JP4961203B2 - Pressure vessel and method for manufacturing the same - Google Patents

Description

  The present invention relates to a pressure vessel and a method for manufacturing the same, and more specifically, improves the adhesive force between the inner wall of a hollow container formed of a synthetic resin liner material and a die member, and improves the hermetic sealing performance, and the die member The present invention relates to a pressure vessel in which various problems such as prevention of rotation of the pressure vessel are solved, and a manufacturing method capable of manufacturing the pressure vessel in a simple process and 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 synthetic resin 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. Therefore, it is lighter than metal ones and can be expected to improve fuel efficiency.

  Such a pressure vessel is provided with a nozzle mounting member in order to attach a nozzle for filling a gas into the vessel or taking out the gas from the vessel. 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, a sealing property at the joint portion or interface portion between the container 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 disk-shaped flange portion of the base member, and a tab that matches the upper and lower locking grooves is formed at the end of the inner liner and joined together. Reducing the risk of causing leakage between the outer shell and the liner.
However, this pressure vessel also exposes the end of the base member 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, which may cause gas leakage for the same reason as described above. There is.

  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 (O-ring, etc.) 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 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 8 is preferably an unsaturated carboxylic acid functional group-containing 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 olefin copolymers are used (see Patent Document 5, paragraph [0025]).

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.
In Patent Document 9, when a parison for forming a synthetic resin liner material is cooled and contracted by blow molding and a metal insert part (a base member or the like) is bonded, the insert part may come off without sufficient adhesion. The problem of sliding is solved by providing an engagement portion having an enlarged diameter and a reduced diameter on a part of the outer surface of the insert part.

  Further, in Patent Document 10, when molding is performed by blow molding, a plurality of through holes are provided in the face wall of the flange of the base, and the outer meat wall in contact with the outer surface of the flange and the inner meat wall in contact with the inner surface are externally communicated. By making it integrated through the bridging part that fills the hole, the detent of the base is eliminated.

  As described above, the conventional pressure vessel exhibits airtightness especially for natural gas having a relatively large molecular weight, but maintains sufficient hydrogen gas permeability resistance for hydrogen gas having a small molecular weight. However, there are demands for high-performance bonding performance, high-quality products, various problems such as prevention of rotation of the base part during molding, and manufacturing at a lower cost and with a simple manufacturing process.

Japanese Patent Publication No. 5-88665 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 JP-A-7-158797

  The object of the present invention relates to a pressure vessel and a method for manufacturing the same in view of the above-mentioned problems of the prior art. More specifically, the adhesive force between the inner wall of a hollow vessel formed of a synthetic resin liner material and a cap member is improved. Another object of the present invention is to provide a pressure vessel in which hermetic sealing properties are improved and various problems such as prevention of rotation of the base member are solved, and a manufacturing method capable of manufacturing the pressure vessel easily and economically.

As a result of intensive studies in order to solve the above problems, the present inventors have found that a hollow container formed of a synthetic resin liner material and a reinforcing material formed of a reinforcing material provided on the outer layer of the hollow container A pressure vessel having a layer and having at least one base member, the base member being provided with line engravings and / or grooves and having a specific adhesion so as to be buried in the line engravings and / or grooves The above-mentioned problems can be solved by a pressure vessel in which a specific form of an adhesive layer is formed by an agent, and a hollow container and a base member are bonded or welded via the adhesive layer, and its manufacturing method. More specifically, with respect to the manufacturing method, the adhesive force between the inner wall of the hollow container formed of the synthetic resin liner material and the base member is improved, the hermetic seal is improved, and various problems such as prevention of the rotation of the base member occur. Solved Force vessels and simple process that a pressure vessel, and found to be able to provide a production method can be economically produced, and have completed 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 A pressure vessel having at least one base member,
The base member is provided with line engravings and / or grooves, and an adhesive layer is formed by an adhesive so as to bury the line engravings and / or grooves, and the hollow container and the base member are interposed through the adhesive layer. Is glued or welded,
The adhesive is at least one polyethylene selected from the following (A) to (D) containing at least one functional group of the following (a) to (e) based on the weight of the entire adhesive: (Z1) comprising 5 to 95% by weight of resin (X) and 5 to 95% by weight of at least one unmodified polyethylene resin (Y) selected from the following (A) to (E) not containing a functional group: ) Density 0.86-0.97 g / cm ³ , (z2) melt flow rate 0.01-100 g / 10 minutes of adhesive resin (Z) ,
The thickness of the surface layer of the adhesive layer after being buried is 10 μm or more,
The pressure vessel is a synthetic resin material in which the synthetic resin liner material includes a polyethylene-based resin having a density of at least 0.92 to 0.97 g / cm ³ .
[Functional group]
(A) Carboxylic acid group or carboxylic anhydride group (b) Epoxy group (c) Hydroxyl group (d) Amino group (e) Silyl group (A): (a1) Density 0.94 to 0.97 g / cm ³ (A2) High density polyethylene resin (B) having a melt flow rate of 0.01 to 100 g / 10 min: (b1) Density of 0.90 to less than 0.94 g / cm ³ (b2) Melt flow rate of 0.01 -100 g / 10 min linear low density polyethylene resin (C): (c1) Melt flow rate 0.01-100 g / 10 min high pressure radical polyethylene resin (D): (d1) density 0.86- Less than 0.90 g / cm ³ , (d2) Ultra-low density polyethylene resin (E) with a melt flow rate of 0.01 to 100 g / 10 minutes (E): Thermoplastic elastomer

  According to the second invention of the present invention, in the first invention, there is provided a pressure vessel in which the adhesive layer is formed by powder coating or injection molding.

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

According to a fourth invention of the present invention, in any one of the first to third 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 fifth invention of the present invention, in any one of the first to fourth inventions, 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 sixth invention of the present invention, in any one of the first to fifth inventions, the synthetic resin liner material is formed of a laminate including at least a thermoplastic resin layer / adhesive layer / barrier layer. A container is provided.

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

Further, according to the eighth invention of the present invention, it 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 A method for producing a pressure vessel having at least one base member, wherein the base member is provided with a line and / or groove, and an adhesive layer is formed by burying an adhesive in the line and / or groove, A method for producing a pressure vessel according to any one of the first to seventh aspects of the present invention is provided, in which a synthetic resin liner material and a base member are bonded or welded via the adhesive layer.

According to a ninth aspect of the present invention, there is provided a pressure vessel manufacturing method according to the eighth aspect , wherein the hollow container is formed by blow molding and the adhesive layer is formed by powder coating or injection molding. Is done.

According to a tenth aspect of the present invention, there is provided the method for producing a pressure vessel according to the eighth or ninth aspect , wherein the base member is previously treated with a ground treatment agent before forming the adhesive layer. .

ADVANTAGE OF THE INVENTION According to this invention, the adhesive force of the inner side wall of a hollow container formed with a synthetic resin liner material and a nozzle | cap | die member is improved, and the pressure vessel which airtight sealing property was improved is obtained. This is a resin that can be used as liquefied petroleum gas containers for home use, liquefied petroleum gas containers for automobiles, compressed natural gas (CNG), industrial pressure vessels for storing oxygen, nitrogen, etc., hydrogen tanks for fuel cells, etc. The pressure vessel made. That is, the present invention provides a synthetic resin liner material in which an anchor effect is generated by forming an adhesive layer embedded in the line engraving and / or groove portion by providing a line engraving and / or groove portion in the base member. And a pressure vessel having a very strong adhesive force.
In addition, if the adhesive layer is preferably formed by powder coating, injection molding, or the like, even if it is a complicated line engraving or deep groove, the adhesive spreads through a simpler process, so that a detailed groove is formed. Resin can be injected, a uniform film can be formed, and very strong adhesion or welding is possible.
Furthermore, it has the effect that the twist and rotation of the base member at the time of joining the synthetic resin liner material and the base member during molding of the hollow container are suppressed.
In addition, by applying a base treatment agent to the metal of the base member in advance, the adhesive force between the synthetic resin liner and the adhesive is greatly improved.

  As described above, a pressure vessel having a strong adhesive force between a hollow container formed from a synthetic resin liner material and a cap member, having a high hermetic sealing property, and a high performance, and a method for producing the same are provided by a simpler method. It became possible. Such a container is suitable not only for low pressure vessels such as natural gas but also for high-performance high-pressure vessels because it can maintain sufficient hydrogen gas permeability even for hydrogen gas with a low molecular weight. Can be used.

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 base member is provided with a line and / or groove, and an adhesive layer is formed by a specific adhesive so as to be buried in the line and / or groove. It is a pressure vessel in which a hollow container and a base member are bonded or welded via an agent layer.

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 base members, wherein the base member is provided with a line and / or groove, and a specific adhesive is buried in the line and / or groove to form an adhesive layer, In the method for manufacturing the pressure vessel, the synthetic resin liner material and the base member are bonded or welded via the adhesive layer.
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. The base member 3 is composed of a material layer 2 (outer wall), and a base member 3 for attaching a nozzle for filling and discharging high-pressure gas is attached to at least one end of the hollow container 1. An adhesive is buried in the line engraving and / or the grooves 4a (4a ′), 4b (4b ′), and 4c (4c ′) provided in the portion 8 to form an adhesive layer 4, and the adhesive layer 4 is interposed therebetween. The shoulder portion 7 of the hollow container 1 formed of a synthetic resin liner material and the disk portion 8 of the base member 3 are bonded or welded to form a hollow container with a base, and the outer layer of the hollow container is covered with a fiber reinforcing material. The pressure vessel 10 is formed by forming the reinforcing material layer 2.

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, and if it is within such a range, there is no occurrence of unevenness of extrusion, rough surface, etc. during blow molding in parison extrusion. It is preferable from the occurrence of uneven thickness of the liner and rough surface.
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. For example, it may be formed of a composite material in which an engineering plastic, a metal member, and an inorganic filler are dispersed in a high-density polyethylene resin layer, or from a multilayer structure including at least a thermoplastic resin layer / adhesive layer / barrier layer. It is good also as a laminated body.

  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-described high-density polyethylene, three-layer structure, thermoplastic resin layer / adhesive layer / barrier layer / adhesive layer Laminates of 3 types and 5 layers of thermoplastic resin layer, 3 layers or more of 4 layers and 6 layers of thermoplastic resin layer / regrind layer / adhesive layer / barrier layer / adhesive layer / thermoplastic resin layer In addition, there may be mentioned laminates composed of two layers / two layers of thermoplastic layer / adhesive layer and two layers / three layers of adhesive layer / barrier layer / adhesive layer.
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, an adhesive resin (Z) of the present invention to be described later or a general adhesive resin such as an epoxy resin or a polyurethane resin can be used.
In the case of using these liner materials 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 As shown in FIG. 1, the reinforcing material forming the reinforcing material layer 2 covers the outer layer of the hollow container 1 formed from a synthetic resin liner material, and improves the pressure resistance of the pressure container 10. It may be made of a lightweight metal material such as aluminum, titanium, or light alloy, but fiber reinforced plastics (FRP: fiber reinforced plastics) when molding processability and weight reduction are considered. Or it is suitable to comprise with a 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.

  As the resin for forming the reinforcing material 2 on the outer side wall, epoxy resin, unsaturated polyester resin, urea resin, phenol resin, melamine resin, polyurethane resin, polyimide resin, thermosetting resin, polyamide resin, polyethylene terephthalate, polybutylene terephthalate Polyester resins such as ABS, engineering plastics such as polyether ketone and polyphenylene sulfide, and thermoplastic resins such as polypropylene and poly-4-methyl-1-pentene resin. Among these, thermosetting resins are generally preferred from the viewpoints of performance such as heat resistance and strength, and economical efficiency.

(3) Base Member The base member 3, 3 ′ of the present invention is installed for attaching a nozzle for filling and discharging high-pressure gas, for example, one end has the shape of the disk portion 8, and pressure At least one end of a cylindrical container composed of a hollow container 1 inside the container 10 and an outer reinforcing material layer 2 is attached to the hemispherical shoulder 7 inside the hollow container 1 of the pressure container. ′ Disk part 8 is embedded so as to be embedded, preferably with a roughening or pretreatment agent in advance, and the disk part 8 of the base member 3, 3 ′ provided with adhesive layers 4, 4 ′ and synthetic resin The shoulder 7 of the hollow container 1 formed from a liner material is brought into contact with and bonded 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, functional group-containing 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 aluminum which is lightweight, has high mechanical strength, and is relatively inexpensive is preferable.

  The disk portion 8 of the base member 3, 3 ′ embedded in the shoulder 7 of the inner hollow container 1 has a roughened surface or a ground treatment in order to increase the adhesive strength with the adhesive 4, 4 ′. It is desirable to be treated with an agent. 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.

  In the present invention, the line engraving and / or the groove (4a, 4b, 4c, 4a ′, 4b ′, 4c ′) provided on the base member is a regular and / or irregular line, strip, or dot ( (Circle, Δ, □, star shape, etc.), spiral shape, spiral shape, geometric pattern and the like are not particularly limited. In addition, it is preferable that the groove portion has a structure in which the lower portion is widened, such as an inverted V shape, a trapezoidal shape, or a circle, because an anchor effect is exhibited.

(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, mellitic 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 The adhesive layer of the present invention includes a thermosetting resin such as an epoxy resin, a polyurethane resin, a polyester resin, an acrylic resin, or (a) a carboxylic acid group or a carboxylic anhydride group, (b) Common adhesives such as thermoplastic resins such as polyolefin resins containing functional groups such as epoxy groups, (c) hydroxyl groups, (d) amino groups, and (e) silyl groups 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.

  Functional group (a) As a compound for introducing a carboxylic acid group or a carboxylic acid anhydride group, α, β-unsaturated dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, itaconic acid or the like, anhydride thereof, acrylic Examples thereof include unsaturated monocarboxylic acids such as acid, methacrylic acid, furanic acid, crotonic acid, vinyl acetic acid and pentenoic acid.

  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 the polymer component of the present invention, a method of introducing a functional group-containing polyolefin resin in which at least one functional group-containing monomer is grafted, a functional group such as ethylene, propylene, or the like is used. Examples thereof include a method in which a random copolymer of an olefin and a functional group-containing compound is mixed and introduced into a resin component.
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. Is suitable, and in the case of a random copolymer, it is suitable that it is 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 that it is difficult to perform, deterioration is likely to occur, handling and workability are poor, and it is 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 the organic peroxide 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, the adhesive resin (Z) composed of a preferable polyethylene resin in the present invention 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 with various polymerization apparatuses, polymerization conditions, and catalysts in each polymerization mode of Ziegler catalyst, single site catalyst, etc., slurry method, solution method, and gas phase method. As a single site catalyst resin, Nippon Polyethylene Co., Ltd., trade name: Harmolex, trade name: Kernel, Nihon Evolue Co., Ltd., trade name: Evolue, Dow Chemical Co., Ltd. Product name: Engage, etc.

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) obtained by a high-pressure radical polymerization method having a melt flow rate of 0.01 to 100 g / 10 min, ethylene vinyl. Ester copolymers and copolymers of ethylene and α, β-unsaturated carboxylic acids or derivatives thereof, and the like. These low-density polyethylene resins and the like are produced by a known high-pressure radical polymerization method, such as a tubular method and an autoclave. You may manufacture by any method of a method.
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. As a method for producing the block copolymer, many methods have been proposed. 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 when functional groups are contained, or may be preliminarily mixed with a known mixer such as a kneader or a Henschel mixer to contain functional groups.
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. A particularly preferable combination is a functional group-containing product of the component (B), and a functional group-containing product having a linear low density polyethylene resin as a main component by a single site catalyst 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.
The content is such that the amount of at least one monomer selected from the group consisting of an unsaturated carboxylic acid or a derivative thereof is 0.001 to 10% by weight, preferably 0.01 to the resin component. 5% by weight, more preferably 0.1 to 3% by 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 As the radical initiator used when grafting a functional group to the polyethylene resin of the present invention, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl is used. -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-butyldiperoxyisof Tartrate, n-butyl-4,4-bis (t-butylperoxy) valerate, t-butylperoxybenzoate, t-butylperoxyacetate, cyclohexanone peroxide, t-butylperoxylaurate, acetyl peroxide, etc. Of organic peroxides.
Among these, a decomposition temperature for obtaining a half-life of 1 minute is 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 compounding amount of the radical initiator is usually 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.3 parts by weight based on 100 parts by weight of the total resin component including the polyethylene resin at the time of primary modification. Used in the range of parts. 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. Add 0 parts by weight and 0.005 to 0.5 parts by weight of radical initiator, and use a single screw extruder and / or twin screw extruder, one or more reactors, etc., and melt-kneading or containing functional groups in a solvent Is achieved.
Specifically, a melt kneading method using an extruder, a Banbury mixer, a kneader, etc., a solution method dissolved in an appropriate solvent, a slurry method suspended in an appropriate solvent, or a so-called gas phase grafting method can be mentioned.
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 the production of the functional group-containing polyethylene resin (X) according to the present invention, for the purpose of improving its performance, a method already known as described in JP-A-62-10107, for example, containing the above-mentioned graft functional group A method of treating with an epoxy compound or a polyfunctional compound containing an amino group or a hydroxyl group at the time or after containing a functional group, unreacted monomer (unsaturated carboxylic acid or derivative thereof) or various components by-produced by heating or washing It is possible to adopt a method of removing
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 carried out at such a high temperature, it is necessary to suppress the mixing of air into the extruder and the reactor as much as possible. In melt-kneading, it is also necessary to avoid the resin 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 that the polyolefin-based resin material contains a functional group in a plurality of orders, and thereby a relatively expensive monomer, an unsaturated carboxylic acid and its The functional group content of at least one functional group-containing monomer selected from the group consisting of derivatives is sufficiently increased to improve economy, and a high functional group content is achieved with a relatively small amount of functional group-containing monomer. It is possible to produce a high-quality functional group-containing polyolefin resin (X) that has excellent adhesion performance, no unreacted functional group-containing monomers, and no gel or resin burns. .
The grafting functional group content (measurement method: by infrared spectrophotometer) obtained by the functional group containing (addition) method in such melt kneading is generally about 0.2 to 2.5% by weight. The upper limit of the grafting functional group content of the final functional group-containing polyethylene resin (X) 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 it is desirable to have a higher functional group content.

(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) density 0.90 to less than 0.94 g / cm ³ , (b2) linear shape with melt flow rate 0.01 to 100 g / 10 min Low density 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) At least one unmodified polyethylene selected from an ultra-low density polyethylene-based resin (D) and a thermoplastic elastomer (E) having a melt flow rate of 0.01 to 100 g / 10 min. It is a 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 it may cause an adverse effect that excessive resin deterioration or gel may occur during molding. It is preferable to use the component (Y) because it is easy to adjust the functions such as density, heat resistance, mechanical properties, rigidity, and flexibility, or is economical.
In addition, at least one of (A), (B) and (D) used for the functional group-containing polyethylene resin (X) or unmodified polyethylene resin is produced with a single site catalyst. However, it is also preferable from the fact that there are few low molecular weight components and the resin deterioration and the generation of gel when containing functional groups are suppressed, and the performance such as mechanical strength and adhesive strength is improved.

(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): It is an adhesive resin (Z) consisting of 99.5% by weight (z1) density 0.86 to 0.97 g / cm ³ , (z2) melt flow rate 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 of 0.01 to 100 g / 10 min (B): (b1) Density 0.90 ˜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): (c1) melt flow rate of 0.01 to 100 g / 10 min High pressure radical polyethylene resin (D): (d1) density 0.86 to less than 0.90 g / cm ³ , (d2) ultra low density polyethylene resin (E) with a melt flow rate of 0.01 to 100 g / 10 min: 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, in view of adhesiveness, heat resistance, strength, and easy moldability, a preferable combination is modified polyethylene of component (B) + unmodified polyethylene of component (A + B). A particularly preferable blending ratio is 10 to 30% by weight of the modified linear low density polyethylene resin (B) and 90 to 70% of the unmodified polyethylene resin (resin A / resin B = 0 to 30% by weight / 100 to 70% by weight). It is a composition mixed in a proportion 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 (z1) density 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 0.92 to 0.95. is there. If the density is less than 0.86 g / cm ³ , the adhesive strength may be lowered. If the density is more than 0.97 g / cm ³ , industrial mass production is difficult, and durability may be lowered. Occurs.
The melt flow rate (z2) 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 40 g / 10 minutes. When the MFR is less than 0.01 g / 10 minutes, there is a difficulty in molding processability, and when it exceeds 100 g / 10 minutes, the strength such as impact strength may be lowered.

The adhesive of the present invention forms an adhesive layer so as to be embedded by engraving (line engraving and / or groove) on part or all of the cap member by powder coating, injection molding, or the like. When filling and discharging high-pressure gas, the inner synthetic resin liner material shrinks and expands, responds to temperature changes, changes over time, resistance to contents, etc. Since those having excellent durability are required, among the above-mentioned adhesives, an adhesive resin (Z) that satisfies these various performances and is relatively inexpensive and advantageous in terms of economy is preferable.
Further, in the present invention, in order to further strengthen the adhesive strength between the die member and the adhesive, a surface treatment such as the above-described roughening treatment or base treatment agent is performed on a part or the whole of the die member. It is desirable.

  Examples of the powder coating generally include an electrostatic powder coating method, a fluid immersion method, a powder spraying method, and the like, but are not particularly limited in the present invention, but among them, the electrostatic coating method is preferable. In the electrostatic powder coating method, when the plastic powder is negatively charged at the outlet of the spray gun and sprayed toward the grounded coated product, the plastic powder is evenly applied to the surface of the product by electrostatic attraction. There are a method of using a spray gun that adheres and sends it to a heating furnace and melts the powder to form a uniform coating film, an electrostatic fluidized immersion method, and the like.

  Another preferable example of providing the adhesive layer 4 on the base members 3 and 3 'is an injection molding method. According to the injection molding method, it is possible to inject the adhesive at a high speed up to the details of the groove portion of the disk portion 7 of the base member 4, and it is possible to provide an inexpensive, high-quality product that is excellent in economy and workability.

The adhesive powder used for the powder coating has a density of 0.90 to 0.96 g / cm ³ , preferably 0.915 to 0.95 g / cm ³ , more preferably 0.92 to 0.94. It is preferable that If the density is less than 0.90 g / cm ³ , it may not be easily pulverized, and if it exceeds 0.96 g / cm ³ , the durability may decrease.
The melt flow rate is preferably in the range of 0.01 to 100 g / 10 minutes, preferably 0.1 to 50 g / 10 minutes, more preferably 0.3 to 30 g / 10 minutes. When the MFR is less than 0.01 g / 10 minutes, there is a difficulty in molding processability, and when it exceeds 100 g / 10 minutes, the strength such as impact strength may be lowered.
As the adhesive used for the powder coating, the above-mentioned adhesive (Z) is preferable.

The median particle size is 90 to 150 mesh (standard sieve: JIS Z8801), preferably 100 to 140 mesh, more preferably 110 to 130 mesh, and the bulk specific gravity (based on JIS K8721) is 0.20 to 0.00. It is 50 g / cc, preferably 0.25 to 0.40, more preferably 0.30 to 0.35.
Further, the static friction coefficient (conforming to JIS K8721) of the powder is 0.7 to 0.9, preferably 0.75 to 0.85. When the particle size, bulk specific gravity, and static friction coefficient of these powders deviate from the above ranges, there may be cases where the coating cannot be performed well to a uniform coating film or details such as a locking groove.

Further, the thickness of the surface layer of the adhesive layer after being buried according to the present invention is desirably 10 μm, preferably 50 μm to 5 mm, more preferably 300 μm to 3 mm.
However, in powder coating, a thickness of about 10 μm to 2 mm is preferable from the viewpoint of workability and coating film workability. If it is 2 mm or more, the number of times of coating becomes complicated, which is not practical.
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. As shown in FIG. 1, the pressure vessel according to the present invention is provided in a hollow container 1 (inner wall) formed of an inner synthetic resin liner material and an outer layer of the hollow container 1. A pressure vessel 10 having at least one base member 3, and a base for attaching a nozzle for filling and discharging high-pressure gas to at least one end of the hollow container. The member 3 is mounted, and the adhesive is buried in the line engraving and / or the grooves 4a (4a ′), 4b (4b ′), and 4c (4c ′) provided in the disk portion 8 of the base member 3. The agent layer 4 is bonded or welded to the shoulder 7 of the hollow container 1 formed from the synthetic resin liner material and the disk part 8 of the base member 3 through the adhesive layer 4 to form a hollow container with a base. Further, the outer layer of the hollow container 1 is covered with a fiber reinforcement 2 and the pressure capacity is increased. The container 10 is used.

In the method for manufacturing a pressure vessel according to the present invention, the method of forming the adhesive layer 4 by burying the adhesive in the line and / or groove provided in the disk part of the base member includes powder coating, injection molding It is preferable to carry out by a method. With the powder coating method and injection molding method, it is possible to inject the adhesive to the details even with complicated shapes such as complicated lines and patterns, deep grooves and diverging, and uniformly the adhesive layer Can be formed.
The base member is preferably treated with a base treatment agent before forming the adhesive layer, but may be treated with a base treatment agent before forming the line engraving and / or the groove. In addition, either or both of the surface treatment and the roughening treatment with the base treatment agent may be performed, and the step of forming the line engraving and / or the groove and the order of the above treatments are appropriately determined. However, it is preferable from the viewpoint of improving the adhesive strength that the roughening treatment is performed after the step of forming the line engraving and / or the groove is performed, and finally the treatment with the base treatment agent is performed. .

  The method for producing a hollow container formed of a synthetic resin liner is not limited to the blow molding method, and may be produced by injection molding, rotational molding, compression molding, etc. Since the die member can be integrated at the same time as the formation, the manufacturing process is simple, the manufacturing cost is low, and it is economical, it is preferable to adopt the blow molding method.

As a method of manufacturing a hollow container by blow molding, a synthetic resin for forming a synthetic resin liner material is molded into a cylindrical shape by blow molding, and then an adhesive film is formed in advance on the disk part of the base member by powder coating The base member is inserted into at least one end portion of the cylindrical synthetic resin liner material, and the end portion of the synthetic resin liner material is reduced in diameter by closing the die, and the disc portion of the base member and the A method of bonding or welding the inner shoulder portion of the synthetic resin liner material of the hollow container via the adhesive is preferable from the viewpoint of airtightness.
In addition, the adhesive layer and the hollow container can be simultaneously molded by an injection molding method, which can simplify the manufacturing process, which is preferable.

FIG. 2 shows 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.
In FIG. 2, the disk portion 8 of the base member 3, 3 ′ (see FIG. 1), which has been preferably surface-treated or treated with a base material in advance, has grooves 4 a (a ′), 4 b (b ′) along the circumference. 4c (c ') is provided, and the groove part 4a, 4b, 4c is coated or injected with an adhesive by powder coating or injection molding, and is buried, and the base member 3 having the adhesive layer 4 is produced. Is done. Next, after the base member 3 with the adhesive layer 4 is supported on the upper and lower sides of the support portion 14 associated with the support base 15 attached to the blow molding apparatus, the density is increased from the die 11 of the extruder of the blow molding machine (not shown). A synthetic resin liner made of a thermoplastic resin such as polyethylene resin is extruded as a cylindrical parison 12 (a, b), and the discs of the cap members 3, 3 ′ are placed between the molds 13 (a, b). The parison is suspended so as to cover the part 8. Next, the mold 13 (a, b) is closed with the parison 12 (a, b) still soft enough, the diameter of the parison 12 (a, b) is reduced, and the necks of the base members 3, 3 ′ Is pinched at the same time as the parison 12 (a, b), and blows up a gas such as air into the mold to expand the parison 12 (a, b) and press it against the wall of the mold 13 (a, b) Then, the hollow container 1 is formed by cooling and solidifying. On the other hand, the shoulder portion 7 of the hollow container 1 formed from the synthetic resin liner material and the disk portion 8 of the base member 3, 3 ′ cause the base member 3, 3 ′ (rod) to be the synthetic resin liner material. After being pressed and adhered to the shoulder portion 7 and fused, the mold is cooled to produce the hollow container 1 with a cap. Next, the outer periphery of the hollow container 1 with a mouthpiece is impregnated with a thermosetting resin such as an epoxy resin or an unsaturated polyester resin, with a fiber yarn such as a carbon fiber yarn or a bundle, a glass fiber yarn or a bundle, a bundle, a mat, or the like. The pressure vessel 10 is manufactured by coating and curing the thermosetting resin to form the fiber reinforcing material (CFRP, GFRP, etc.) layer 2.
The manufacturing method of the hollow container of the present invention is not limited to the above blow molding method, and may be manufactured by injection molding, rotational molding, compression molding or the like.

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 made 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 minutes): 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 layer thickness: Select any part (5 places) of the disk-shaped part of the base member to which the adhesive resin is bonded, and use the following thickness gauge (EX-V manufactured by Keyence Corporation) to form the adhesive layer The thickness was measured (measured value is an average value of 5 points).
[Thickness gauge]
High-accuracy overcurrent type using a digital displacement sensor: As the distance between the object and the sensor head approaches, the overcurrent increases and the transmission amplitude decreases. This transmission amplitude is rectified to change the DC voltage. The rectified signal and the distance are substantially proportional to each other, and linearity is corrected by a linearize circuit to obtain a linear output proportional to the distance. The thickness is displayed digitally.
(5) 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 peeling (measured value is an average value of 5 points).
(6) Drop impact test: The state of the container after the pressure container was dropped from a height of 5 m with the cap portion facing downward at −40 ° C. was observed.
(7) Gas leak test: The pressure vessel 10 is filled with 30 MPa hydrogen gas, and the pressure in the tank after standing for 60 days at 60 ° C. is based on the change over time (◯: no gas leak, x: gas leak).

2. Raw material (1) Production of functional group-containing polyethylene resin (X) (i) [Production of functional group-containing polyethylene resin (X1)]
Powdered polyethylene resin (made of linear low density polyethylene resin (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Novatec LL, Z50MG, B1 manufactured by Nippon Polyethylene Co., Ltd.)) B) 0.8 parts of maleic anhydride and 0.02 parts of 2,5-dimethyl-di- (t-butylperoxy) hexane are added to 100 parts by weight and mixed with a Henschel mixer. ) Using a 50 mm single screw extruder, melt kneaded 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. A 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, UJ370G, 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 a screw speed of 50 rpm and a resin temperature of 280 ° C., MFR 8 g / 10 min, density 0. A functional group-containing polyethylene resin (X2) having a weight of 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. Using a 50 mm single screw extruder, melt kneaded under conditions of a screw speed of 50 rpm and a resin temperature of 280 ° C., containing a functional group with an MFR of 2 g / 10 minutes, a density of 0.930 g / cm ³ , and a grafting rate of 0.4 wt% Polyethylene 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 base with adhesive]
As shown in FIG. 1, the upper (4a), middle (4b), and lower (4c) three trapezoids (inlet width 2 mm × bottom part) are equally spaced around the entire circumference of the disk part 6 of the aluminum base member 3. (4 mm wide × 3 mm deep) is engraved to provide a groove, and then the adhesive (Z1) is injected into the groove by injection molding to form a 0.3 mm thick adhesive layer 4 on the entire surface of the disk 6. A base member with an adhesive was prepared.

[Manufacture of pressure vessels]
As shown in FIG. 2, the base members 3 and 3 'provided with the adhesive layer 4 are installed above and below the support portion 14 associated with the support base 15, and NB150 continuous multilayer made by Nippon Steel Works, Ltd. Using a hollow molding machine, a synthetic resin liner material having the following configuration is extruded from a die 11 of a blow molding machine (not shown) into a cylindrical parison 12 (a, b) under the following conditions. a) and b), the mold 13 (a, b) is closed in a state where the parison is still sufficiently soft, the diameter of the parison 12 (a, b) is reduced, and the neck of the base member 3 is attached to the parison. After pinching simultaneously with air 12, air is blown up and blown up to press the parison 12 against the wall of the mold 13 to mold it from the synthetic resin liner material into the hollow container, and then cool the mold to remove the hollow container 1. Formed. At that time, the disk portion 8 of the base member 3 is formed of a synthetic resin liner that is pressed and brought into close contact with the inner shoulder portion 7 of the hollow container formed of the synthetic resin liner material 1 by air pressure. The shoulder portion 7 of the hollow container and the disc portion 8 of the base member 3 were fused to produce a hollow container having a volume of 30 liters. 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 with an epoxy resin. The material (CFRP) was fused, the epoxy resin was cured, and the reinforcing material layer 2 was formed, 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]
From the outer layer side / high density polyethylene layer / regrind layer / adhesive layer / gas barrier layer (EVOH layer) / adhesion under conditions of molding temperature 210 ° C., blow pressure 1.4 MPa, mold temperature 20 ° C., blowing time 130 sec. Cylindrical hollow containers of 4 layers of material layer / high density polyethylene layer / (layer thickness: 0.7 mm / 2.0 mm / 0.1 mm / 0.15 mm / 0.1 mm / 2.0 mm were manufactured. The specific layer structure 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 , high load 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) manufactured by Kuraray Co., Ltd.

<Comparative Example 1>
Production of a pressure vessel was attempted in the same manner as in Example 1 except that the adhesive (Z) was not used in the engraved part of the base member in Example 1, but the resin did not enter the engraved part during blow molding. The evaluation results are shown in Table 1.

<Example 2>
[Manufacture of adhesive resin (Z4)]
Functional group-modified polyethylene resin (X1) 2% by weight and unmodified polyethylene resin (Y1) linear low-density polyethylene (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Z50MG, Nippon Polyethylene (Made by Co., Ltd.) After 98% by weight of melt kneading or dry blending, mixing with a Henschel mixer, using a 50 mm single screw extruder made by Modern Machinery Co., Ltd. under the conditions of a screw speed of 50 rpm and a resin temperature of 280 ° C. After melt-kneading, pelletizing was performed to prepare adhesive resin (Z4) pellets having the properties shown in Table 1.
The adhesive layer 4 was provided on the base member 3 in the same manner as in Example 1 using the adhesive resin (Z4).
Table 1 shows the results of producing and evaluating a pressure vessel in the same manner as in Example 1 using the base member 3 with adhesive.

<Comparative example 2>
[Manufacture of base with adhesive]
Directly on the disk part 6 of the aluminum base member 3 (without engraving (groove part)), the same adhesive (Z1) as in Example 1 is applied to the surface of the disk part 8 with an overall thickness of 0.3 mm. Table 1 shows the results of manufacturing a pressure vessel in the same manner as in Example 1 using the base member 3 with adhesive, and producing and evaluating the pressure vessel.

<Example 3>
[Production of Adhesive Resin (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: Z50MG, manufactured by Nippon Polyethylene Co., Ltd. (B1)) Adhesive resin (Z2) pellets having properties as shown in Table 1 were prepared in the same manner as Example 1 using 80% by weight. The density and MFR as the adhesive resin (Z2) were values as shown in Table 1, respectively.
Using the adhesive resin (Z2), a pressure vessel was produced in the same manner as in Example 1, and the evaluation results are shown in Table 2.

<Example 4>
[Production of Adhesive Resin (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: Z50MG, manufactured by Nippon Polyethylene Co., Ltd. (B1)) Adhesive resin (Z3) pellets having the properties shown in Table 1 were prepared in the same manner as in Example 1 using 80% by weight. The density and MFR as the adhesive resin (Z3) were values as shown in Table 2, respectively.
Using the adhesive resin (Z3), a pressure vessel was produced in the same manner as in Example 1, and the evaluation results are shown in Table 2.

<Example 5>
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 6>
A pressure vessel was prepared and evaluated in the same manner as in Example 1 except that a base member treated with the following base treatment agent was used for the disk-shaped portion of the base member formed by engraving in advance to form a groove portion. Indicated.
[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, after applying the surface treatment agent to the disk-shaped portion of the aluminum base member with a roll coater, the surface treatment layer (film) was formed by heating and drying at 200 ° C. for 30 seconds. Similarly, an adhesive layer was formed.

4). Evaluation results As shown in Examples 1 to 6 of Tables 1 and 2, in the present invention, the die member is provided with line engravings and / or grooves, and the adhesive is buried in the line engravings and / or grooves. By doing so, it is possible to provide a pressure vessel and a method for producing the same that have dramatically improved adhesive strength and improved hermetic sealing performance. Moreover, the adhesive force of a synthetic resin liner material and a nozzle | cap | die member further improved by giving a base-treatment agent to a nozzle | cap | die member previously.
On the other hand, when the functional group-containing polyethylene resin (X) is outside the scope of the present invention as in Comparative Examples 1 and 2, or the cap member of Comparative Example 3 has no groove, in the drop impact test and the gas leak test, The goal could not be achieved.

  In the pressure vessel (pressure vessel) and the manufacturing method thereof according to the present invention, the adhesive force between the inner wall of the hollow vessel formed by the synthetic resin liner material and the base member is formed through a uniform adhesive layer by powder coating. It is possible to provide an improved pressure vessel with improved hermetic sealing and a manufacturing method capable of economically producing the pressure vessel with a simple process. Therefore, it is possible to provide a domestic liquefied petroleum gas container, an automobile liquefied petroleum gas container, and a compressed natural gas. (CNG: Compressed Natural Gas), industrial pressure vessels for storing oxygen, nitrogen, etc., pressure vessels made of resin that can be used as hydrogen tanks for fuel cells, etc. Very 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

1: Hollow container 2: Reinforcement material layer 3, 3 ′: Base member 4, 4 ′: Adhesive 4a, 4b, 4c, 4a ′, 4b ′, 4c ′: Line engraving, groove part 5: Outer base part 6: O Ring 7: shoulder 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 (10)

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;
The base member is provided with line engravings and / or grooves, and an adhesive layer is formed by an adhesive so as to bury the line engravings and / or grooves, and the hollow container and the base member are interposed through the adhesive layer. Is glued or welded,
The adhesive is at least one polyethylene selected from the following (A) to (D) containing at least one functional group of the following (a) to (e) based on the weight of the entire adhesive: (Z1) comprising 5 to 95% by weight of resin (X) and 5 to 95% by weight of at least one unmodified polyethylene resin (Y) selected from the following (A) to (E) not containing a functional group: ) Density 0.86-0.97 g / cm ³ , (z2) melt flow rate 0.01-100 g / 10 minutes of adhesive resin (Z) ,
The thickness of the surface layer of the adhesive layer after being buried is 10 μm or more,
The pressure vessel which is a synthetic resin material in which the synthetic resin liner material includes a polyethylene resin having a density of at least 0.92 to 0.97 g / cm ³ .
[Functional group]
(A) Carboxylic acid group or carboxylic anhydride group (b) Epoxy group (c) Hydroxyl group (d) Amino group (e) Silyl group (A): (a1) Density 0.94 to 0.97 g / cm ³ (A2) High density polyethylene resin (B) having a melt flow rate of 0.01 to 100 g / 10 min: (b1) Density of 0.90 to less than 0.94 g / cm ³ (b2) Melt flow rate of 0.01 -100 g / 10 min linear low density polyethylene resin (C): (c1) Melt flow rate 0.01-100 g / 10 min high pressure radical polyethylene resin (D): (d1) density 0.86- Less than 0.90 g / cm ³ , (d2) Ultra-low density polyethylene resin (E) with a melt flow rate of 0.01 to 100 g / 10 minutes (E): Thermoplastic elastomer   The pressure vessel according to claim 1, wherein the adhesive layer is formed by powder coating or injection molding. The pressure vessel according to claim 1 or 2 , wherein (A), (B) or (D) is a polyethylene resin produced with a single site catalyst. Wherein the adhesive, the (a) ~ at least one functional group, based on the weight of the entire adhesive, any one of claims 1 to 3 containing 0.001 to 30% by weight of (e) A pressure vessel according to 1. The pressure vessel according to any one of claims 1 to 4 , 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 5 , 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 6 , 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 The die member is provided with a line and / or groove, and an adhesive layer is formed by burying an adhesive in the line and / or groove, and the synthetic resin liner material is interposed through the adhesive layer. method for manufacturing a pressure container according to any one of claim 1 to 7 for bonding or welding a cap member. The method for producing a pressure vessel according to claim 8 , wherein the hollow container is formed by blow molding, and the adhesive layer is formed by powder coating or injection molding. The method for manufacturing a pressure vessel according to claim 8 or 9 , wherein the base member is previously treated with a base treatment agent before the adhesive layer is formed.

Images