt kneading method as an example, it is usually 190 to 350 ° C., and 200 to 300 ° C. is particularly preferable.
In producing the functional group-containing polyethylene resin (X) according to the present invention, for the purpose of improving its performance, as described in JP-A-62-10107, an already known method such as the graft modification or A method of treating with an epoxy compound or a polyfunctional compound containing an amino group or a hydroxyl group after modification, and a method of removing unreacted monomers (unsaturated carboxylic acid and derivatives thereof) and various by-products by heating or washing. Can be adopted.
The higher the graft amount of at least one monomer selected from the group consisting of the unsaturated carboxylic acid and its derivative, the better, but generally it is in the range of 0.001 to 10% by weight (measurement method of graft amount: infrared spectroscopy). By a photometer).

Using the above radical initiator, the reaction to polyethylene-based resin, etc., grafting reaction and polyethylene micro-crosslinking occur simultaneously in parallel, but by setting the resin temperature during melt-kneading to 250 ° C. or higher, grafting The reaction takes place preferentially to achieve a high monomer addition rate. On the other hand, when the resin temperature is less than 250 ° C., the fine crosslinking of the polyethylene resin or the like occurs preferentially, resulting in an increase in gel and resin burning, and the quality of the functional group-containing polyethylene resin (X) obtained is lowered. Further, when the resin temperature exceeds 310 ° C., the deterioration of the polyethylene itself is accelerated, so that gels and resin burns increase drastically, which also deteriorates the quality.
In addition, since the reaction is performed at such a high temperature, it is necessary to suppress air from entering the inside of the extruder or the reactor as much as possible. In melt-kneading, it is necessary to avoid the resin from staying in the extruder for a long time. I must. For this reason, it is extremely preferable to perform nitrogen feed in the vicinity of the raw material resin inlet.

  In the production of the functional group-containing polyethylene-based resin (X) of the present invention, it is preferable to modify the polyolefin-based resin material over a plurality of orders, and thereby from a relatively expensive monomer, an unsaturated carboxylic acid and a derivative thereof. The modification rate of at least one modification monomer selected from the group is sufficiently increased to improve economy, and a high modification rate can be achieved with a relatively small amount of modification monomer. It is possible to produce a high-quality functional group-containing polyolefin resin (X) that is excellent and has no unreacted functional group-containing monomer and does not cause gel or resin burn.

  Graft modification rate (measurement method: by infrared spectrophotometer) obtained by such a melt-kneading modification method is generally in the range of about 0.2 to 2.5% by weight. The upper limit of the graft modification rate of the resin (A) is preferably as high as possible, but is generally in the range of 0.55 to 3% by weight. However, it is not particularly limited to this range, and a higher modification rate is desirable.

(Vi) Configuration of Unmodified Polyethylene Resin (Y) The unmodified polyethylene resin (Y) according to the present invention has (a1) a density of 0.94 to 0.97 g / cm ³ , (a2) a melt flow rate of 0.8. High density polyethylene resin (A) having 01 to 100 g / 10 min, (b1) linear low density having a density of 0.90 to less than 0.94 g / cm ³ and (b2) melt flow rate of 0.01 to 100 g / 10 min Polyethylene (B), (c1) high pressure radical polyethylene resin (C) having a melt flow rate of 0.01 to 100 g / 10 min, and (d1) density of 0.86 to less than 0.90 g / cm ³ , (d2) melt At least one unmodified poly selected from an ultra low density polyethylene resin (D) and an elastomer (E) having a flow rate of 0.01 to 100 g / 10 min It is a styrene-based resin.

  The above component (A), component (B), component (C), component (D) and component (E) may be the same as the resin used in the functional group-containing polyethylene resin (X). A + B), (A + C), (A + D), (A + E), (B + C), (B + D), (B + E), (C + D), (D + E), (A + B + C), (A + B + D), (A + B + E), (A + C + D) , (A + C + E), (B + C + D), (B + C + E), (B + D + E), (C + D + E), (A + B + C + D), (A + B + C + E), (A + C + D + E), (B + C + D + E), (B + C + D + E), (A + B + C + D + E) unmodified polyethylene, etc. You may mix resin and its composition.

The component (Y) is not essential. However, when the component (X) is used alone, there is a concern that there may be an adverse effect that excessive resin deterioration or gel may occur during molding. The above component (Y) is used because it is easy or economical to adjust functions such as group content, MFR, density, heat resistance, mechanical properties, rigidity, and flexibility. It is preferable.
In addition, it is preferable that at least one of (A), (B) and (D) used in the modified or unmodified resin is produced with a single site catalyst so that there are few low molecular weight components and functional groups. It is also preferable from the viewpoint of suppressing the deterioration of the resin and the generation of gel, and improving the performance such as mechanical strength and adhesive strength.

(Vii) Adhesive resin (Z)
The adhesive resin (Z) of the present invention suppresses gas leakage between the inner shoulder portion 7 of the hollow container 1 formed of a synthetic resin liner material and the disc portion 8 formed at one end of the base member 3. Therefore, from the following (A) to (D), which is used for welding via the adhesive resin (Z) 4 and contains at least one functional group of the above (a) to (e). 0.5 to 100% by weight of the selected at least one functional group-containing polyethylene resin (X) and at least one unmodified polyethylene resin (Y) 0 selected from the following (A) to (E): (Z1) an adhesive resin (Z) having a density of 0.86 to 0.97 g / cm ³ and (z2) a melt flow rate of 0.01 to 100 g / 10 min.
(A): (a1) density 0.94 to 0.97 g / cm ³ , (a2) high density polyethylene resin having a melt flow rate 0.01 to 100 g / 10 min (B): (b1) density 0.90 Less than 0.94 g / cm ³ , (b2) linear low density polyethylene resin (C) having a melt flow rate of 0.01 to 100 g / 10 min: (c1) high pressure radical method having a melt flow rate of 0.01 to 100 g / 10 min Polyethylene resin (D): (d1) Ultra low density polyethylene resin (E) having a density of 0.86 to less than 0.90 g / cm ³ and (d2) melt flow rate of 0.01 to 100 g / 10 min (E): thermoplastic elastomer

  More specifically, a resin selected from one of (A), (B), (C) and (D) of the functional group-containing polyethylene resin (X) or a resin composition thereof, for example, (A) + (B), (B) + (C), (A) + (C), (A) + (D) or (A) + (B) + (C), (A) + (B) + ( D), (A) + (C) + (D), (B) + (C) + (D) and (A) + (B) + (C) + (D) Containing polyethylene-based resin composition (X ′) and one or more of unmodified polyethylene-based resin (Y) (A) to (E) or at least one unmodified polyethylene resin composition (Y ′) It is characterized by being mixed.

  Among these, from the viewpoint of adhesiveness, heat resistance, strength, and easy moldability, a preferable combination is a modified polyethylene resin of resin (B), an unmodified high-density polyethylene resin, and an unmodified linear low-density polyethylene resin. This is an unmodified polyethylene resin. A particularly preferred blending ratio is 10 to 30% by weight of the modified linear low density polyethylene resin of the resin (B) and an unmodified polyethylene resin (resin A / resin B = 0 to 30% by weight / 100 to 70% by weight). It is a composition blended at a ratio of 90 to 70% by weight.

  The blending ratio (X) / (Y) of the functional group-containing polyethylene resin (X) and the unmodified polyethylene resin (Y) varies depending on the functional group-containing concentration of the functional group-containing polyethylene resin (X). Generally, it is selected within the range of 100 to 0.5 / 0 to 99.5% by weight, preferably 95 to 5/5 to 95% by weight, more preferably 50 to 10/50 to 90% by weight. desirable.

The density (Z1) of the adhesive resin (Z) is 0.86 to 0.97 g / cm ³ , preferably 0.90 to 0.96 g / cm ³ , more preferably 0.91 to 0.96. It is desirable to be. If the density is less than 0.86 g / cm ³ , the adhesive strength may decrease. If it exceeds 0.97 g / cm ³ , it is difficult to produce industrially in large quantities and the durability may decrease. Arise.
Moreover, a melt flow rate (Z2) is 0.01-100 g / 10min, Preferably it is 0.05-50 g / 10min, More preferably, it is the range of 0.1-40 g / 10min. When the MFR is less than 0.01 g / 10 min, there is a difficulty in moldability, and when it exceeds 100 g / 10 min, the strength such as impact strength may be lowered.

  The adhesive layer 4 of the present invention is formed on the outer layer of the hollow container 1 formed of a synthetic resin liner material. Preferably, the adhesive layer 4 ′ is further formed on the hollow container 1 formed of a synthetic resin liner material. The innermost layer is formed by a molding method such as multilayer blow molding, multilayer injection molding, or rotational molding, and the adhesive used for the adhesive layer is preferably a polyolefin-based resin containing the functional group described above. Yes, initial adhesive strength, inner hollow container 1 when filling and discharging high pressure gas, shrinkage, expansion, etc., response to temperature change, repeated changes over time, resistance to contents Such durability is excellent.

The adhesive of the present invention satisfies the above-mentioned properties, and in the case of a reinforcing material or innermost layer, it is made of an inner synthetic resin when filling and discharging the initial adhesive strength with the base member and high-pressure gas. The liner material has excellent durability such as shrinkage and expansion, adaptability to temperature changes, repeated changes over time, resistance to contents, etc. These adhesive resins (Z) It is important to form the outer layer (adhesive layer) of the resin liner material. In particular, providing an adhesive layer using a multi-layer extrusion die (multi-layer blowing method) can form a synthetic resin liner layer and an adhesive layer at the same time, and is efficient because it is produced in a single process. This is preferable because it can improve the film thickness, form a uniform coating film, and exhibit performance such as adhesive strength.
In the present invention, when an adhesive layer is simultaneously provided on the outer layer and the innermost layer of the hollow container 1 to bond both the reinforcing material and the base member, the adhesive strength between the base member and the adhesive is further strengthened. For this purpose, it is desirable that a part or the entire surface of the base member is subjected to surface treatment such as the above-described roughening treatment or a base treatment agent.

  Further, the thickness of the adhesive is desirably 10 μm to 5 mm, preferably 50 μm to 3 mm, and more preferably 100 μm to 2 mm. If the thickness is less than 10 μm, the adhesive strength is not sufficient, and there is a concern that gas leakage may occur due to repeated contraction motions. The thickness of the adhesive may be thick, but about 5 mm is appropriate in consideration of economy and adhesive strength. Moreover, even if it is 5 mm or more thick, the adhesive strength is not improved and the economy is impaired.

3. Manufacturing method of pressure vessel The manufacturing method of the pressure vessel of the present invention will be specifically described in detail below.
As described above, the pressure vessel according to the present invention is formed of a hollow container 1 (inner wall) formed of a synthetic resin liner material and a reinforcing material on the outer layer of the hollow container 1 as shown in FIG. A pressure vessel comprising a reinforcing material layer 2 (outer wall), and having a base member 3 for attaching a nozzle for filling and discharging a high-pressure gas at at least one end of the hollow vessel 1, An adhesive layer 4 is provided on the outer layer of the hollow container 1 formed of a synthetic resin liner, and an adhesive layer 4 ′ is provided on the innermost layer of the hollow container 1, if desired. This is a pressure vessel 10 formed by bonding or welding the vessel 1 and the reinforcing material 2.

FIG. 2 shows a cross-sectional view of the main part of a multilayer blow molding method which is an example of a preferred production method of the present invention.
In FIG. 2, the base members 3 and 3 ′, which are preferably surface-treated or ground-treated in advance, are supported on the upper and lower sides of the support portion 14 that is engaged with the support base 15, and are high from the multilayer die 11 of a blow molding machine (not shown). Synthetic resin formed of a synthetic resin liner composed of adhesive layers 4 and 4 'such as an adhesive resin (Z) on the outer side of a thermoplastic resin such as a density polyethylene resin and, if desired, the innermost layer A cylindrical parison 12 (a, b) formed of a liner material is extruded, and the parison is suspended between the molds 13 (a, b) so as to cover the disk portions 8 of the base members 3, 3 ′. Next, the mold 13 (a, b) is closed with the parison 12 still sufficiently soft, the diameter of the parison 12 (a, b) is reduced, and the necks of the base members 3, 3 ′ are attached to the parison 12 (a , B) is pinched simultaneously and blown up to expand the parison 12 (a, b) and press against the inner wall of the mold 13 (a, b) to form the hollow container 1. On the other hand, the shoulder portion 7 of the synthetic resin liner material 1, the disk portion 8 of the base member 3, 3 ′, and the adhesive 4 ′ are caused by internal pressure, and the base member 3, 3 ′ (rod) is a synthetic resin liner material. The hollow container 1 with a cap member is manufactured by being pressed against and closely adhered to the shoulder portion 7 of the hollow container 1 to be formed and bonded or fused. Next, the outer circumference of the hollow container is impregnated with a thermosetting resin such as an epoxy resin or an unsaturated polyester resin through the adhesive layer 4, a fiber yarn such as a carbon fiber yarn or a bundle, a fiber yarn such as a glass fiber yarn or a bundle, a bundle, The pressure vessel 10 is manufactured by covering with a mat or the like and curing to form a fiber reinforcing material 2 (CFRP, GFRP, etc.) layer.

  In the method for producing a pressure vessel of the present invention, the method for producing a hollow container and an adhesive layer formed of a synthetic resin liner is not limited to the above blow molding method, but includes injection molding, rotational molding, compression molding, and the like. However, as described above, since the cap member can be integrated with the formation of the hollow container and the adhesive layer at the time of manufacture, the manufacturing process is simple, the manufacturing cost is low, and it is economical. It is preferable to employ a molding method.

4). Use of pressure vessel The pressure vessel according to the present invention is not limited to the type of gas charged therein, and natural gas, liquefied petroleum gas, nitrogen, oxygen, hydrogen, helium gas, argon gas, rocket fuel, etc. The pressure vessel can be suitably used for any of the points such as high adhesive force between the base member and the hollow container formed of the synthetic resin liner material and excellent airtightness.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not restrict | limited by these Examples, unless it deviates from the summary. In Examples and Comparative Examples, physical properties are evaluated as follows.

1. Measurement method (1) Density (unit: g / cm ³ ): Measured according to JIS K6760.
(2) Melt flow rate: MFR (unit: g / 10 min): Measured according to JIS K6922-1 (1997), condition D (temperature 190 ° C., load 21.18 N).
(3) High load melt flow rate: HLMFR (unit: g / 10 min): Measured according to JIS K6922-1 (1997), condition D (temperature 190 ° C., load 211.8 N).
(4) Adhesive strength: Tensilon was used to measure the adhesive strength at a tensile speed of 50 mm / min, a length of 5 cm, and a 180 degree peel (measured value is an average value of 5 points).
(5) Drop impact test:
Reinforcing material / liner material: The state of the container after the pressure container was dropped obliquely from a height of 3 m with the shoulder part down at room temperature was observed.
Base member / liner material: The state of the container after the pressure vessel was dropped from a height of 3 m at −40 ° C. with the base portion facing downward was observed.
(6) Gas leak test: The pressure vessel 10 was filled with 30 MPa of hydrogen gas, and was allowed to stand at room temperature for 30 days, after which the pressure in the tank changed with time (◯: no gas leak, x: gas leaked).

2. Raw material (1) Production of functional group-containing polyethylene resin (X) (i) [Production of functional group-containing polyethylene resin (X1)]
Powdered polyethylene system composed of linear low density polyethylene resin (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Novatec LL, Z50MG, manufactured by Nippon Polyethylene Co., Ltd. (referred to as B1)) To 100 parts by weight of resin (B), 0.8 part of maleic anhydride and 0.02 part of 2,5-dimethyl-di- (t-butylperoxy) hexane are added and mixed with a Henschel mixer. Using a 50 mm single screw extruder manufactured by Co., Ltd., melt kneading under the conditions of a screw speed of 50 rpm and a resin temperature of 280 ° C., MFR 4 g / 10 min, density 0.925 g / cm ³ , and the amount of graft monomer is 0.5% by weight. Functional group-containing polyethylene resin (X1) was obtained.

(Ii) [Production of functional group-containing polyethylene resin (X2)]
High-density polyethylene resin (density: 0.958 g / cm ³ , MFR: 20 g / 10 min, brand: Novatec HD HS490P, Nippon Polyethylene Co., Ltd., A1) 80 parts by weight and linear low-density polyethylene resin (density) : 0.921 g / cm ³ , MFR: 16 g / 10 min, Brand: Novatec LL, US370G, Nippon Polyethylene Co., Ltd. B2) 20 parts by weight of powdered polyethylene resin (A + B) 100 parts by weight Then, 0.8 parts of maleic anhydride and 0.02 parts of 2,5-dimethyl-di- (t-butylperoxy) hexane were added, mixed with a Henschel mixer, and then 50 mm single screw extrusion manufactured by Modern Machinery Co., Ltd. Machine, melt kneading under conditions of screw rotation speed 50rpm and resin temperature 280 ° C, MFR 8g / 10min, density A functional group-containing polyethylene resin (X2) having 0.950 g / cm ³ and a graft monomer amount of 0.5% by weight was obtained.

(Iii) [Production of functional group-containing polyethylene resin (X3)]
Powdered polyethylene resin (B) comprising a single site polyethylene resin (density: 0.930 g / cm ³ , MFR: 3 g / 10 min, brand: Harmolex NW584N, referred to as B3 manufactured by Nippon Polyethylene Co., Ltd.) To 100 parts by weight, 0.6 parts of maleic anhydride and 0.02 parts of 2,5-dimethyl-di- (t-butylperoxy) hexane are added, mixed with a Henschel mixer, and then manufactured by Modern Machinery Co., Ltd. Functional group-containing polyethylene having a MFR of 2 g / 10 min, a density of 0.930 g / cm ³ , and a grafting rate of 0.4% by weight using a 50 mm single screw extruder under conditions of a screw speed of 50 rpm and a resin temperature of 280 ° C. System resin (X3) was obtained.

3. Example <Example 1>
[Production of adhesive (Z1)]
20% by weight of a functional group-containing polyethylene resin (X1) and a linear low density polyethylene resin (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Novatec as unmodified polyethylene resin (Y1) LL, Z50MG, Nippon Polyethylene Co., Ltd. (B1) 80% by weight was mixed with a Henschel mixer, and then a modern machinery Co., Ltd. 50 mm single screw extruder was used, with a screw speed of 50 rpm and a resin temperature of 280 ° C. After melt-kneading under these conditions, pelletizing was performed to produce adhesive (Z1) pellets having properties as shown in Table 1.

[Manufacture of pressure vessels]
As shown in FIG. 2, the base members 3, 3 ′ are inserted above and below the support portion 14 engaged with the support base 15, and the base members 3, 3 ′ are installed. Using a continuous multilayer hollow molding machine, a high-density polyethylene resin layer, an outer layer 4 and an innermost layer 4 ′ are formed from an adhesive layer (Z1) from a die 11 of a multilayer blow molding machine (not shown) under the following conditions. The cylindrical parison 12 (a, b) is extruded and suspended between the molds 13 (a, b), and the mold 13 (a, b) is closed while the parison is still sufficiently soft. 12 (a, b) is reduced in diameter, the neck portion of the base material 3 is pinched simultaneously with the adhesive layer 4 ′ inside the parison 12, and a gas such as air is blown to make the parison 12 on the wall of the mold 13. The hollow container 1 formed by the synthetic resin liner material is formed by pressing. On the other hand, the shoulder portion 7 of the liner material 1 and the mouthpiece member 3 are pressed against the inner shoulder portion of the synthetic resin liner material 1 by internal pressure by the inner pressure, and are fused, and have a volume of 30 liters. A container was prepared. Next, the outer periphery of the hollow container is impregnated with a thermosetting resin epoxy resin, wound with a carbon fiber bundle, and then heated and pressed to impregnate the hollow container outer layer adhesive 4 and the epoxy resin. The fiber reinforced material 2 (CFRP) was fused, the epoxy resin was cured to form a reinforcing material layer, and the pressure vessel 10 was manufactured.
Table 1 shows the result of confirming the drop impact test and the presence or absence of gas leakage (average of 5 points) using this pressure vessel 10.

[Blow molding conditions]
Adhesive resin (Z) layer / high density polyethylene layer / regrind layer / adhesive layer / gas barrier layer from the outer layer side under conditions of a molding temperature of 210 ° C., a blow pressure of 1.4 MPa, a mold temperature of 20 ° C., and a blowing time of 130 sec. (EVOH layer) / adhesive layer / high-density polyethylene layer / adhesive resin (Z) layer, five types and eight layers (layer thickness: 0.3 mm ((outer layer = adhesive (Z) layer) /0.7 mm / 2. A cylindrical hollow container of 0 mm / 0.1 mm / 0.15 mm / 0.1 mm / 2.0 mm / 0.3 mm (innermost layer = adhesive (Z) layer)) was produced. It is as follows.

<Layer structure>
[Internal and external high density polyethylene resin layers]
Product name: Novatec HD HB111R, manufactured by Nippon Polyethylene Co., Ltd.
Density = 0.945 g / cm ³ , melt flow rate (HLMFR: measurement temperature 190 ° C., load 211.8 N) 6 g / 10 min [regrind material layer]
The composition ratios of the high-density polyethylene resin, the adhesive, and the ethylene-vinyl alcohol copolymer are 87.2% by weight, 6.5% by weight, and 6.3% by weight, respectively.
[Adhesive layer]
Product name: Adtex FT61AR3, manufactured by Nippon Polyethylene Co., Ltd., density 0.933 g / cm ³ , MFR 0.6 g / 10 min.
[Gas barrier layer]
Ethylene-vinyl alcohol copolymer layer (EVOH layer)
Product name: Eval F101B Kuraray Co., Ltd.

<Example 2>
[Production of adhesive (Z5)]
Functional group-modified polyethylene resin (X1) 20% by weight and unmodified polyethylene resin (Y2) linear ultra-low density polyethylene (density: 0.870 g / cm ³ , MFR: 5 g / 10 min, brand: engage 8200, 80% by weight (made by Dow Chemical Japan Co., Ltd.) is melt kneaded or dry blended, mixed with a Henschel mixer, and then using a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd., with a screw speed of 50 rpm and a resin temperature of 280 ° C. After melt-kneading under these conditions, pelletizing was performed to produce adhesive (Z5) pellets having the properties shown in Table 1.
A pressure vessel was produced using the adhesive (Z5) in the same manner as in Example 1, and the evaluation results are shown in Table 1.

<Comparative Example 1>
A pressure vessel was produced in the same manner as in Example 1 except that the adhesive resin (Z1) in Example 1 was not used, and the evaluation results are shown in Table 1.

<Example 3>
[Production of adhesive (Z4)]
2% by weight of functional group-modified polyethylene resin (X1) and linear low-density polyethylene (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Z50MG, as unmodified polyethylene resin (Y1) Nippon Polyethylene Co., Ltd. (98% by weight) was melt-kneaded or dry blended, mixed with a Henschel mixer, and then using a modern machinery Co., Ltd. 50 mm single screw extruder with a screw speed of 50 rpm and a resin temperature of 280 ° C. After melt-kneading under conditions, pelletizing was performed to produce adhesive (Z4) pellets having properties as shown in Table 1.
A pressure vessel was produced in the same manner as in Example 1 using the adhesive (Z4), and the evaluation results are shown in Table 1.

<Example 4>
[Manufacture of adhesive (Z2)]
Functional group-modified polyethylene resin (X2) 20% by weight and linear low density polyethylene resin (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Novatec LL, Z50MG, manufactured by Nippon Polyethylene Co., Ltd. ( B1)) Adhesive (Z2) pellets having properties as shown in Table 2 were prepared in the same manner as in Example 1 using 80% by weight. The density and MFR as the adhesive (Z2) were values as shown in Table 2, respectively.
Using the adhesive (Z2), a pressure vessel was produced in the same manner as in Example 1, and the evaluation results are shown in Table 2.

<Example 5>
[Manufacture of adhesive (Z3)]
Functional group-modified polyethylene resin (X3) 20% by weight and linear low density polyethylene resin (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Novatec LL, Z50MG, manufactured by Nippon Polyethylene Co., Ltd. ( B1)) Adhesive (Z3) pellets having properties as shown in Table 2 were prepared in the same manner as in Example 1 using 80% by weight. The density and MFR as the adhesive (Z3) were values as shown in Table 2, respectively.
Using the adhesive (Z3), a pressure vessel was produced in the same manner as in Example 1, and the evaluation results are shown in Table 2.

<Example 6>
Random terpolymer of ethylene-maleic anhydride (MAH) -methyl acrylate (MA) as the functional group-containing polyethylene (X) (density = 0.94 g / cm ³ , MFR = 8, MAH = 3 wt%, MA = 10% by weight, 20% by weight of Nippon Polyethylene Co., Ltd. ET) and linear low density polyethylene resin (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Z50MG, Nippon Polyethylene) (B2) (made by Co., Ltd.) 80 wt% was made in the same manner as in Example 1 to produce adhesive resin (Z5) pellets having properties as shown in Table 2. Using the adhesive resin (Z5), a pressure vessel was produced in the same manner as in Example 1, and the evaluation results are shown in Table 2.

<Example 7>
A pressure vessel was prepared in the same manner as in Example 1 except that the base member 3 previously treated with the following base treatment agent was used for the disk portion 8 of the base member 3, and the results of evaluation were shown in Table 2.
[Base treatment of base member]
The liquid which mixed 500 mass parts of water, 10 mass parts of glycerylated chitosan, and 10 mass parts of 1,2,3,4-butanetetracarboxylic acid was stirred for 4 hours, and the glycerylated chitosan was fully dissolved. 5 parts by mass of chromium fluoride (trivalent Cr) was added to the resulting solution to obtain a base treatment agent. Next, the base treatment agent was applied to the disk-shaped portion of the aluminum base member with a roll coater, and then heat-dried at 200 ° C. for 30 seconds to form a base treatment layer (film).

The results of an attempt to optimize the pressure vessel of the present invention as a synthetic resin liner are shown below.
<Reference Examples 1-4>
The high density polyethylene resin used for the pressure vessel of Example 1 was used as Reference Example 1 as the synthetic resin liner material. In addition, as Reference Examples 2 to 4, using the adhesive used in Example 1, the high density polyethylene resin of the synthetic resin liner material was changed to the following, and the results evaluated in the same manner as in Reference Example 2 were evaluated. It is shown in Table 3.
[High-density polyethylene resin]
HDPE (A): Trade name: Novatec HD HB111R, manufactured by Nippon Polyethylene Co., Ltd., density = 0.945 g / cm ³ , melt flow rate (HLMFR: measuring temperature 190 ° C., load 211.8 N) 6 g / 10 min HDPE ( B): Product name: Novatec HD, manufactured by Nippon Polyethylene Co., Ltd., density = 0.945 g / cm ³ , melt flow rate (HLMFR: measurement temperature 190 ° C., load 211.8 N) 1.5 g / 10 min HDPE (C ): Product name: Novatec HD, manufactured by Nippon Polyethylene Co., Ltd., density = 0.945 g / cm ³ , melt flow rate (HLMFR: measuring temperature 190 ° C., load 211.8 N) 60 g / 10 min HDPE (D): product name: Novatec HD, Japan polyethylene Co., Ltd., density = 0.945g / cm ^3, a melt flow rate (HL FR: measuring temperature 190 ℃, load 211 · 8N) 100g / 10 minutes

3. Evaluation results As shown in Examples 1 to 6 of Tables 1 and 2, in the present invention, by providing an adhesive on the outer layer of the synthetic resin liner material, a fiber with a conventional reinforcing material is used. There is no deviation, and the fiber can be wound uniformly, so that not only the reinforcing effect is improved, but also a pressure vessel with a good appearance is provided. In addition, by providing an adhesive layer as the innermost layer of the hollow container, there is no need to perform coating or sheeting on the disk part of the base member in advance like powder coating, and a synthetic resin liner material by multilayer blow molding or the like. And the innermost adhesive can be extruded at the same time. These effects can be manufactured by a simple process of continuous one-step adhesion of the inner surface of the hollow container formed of a synthetic resin liner material and the base member, the manufacturing cost is greatly reduced, Not only is it economical, but manufacturing speed and work efficiency are improved.
Also, as shown in Reference Examples 1, 4 and 2 and 3 of Table 3, by using a high density polyethylene resin having a specific range of HLMFR as a synthetic resin liner material and combining with an adhesive having a specific viscosity Thus, it is possible to provide a pressure vessel and a method for manufacturing the same that have dramatically improved adhesive strength and improved hermetic sealability.
Further, as shown in Example 7, by applying a metal base treatment agent to the die member in advance, the adhesive of the innermost layer of the liner and a strong adhesive force were obtained.

  By providing an adhesive on the outer layer of a hollow container formed of a synthetic resin liner material by the pressure container (pressure container) of the present invention and its manufacturing method, fiber deviation from a conventional reinforcing material does not occur, A pressure vessel with improved airtight sealability with improved reinforcement effect because fibers can be wound evenly, and at the same time an adhesive layer is provided on the innermost layer of the hollow container, thereby improving the adhesive force with the base member. And a manufacturing method capable of economically manufacturing the pressure vessel with a simple process, such as household liquefied petroleum gas containers, automotive liquefied petroleum gas containers, compressed natural gas (CNG), oxygen and nitrogen, etc. Can be used particularly favorably for resin pressure vessels that can be used as industrial pressure vessels, hydrogen tanks for fuel cells, etc. Therefore, its industrial value is extremely large.

FIG. 1 is a partially cutaway sectional view of an example of the pressure vessel of the present invention. FIG. 2 is a cross-sectional view of the main part of a blow molding method which is an example of a preferred production method of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hollow container 2 Reinforcement material layer 3, 3 'base member 4, 4' Adhesive 5 Outer base part 6 O-ring 7 Shoulder part of hollow container (liner material) 8 Disc part of base 10 Pressure vessel 11 Extrusion die 12a Parison a
12b Parison b
13a Mold a
13b Mold b
14 support part 15 support stand

Claims (19)

  A pressure vessel having a hollow container formed of a synthetic resin liner and a reinforcing material layer formed of a reinforcing material provided on an outer layer of the hollow container, and having at least one base member; A pressure vessel in which a hollow vessel and a reinforcing material layer are bonded or welded via an adhesive layer provided on an outer layer of the hollow vessel.   The pressure container according to claim 1, wherein the hollow container has an adhesive layer formed in an innermost layer thereof.   The pressure vessel according to claim 2, wherein the hollow container and the base member are bonded or welded via an adhesive layer formed in the innermost layer of the hollow container.   The pressure vessel according to any one of claims 1 to 3, wherein a thickness of the adhesive layer is in a range of 10 µm to 5 mm. The adhesive which forms the said adhesive bond layer is the adhesive which consists of a polyolefin-type resin containing the at least 1 sort (s) of following functional group (a)-(e), or its composition. Item 1. The pressure vessel according to item 1.
[Functional group]
(A) carboxylic acid group or carboxylic anhydride group (b) epoxy group (c) hydroxyl group (d) amino group (e) silyl group The adhesive comprises at least one polyethylene resin (X) selected from the following (A) to (D) containing at least one functional group of (a) to (e): 0.5 to 100 (Z1) density 0.86 to 0.97 g / consisting of 0 wt.% And at least one unmodified polyethylene resin (Y) selected from the following (A) to (E): 0 to 99.5 wt% cm ^3, the pressure vessel according to claim 5 consisting of (z2) a melt flow rate 0.01 to 100 g / 10min adhesive resin (Z).
(A): (a1) density 0.94 to 0.97 g / cm ³ , (a2) high density polyethylene resin having a melt flow rate 0.01 to 100 g / 10 min (B): (b1) density 0.90 Less than 0.94 g / cm ³ , (b2) linear low density polyethylene resin (C) having a melt flow rate of 0.01 to 100 g / 10 min: (c1) high pressure radical method having a melt flow rate of 0.01 to 100 g / 10 min Polyethylene resin (D): (d1) Ultra low density polyethylene resin (E) having a density of 0.86 to less than 0.90 g / cm ³ and (d2) melt flow rate of 0.01 to 100 g / 10 min (E): thermoplastic elastomer   The pressure vessel according to claim 6, wherein (A), (B) or (D) is a polyethylene resin produced with a single site catalyst.   The pressure vessel according to claim 6 or 7, wherein the adhesive resin (Z) comprises 5 to 95% by weight of a functional group-containing polyethylene resin (X) and 5 to 95% by weight of an unmodified polyethylene resin (Y). .   9. The adhesive according to claim 6, wherein the adhesive contains 0.001 to 30 wt% of at least one functional group of (a) to (e) based on the weight of the entire adhesive. A pressure vessel according to 1. The pressure vessel according to any one of claims 1 to 9, wherein the synthetic resin liner material is a synthetic resin material containing at least a polyethylene-based resin having a density of 0.92 to 0.97 g / cm ³ .   The pressure vessel according to any one of claims 1 to 10, wherein the synthetic resin liner material is a synthetic resin material containing a polyethylene resin having a high load melt flow rate of 2 to 70 g / 10 min.   The pressure vessel according to any one of claims 1 to 11, wherein the synthetic resin liner material is a composite material in which at least one of an engineering plastic, a metal member, and an inorganic filler is dispersed in a resin.   The pressure vessel according to any one of claims 1 to 12, wherein the synthetic resin liner material comprises a laminate including at least a thermoplastic resin layer / adhesive layer / barrier layer.   The pressure vessel according to any one of claims 1 to 13, wherein the reinforcing material is a fiber reinforcing material.   A method of manufacturing a pressure vessel having a hollow container formed of a synthetic resin liner material and a reinforcing material layer formed of a reinforcing material provided on an outer layer of the hollow container and having at least one cap member A method for producing a pressure vessel, wherein an adhesive layer is provided on the outer layer of the hollow container, and the hollow container and the reinforcing material layer are bonded or welded via the adhesive layer.   Furthermore, the manufacturing method of the pressure vessel of Claim 15 which provides an adhesive bond layer in the innermost layer of the said hollow container, and adhere | attaches or welds a hollow container and a nozzle | cap | die member through this adhesive bond layer.   The method for producing a pressure vessel according to claim 15, wherein the hollow vessel and the adhesive layer of the outer layer of the hollow vessel are simultaneously formed by multilayer blow molding.   The method for producing a pressure vessel according to claim 16, wherein the hollow vessel and the outermost layer and the innermost adhesive layer of the hollow vessel are simultaneously formed by multilayer blow molding. The method for manufacturing a pressure vessel according to any one of claims 15 to 18, wherein the base member is previously treated with a base treatment agent.

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