JP4714672B2 - Pressure vessel and method for manufacturing the same - Google Patents

Description

  The present invention relates to a pressure vessel and a method for producing the same, and more specifically, a hollow vessel formed of a synthetic resin liner and a base member are bonded to each other with a specific modified high density polyethylene resin having a narrow molecular weight distribution as an essential component. By adhering or welding via a resin, the adhesive force between the inner wall of the hollow container and the base member can be improved, and the pressure vessel with improved hermetic sealing and the pressure vessel can be manufactured economically with a simple process. It relates to a manufacturing method.

  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 locking grooves are provided on the upper and lower surfaces of the disk-shaped flange portion of the base member, and tabs that match the upper and lower locking grooves are 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 disc 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.

However, in the above-mentioned patent documents, the properties of the adhesive and the specific description thereof are not shown in the examples.
Hydrogen gas with a small molecular weight, although it is airtight for natural gas with a relatively high molecular weight, especially in the conventional pressure vessel, especially in demanding quality control of today's strict products, higher pressure gas filling. It is difficult to say that sufficient hydrogen gas permeability is maintained, and higher performance adhesive performance is required.

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

  An object of the present invention is to provide a hollow container formed of a synthetic resin liner material and a base member in view of the above-described problems of the prior art, and an adhesive resin in which a specific modified high-density polyethylene resin having a narrow molecular weight distribution is essential. By adhering or welding via a pressure vessel, the adhesive force between the inner wall of the hollow vessel and the base member is improved, and the pressure vessel with improved hermetic sealing and the pressure vessel that can be manufactured economically in a simple process It is to provide a method.

As a result of intensive studies to solve the above problems, the present inventors have a hollow container formed of a synthetic resin liner material and a reinforcing material provided on the outer layer of the hollow container, and at least A pressure vessel having one cap member, wherein the hollow vessel and the cap member are 30 to 100 parts by weight of a high-density polyethylene resin (A) that satisfies the following characteristics (a1) to (a3): From the compound having the functional groups of the following (a) to (e), 0 to 70 parts by weight of the polyethylene resin (b) satisfying the following characteristics (b1) and (b2) and different from (a): Grafted with at least one selected compound, (x1) density is 0.91 to 0.97 g / cm ³ , and (x2) melt flow rate is 0.01 to 30 g / 10 min. A graft modified polyethylene The above-mentioned problems can be solved by a pressure vessel bonded or welded via an adhesive resin (Z) containing an epoxy resin (X) and its manufacturing method, and an inner wall and a base member formed of a synthetic resin liner material, The present inventors have found that a pressure vessel with improved adhesive strength and improved hermetic sealability and a production method capable of economically producing the pressure vessel by a simple process can be provided, and the present invention has been completed.
[Characteristic]
(A1) Density 0.94 g / cm ^{3 to} 0.97 g / cm ³ ,
(A2) Melt flow rate (JIS K6922-1 (1997) Condition D (measured at a temperature of 190 ° C. and a load of 21.18 N)) 0.01 to 30 g / 10 minutes,
(A3) Molecular weight distribution (Mw / Mn) is 7 or less (b1) Density 0.90 to 0.97 g / cm ³ ,
(B2) Melt flow rate 0.01-30 g / 10 min [functional group]
(A) carboxylic acid group or carboxylic acid anhydride group (b) epoxy group (c) hydroxyl group (d) amino group (e) silyl group

That is, according to the first 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 pressure vessel having at least one die member, wherein the hollow vessel and the die member are 30 to 100 parts by weight of a high density polyethylene resin (A) satisfying the following characteristics (a1) to (a3): A compound having the functional groups of the following (a) to (e), satisfying the characteristics of the following (b1) and (b2) and having a polyethylene group (b) of 0 to 70 parts by weight different from (a): (X1) density is 0.91 to 0.97 g / cm ³ , and (x2) melt flow rate is 0.01 to 30 g / 10 min. Graft-modified polyethylene A pressure vessel bonded or welded via an adhesive resin (Z) containing a system resin (X) is provided.
[Characteristic]
(A1) Density 0.94 g / cm ^{3 to} 0.97 g / cm ³ ,
(A2) Melt flow rate (JIS K6922-1 (1997) Condition D (measured at a temperature of 190 ° C. and a load of 21.18 N)) 0.01 to 30 g / 10 minutes,
(A3) Molecular weight distribution (Mw / Mn) is 7 or less (b1) Density 0.90 to 0.97 g / cm ³ ,
(B2) Melt flow rate 0.01-30 g / 10 min [functional group]
(A) carboxylic acid group or carboxylic acid anhydride group (b) epoxy group (c) hydroxyl group (d) amino group (e) silyl group

According to the second invention of the present invention, in the first invention, the viscosity curve index (FCI) and the melt flow rate (MFR) of the high-density polyethylene resin (A) are further represented by the following formula ( A pressure vessel satisfying 1) is provided.
FCI ≦ −0.063 × log (MFR) +1.10 (1)

According to the third invention of the present invention, in the first or second invention, the adhesive resin (Z) is a modified polyethylene resin (X) of 0.5 to 100% by weight, and the following (A) to (Z1) density 0.86 to 0.97 g / cm ³ , (z2) comprising at least one unmodified polyethylene resin selected from (E) or thermoplastic elastomer (Y) 0 to 99.5% by weight The pressure vessel according to claim 1 or 2, which is an adhesive resin (Z) having a melt flow rate of 0.01 to 100 g / 10 min.
(A): (a1) density 0.94 to 0.97 g / cm ³ , (a2) high density polyethylene resin having a melt flow rate of 0.01 to 100 g / 10 min (B): (b1) density 0. 90 to less than 0.94 g / cm ³ (b2) linear low density polyethylene resin (C1): (c1) melt flow rate 0.01 to 100 g / 10 min High-pressure radical ethylene (co) polymer (D): minutes: (d1) density: 0.86 to less than 0.90 g / cm ³ , (d2) ultra low density polyethylene with a melt flow rate of 0.01 to 100 g / 10 minutes Resin (E): Thermoplastic elastomer

  According to a fourth invention of the present invention, in any one of the first to third inventions, the resin of (i), (b), (A), (B) or (D) is a single site. There is provided a pressure vessel that is a polyethylene resin produced with a catalyst.

  According to a fifth invention of the present invention, in any one of the first to fourth inventions, the adhesive resin (Z) is 5% to 95% by weight of the functional group-containing polyethylene resin (X), and is unmodified. A pressure vessel comprising 5 to 95% by weight of a polyethylene resin or a thermoplastic elastomer (Y) is provided.

  According to a sixth invention of the present invention, in any one of the first to fifth inventions, the adhesive resin (Z) bonds at least one functional group of the above (a) to (e). A pressure vessel containing 0.001 to 10% by weight based on the total weight of the resin (Z) is provided.

According to a seventh invention of the present invention, in any one of the first to sixth inventions, the synthetic resin liner material includes a polyethylene resin having a density of at least 0.920 to 0.970 g / cm ^3. A pressure vessel that is a synthetic resin material is provided.

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

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

Further, according to the eleventh aspect 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 die member, wherein the hollow vessel and the die member are made of a high density polyethylene resin (ii) 30 to 100 satisfying the following characteristics (a1) to (a3): The functional groups of the following (a) to (e) are mixed with 0 to 70 parts by weight of a polyethylene resin (b) satisfying the following characteristics (b1) and (b2) and different from (a): (X1) density is 0.91 to 0.97 g / cm ³ , and (x2) melt flow rate is 0.01 to 30 g. / 10 minutes graft modified poly A method of manufacturing a pressure vessel that is bonded or welded via an adhesive resin (Z) containing an ethylene-based resin (X) is provided.
[Characteristic]
(A1) Density 0.94 g / cm ^{3 to} 0.97 g / cm ³ ,
(A2) Melt flow rate (JIS K6922-1 (1997) Condition D (measured at a temperature of 190 ° C. and a load of 21.18 N)) 0.01 to 30 g / 10 minutes,
(A3) Molecular weight distribution (Mw / Mn) is 7 or less (b1) Density 0.90 to 0.97 g / cm ³ ,
(B2) Melt flow rate 0.01-30 g / 10 min [functional group]
(A) carboxylic acid group or carboxylic acid anhydride group (b) epoxy group (c) hydroxyl group (d) amino group (e) silyl group

  According to a twelfth aspect of the present invention, in the eleventh aspect, the hollow container is formed by blow molding of a synthetic resin liner material, and the adhesive layer made of the adhesive resin (Z) is formed by powder coating. A method of manufacturing a pressure vessel is provided which is formed on a base member and bonds or welds the hollow container and the base member via the adhesive layer.

  According to a thirteenth aspect of the present invention, in the eleventh or twelfth aspect of the present invention, there is provided a method for manufacturing a pressure vessel in which the base member is previously treated with a ground treatment agent.

According to the present invention, a pressure vessel having an improved hermetic sealing property by improving the adhesive force between an inner wall formed of a synthetic resin liner material and a base member is obtained. It is a resin pressure vessel that can be used as a liquefied petroleum gas container for automobiles, a compressed natural gas (CNG), an industrial pressure container for storing oxygen, nitrogen, etc., a hydrogen tank for fuel cells, and the like. That is, according to the present invention, since a specific film can be formed using a specific adhesive resin, the adhesive force between the inner surface of the liner material and the base member can be strengthened, and the adhesive force is dramatically improved. It is possible to provide a pressure vessel with improved hermetic sealing performance and a method for manufacturing the same. In addition, by performing powder coating such as electrostatic coating on the die member in advance, a strong adhesive force can be obtained even with a uniform film having a relatively thin adhesive resin layer.
Further, in the present invention in which an adhesive resin layer is provided on the outer layer and / or the innermost layer of the liner material by blow molding, or the adhesive resin (Z) is directly blended in the liner material, the adhesive strength is obtained by a simple manufacturing process by blow molding or the like. A high pressure vessel is provided, the manufacturing cost is low, and it is economical.
In addition, the adhesive strength can be remarkably improved by providing the die member with line engravings and / or grooves or treating with a base treatment agent.
Therefore, it can be suitably used as a high pressure vessel such as hydrogen gas as well as a low pressure vessel such as natural gas.

As described above, the present invention includes a hollow container formed of a synthetic resin liner material, and a reinforcing material layer formed of a reinforcing material provided on an outer layer of the hollow container, and at least one base. A pressure vessel having a member, wherein the hollow vessel and the cap member are 30 to 100 parts by weight of a high-density polyethylene resin (A) that satisfies the characteristics (a1) to (a3), (b1) and A polyethylene-based resin (b) that is different from (a) that satisfies the characteristics of (b2) (b) 0 to 70 parts by weight is selected from at least one compound selected from the compounds having the functional groups (a) to (e). Graft-modified polyethylene resin (X) having (x1) density of 0.91 to 0.97 g / cm ³ and (x2) melt flow rate of 0.01 to 30 g / 10 min. Adhesive resin containing (Z ) Is a pressure vessel bonded or welded through.

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 hollow container and the base member are made of 30 to 100 parts by weight of a high-density polyethylene resin (A) that satisfies the characteristics (a1) to (a3), And (b) 0 to 70 parts by weight of a polyethylene resin (b) different from (a) that satisfies the characteristics of (b1) and (b2), and at least selected from the compounds having functional groups (a) to (e) Graft-modified polyethylene obtained by grafting with one compound and having (x1) density of 0.91 to 0.97 g / cm ³ and (x2) melt flow rate of 0.01 to 30 g / 10 min. Resin (X) It is the manufacturing method of the said pressure vessel which adhere | attaches or welds through the adhesive resin (Z) containing.
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. And a base member 3 for attaching a nozzle for filling and discharging a high-pressure gas to at least one end of the hollow container 1, and the synthetic resin liner material. The adhesive layer 4 formed by powder coating or the like so that the shoulder portion 7 inside the hollow container 1 formed by the above and the disk portion 8 formed at one end of the base member 3 prevent gas leakage. It is the pressure vessel 10 which adhere | attaches or welds through.

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 that forms the hollow container 1 needs to contain a high-pressure gas filled in the pressure vessel 10 and have a gas barrier property that does not leak. As high density polyethylene resin, cross-linked polyethylene, polypropylene resin, polyolefin resin such as cyclic olefin resin, polyamide resin such as nylon 6, nylon 6,6, nylon 11 and nylon 12, polyethylene terephthalate, polybutylene terephthalate, etc. Engineering plastics such as polyester resin, acrylonitrile-butadiene-styrene copolymer resin (ABS) resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyimide resin, etc. Examples include sticks. The synthetic resin liner material may be composed of any of a single layer material, a laminated material, and a composite material. Among these, a high-density polyethylene resin is most preferable from the viewpoints of gas barrier properties, workability, 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 0.00. A range of 940 to 0.950 g / cm ³ is desirable.
When the density is less than 0.920 g / cm ³ , the rigidity is insufficient and the rigidity of the tank mouth portion is insufficient, and when the density exceeds 0.970 g / cm ³ , the durability may be lowered.
In the polyethylene resin, the high load melt flow rate: HLMFR (JIS K6922-1 (1997), condition D (measured at a temperature of 190 ° C. and a load of 211.8 N)) is 2 to 70 g / 10 minutes, preferably 3 to 60 g / 10 min, more preferably 4 to 50 g / 10 min is desirable, and within such a range, the synthetic resin liner material and the adhesive may be pressed simultaneously, particularly by multilayer blow molding. This is preferable because there is no layer disturbance and the surface layer is improved.
When the HLMFR is less than 2 g / 10 minutes, the resin pressure increases and the extrusion characteristics deteriorate, and when it exceeds 70 g / 10 minutes, there is a possibility that the impact properties and durability are insufficient.

  These synthetic resin liner materials may be composed of a single layer body, a multilayer body, and a composite material of the thermoplastic resin. 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-based resin layer, or a multilayer including at least a thermoplastic resin layer / adhesive layer / barrier layer It is good also as a laminated body which consists of a structure.

  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.

  Examples of the inorganic filler include talc, silica, calcium carbonate, and mica. Among them, fine powder talc and fine powder mica having a plate crystal structure with an average particle size of 0.5 to 10 μm are preferable. .

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

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

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

(3) Base Member The base member 3 of the present invention is installed for filling and discharging a high-pressure gas nozzle. For example, one end of the base member 3 has the shape of the disk portion 8, and the pressure vessel 10 A disk portion 8 of the base member 3 is provided on at least one end of a cylindrical container composed of an inner hollow container 1 and an outer reinforcing material layer 2, and a hemispherical shoulder 7 inside the hollow container 1 of the pressure container. The shoulder portion 7 of the hollow container 1 and the disc portion 8 of the base member 3 are brought into contact with each other via the adhesive 4 of the disc portion 8 of the base member 3 that is inserted and embedded in advance, and is bonded or welded. To do.

  The material of the base member 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 light and relatively inexpensive, is preferable.

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

(4) Ground treatment agent As a ground treatment agent for a metal material, an anodic oxidation method as disclosed in JP-A-59-132777 and the like, trivalent chromium treatment as in JP-A-5-9746, Alternatively, 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. And one or more chitosans selected from the group consisting of chitosan and chitosan derivatives, and Ti, Hf, Mo, W, Se, Ce, Fe, Cu, Zn, V and 3 It is preferably a film formed by treating the surface of the base member with a base treatment agent containing a metal compound containing one or more metals selected from the group consisting of valence Cr. That's right.
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 resin I Modified polyethylene (X)
(I) Modified polyethylene (X) material [high-density polyethylene resin (a)]
The high density polyethylene resin (A) used as the raw material of the modified polyethylene resin (X) of the present invention has the following specific (a1) density, (a2) melt flow rate (hereinafter sometimes referred to as MFR) and ( a3) A molecular weight distribution (Mw / Mn) of 7 or less, more preferably (a4) an ethylene homopolymer or a copolymer of ethylene and α-olefin satisfying the properties of viscosity curve index and MFR (Formula 1) Point to.

The α-olefin of the copolymer of ethylene and α-olefin is preferably a linear or branched olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene. 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. 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 (a1) of the high-density polyethylene resin (A) is 0.94 to 0.97 g / cm ³ , preferably 0.945 to 0.965 g / cm ³ , more preferably 0.948 to 0.960 g / cm ³ . If the density of the high-density polyethylene resin (A) is less than 0.94 g / cm ³ , the effect of improving the adhesive force does not increase. On the other hand, if the density of the high-density polyethylene resin (A) exceeds 0.97 g / cm ³ , the impact resistance of the adhesive resin may be significantly reduced.
Here, the density is a value measured according to JIS K6922-2.

The (a2) melt flow rate of the high-density polyethylene resin (a) is 0.01 to 30 g / 10 minutes, preferably 0.05 to 20 g / 10 minutes, and more preferably 0.1 to 10 g / minute. 10 minutes. When the MFR of the high-density polyethylene resin (A) is less than 0.01 g / 10 min, when processing into a container using this adhesive resin composition, the processing machine motor is overloaded, so the production efficiency is increased. Reduce significantly. Moreover, when MFR of high density polyethylene-type resin (I) exceeds 30 g / 10min, there exists a possibility that the adhesive strength of the container using an adhesive resin composition may fall remarkably.
Here, the melt flow rate is a value measured at 190 ° C. and a load of 21.18 N in accordance with JIS K6922-2.
The density of (a1) can be controlled by the type and content of α-olefin, and the density tends to decrease as the content increases. The melt flow rate (MFR) of (a2) is Controlled by chain transfer agent such as hydrogen, process, etc. These controls are conventional means well known to those skilled in the art.

The (a3) molecular weight distribution (Mw / Mn) of the high-density polyethylene resin (I) is measured using a measuring device: Gel Permeation Chromatography 150 Cplus manufactured by Waters Co., Ltd., and the column is Shodex manufactured by Showa Denko Co., Ltd. Two HT-806Ms are connected in series, and a differential refractometer 1A manufactured by Miran Co., Ltd. is used as a detector. The measurement temperature is 140 ° C., the eluent is 0.05% by weight of 2,4,6-trimethylphenol dissolved in 1,2,4-trichlorobenzene, and the operation is performed at a flow rate of 1.0 ml / min. . The sample is weighed 3.0 mg and used by dissolving in 3.0 ml of the solvent having the same composition as the eluent by shaking at 150 ° C. for 2 hours, and the injection volume of the sample solution is 300 μl.
The column was calibrated by a monodisperse polystyrene (S-7300 S-3900 S-1950 S-1460 S-1010 S-565 S-152 S-66.0 S-28.5 S-5.05 manufactured by Showa Denko. 0.2 mg / ml solution). n-Eicosane and n-tetracontane were measured, and the logarithmic values of elution time and molecular weight were approximated by a quartic equation. In addition, the following formula was used for conversion of the molecular weight of polystyrene and polyethylene.
M _PE = 0.468 × M _PS
Mw / Mn is calculated from the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by the above measurement.

The molecular weight distribution (Mw / Mn) of the present invention is 7 or less, preferably 1.5 to 6.5, more preferably 2.0 to 5.5. As the molecular weight distribution is increased, the molecular weight distribution is wider, the flow characteristics are improved, and the processing characteristics are improved, but the mechanical characteristics are lowered. Therefore, in the present invention, in consideration of the balance between the two, a specific high-density polyethylene resin (A) having a relatively narrow molecular weight distribution is selected, and by making the molecular weight distribution within this range, the adhesive strength can be drastically improved. It has been found that the balance is improved and the moldability is not impaired.
The adjustment of the molecular weight distribution is controlled by the type of catalyst and comonomer, the polymerization process, and the like, and these controls are also conventional means well known to those skilled in the art.

In the present invention, it is more preferable to select the high-density polyethylene resin (A) that satisfies the following formula (1) of (a4) viscosity curve index FCI to improve the adhesive strength of the adhesive resin more reliably. .
Regarding the viscosity curve index (hereinafter referred to as FCI) of the high-density polyethylene resin (a), it is desirable that the relationship between FCI and MFR satisfies the following formula (1), preferably formula (2).
FCI ≦ −0.063 × log (MFR) +1.10 (1)
FCI ≦ −0.0547 × log (MFR) +1.08 (2)
If the FCI deviates from the above range, the adhesive strength of the adhesive resin remains at the level of the prior art, and there is a possibility that the improvement effect cannot be expected.
Here, (a4) the viscosity curve index FCI is the logarithm of the complex viscosity η * 0.1 at a measurement frequency of 0.1 rad / s at 190 ° C. obtained by using a rotary rheometer, and 190 ° C. Defined by the logarithmic ratio of the complex viscosity η * 10 at a measurement frequency of 10 rad / s and expressed as FCI = log (η * 0.1) / log (η * 10).
In general, the viscosity curve index FCI correlates with the molecular weight distribution of the polyethylene resin, and when the molecular weight distribution is wide, the FCI shows a large value, and when the molecular weight distribution is narrowed, the FCI tends to show a small value.
In addition, by changing the comonomer amount and long-chain branching, this FCI can produce different FCI samples even with the same molecular weight distribution, and long-chain branching can be easily changed mainly depending on the catalyst type.
The method of deriving the formulas (1) and (2) of the viscosity curve index FCI of the present invention is to verify the adhesive strength of the adhesive resin using a sample of high-density polyethylene resin polymerized by the method described in Japanese Patent Publication No. 55-14084. The plot was obtained in the examples described later.

  The high-density polyethylene resin (A) according to the present invention is not particularly limited to a catalyst, a process and the like as long as the above parameters are satisfied. The book “Polyethylene Technology Reader” (written by Kazuo Matsuura and Naotaka Mikami, (Research Committee Publication, 2001) p. It can be produced by the method described in 123-160. That is, it can be produced with various polymerization vessels, polymerization conditions and catalysts in each polymerization mode of Ziegler catalyst, single site catalyst, etc., slurry method, solution method, gas phase method, In order to produce a high-density polyethylene-based resin (A), preferably, a specific Ziegler-type catalyst such as JP-B-55-14084 or a single-site type catalyst is used. It can be suitably produced by controlling the catalyst and the like.

[Polyethylene resin (b)]
The polyethylene resin (b) used as the raw material of the modified polyethylene resin (X) of the present invention is a resin different from the high-density polyethylene of (a), and is produced by a Ziegler catalyst, a single site catalyst, a Philips catalyst, or the like. Ethylene homopolymer (high density polyethylene), ethylene / α-olefin copolymer (medium density polyethylene, linear low density polyethylene, etc.) satisfying the following specific properties (b1) density and (b2) MFR: ) Is included. The α-olefin of the copolymer of ethylene and α-olefin 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 (b1) density of the polyethylene resin (b) of the present invention is 0.90 g / cm ^{3 to} 0.97 cm ³ , preferably 0.91 to 0.965 g / cm ³ , more preferably 0.915 to 0.00. 96 g / cm ³ . If the density is less than 0.90 g / cm ³ , the rigidity of the container may be significantly reduced. Further, the upper limit density is not particularly limited, but if the density of the polyethylene resin composition exceeds 0.97 g / cm ³ , the impact resistance of the container may be lowered, so that it may be selected within these ranges. desirable.

  The (b2) MFR of the polyethylene resin (b) of the present invention is 0.01 to 30 g / 10 minutes, preferably 0.05 to 20 g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes. When the MFR of the polyethylene resin (B) is less than 0.01 g / 10 min, when processing into a container, an overload is applied to the motor of the processing machine, so that the production efficiency is remarkably reduced. Further, (b) if the MFR of the polyethylene resin is larger than 30 g / 10 minutes, the strength of the container may be significantly reduced.

The (b) polyethylene-based resin may be the same type of polyethylene resin as the unmodified polyethylene-based resin (Y) described later, or may be used repeatedly.
The high-density polyethylene resin (A) and the polyethylene resin (B) may be the same type of polyethylene resin, but are not the same resin ((I) ≠ (B)).
The high density polyethylene resin of the polyethylene resin (b) or the ethylene / α-olefin copolymer such as medium density polyethylene resin and linear low density polyethylene is the same as the high density polyethylene resin (a). In addition, it is produced by ionic polymerization, and is not particularly limited to production catalyst, process, etc., but the book “Polyethylene Technology Reader” (edited by Kazuo Matsuura and Naotaka Mikami, published by the Industrial Research Committee, p. 160, p. 163 to 196). That is, it can be produced by various polymerization apparatuses, polymerization conditions, and catalysts in each polymerization mode of Ziegler catalyst, single site catalyst, etc., slurry method, solution method, gas phase method.
In addition, as a resin for a single site catalyst, trade names of Nippon Polyethylene Co., Ltd .: Harmolex, trade names: Kernel, trade names of Nippon Evolue Co., Ltd .: trade names of Evolue, Dow Chemical Co., Ltd. : Engagement.

(Ii) Configuration of Modified Polyethylene Resin (X) The modified polyethylene (X) of the present invention is the above high density polyethylene resin (A) alone or 30 to 100 parts by weight of the high density polyethylene resin (A) and polyethylene. A functional group-modified polyethylene resin (hereinafter simply referred to as modified polyethylene) obtained by graft-reacting 0 to 70 parts by weight of the resin (b) with at least one selected from compounds having the following functional groups (a) to (e): Referred to as a resin).
[Functional group]
(A) carboxylic acid group or carboxylic acid anhydride group (b) epoxy group (c) hydroxyl group (d) amino group (e) silyl group

As the modified polyethylene resin (X) of the present invention, a modified high density polyethylene resin (X1) obtained by modifying the above high density polyethylene resin (A) alone with the functional group-containing compound may be used. Since (X1) has a relatively narrow molecular weight distribution, it is preferably used in combination with a modified polyethylene resin (X2) obtained by modifying a polyethylene resin (b) with a functional group-containing compound in order to prepare various physical properties such as moldability. It is desirable to do. The ratio of the modified polyethylene resin (X1) and (X2) is (X1) 30 parts by weight or more and (X2) 70 parts by weight or less, preferably (X1) / (X2) is 40-90 parts by weight / 60-10. It is selected in the range of parts by weight, more preferably 50 to 85 parts by weight / 50 to 15 parts by weight.
These compositions may be dry-blended at the time of containing a functional group, or may be previously mixed with a known mixer such as a kneader or a Henschel mixer to graft the functional group-containing compound.
In addition, it is preferable that at least one of (a) and (b) is produced with a single site catalyst, since there are few low molecular weight components and the balance between adhesive strength and mechanical strength is good.

Hereinafter, the compounds having the functional groups (a) to (e) will be described in detail. As the compound having the functional group (a) carboxylic acid group or carboxylic acid anhydride group, maleic acid, fumaric acid, citraconic acid, Examples include α, β-unsaturated dicarboxylic acids such as itaconic acid or anhydrides thereof, and unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, furanic acid, crotonic acid, vinyl acetic acid, and pentenoic acid.

  Examples of the functional group (b) compound having an epoxy group include 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 and fumaric acid, or vinyl glycidyl ether, allyl glycidyl ether, glycidyl oxyethyl vinyl ether, glycidyl ethers such as styrene / p-glycidyl ether, p-glycidyl styrene, etc. Particularly preferable examples include glycidyl methacrylate and allyl glycidyl ether.

  Examples of the compound having a functional group (c) hydroxyl group include 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxyethyl (meth) acrylate.

  Examples of the compound having the functional group (d) amino group include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dibutylaminoethyl (meth). Examples include acrylate, aminopropyl (meth) acrylate, phenylaminoethyl (meth) acrylate, and cyclohexylaminoethyl (meth) acrylate.

The compound having a functional group (e) 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.

  In the present invention, among the functional groups, at least one compound selected from the group consisting of unsaturated carboxylic acids including the functional groups (a) to (d) or derivatives thereof is preferable. In particular, the unsaturated carboxylic acid or derivative thereof includes monobasic unsaturated carboxylic acid, dibasic unsaturated carboxylic acid, 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.

  Content of the said functional group is 0.001 to 10 weight% with respect to 100 weight% of resin components, Preferably it is 0.005 to 5 weight%, More preferably, it is 0.01 to 3 weight%. If the content is less than 0.001% by weight, a sufficient adhesive performance which is the original purpose cannot be obtained, and if it is more than 10% by weight, the amount of unreacted monomers increases and gelation or the like occurs. Absent.

(Iii) Radical initiator In the present invention, the radical initiator used for grafting functional group contains dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (T-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (t-butylperoxy) hexane , Lauroyl peroxide, t-butylperoxybenzoate, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, t-butylcumyl peroxide, α, α'-bis (t-butyl Peroxy-m-isopropyl) benzene, di-t-butyldiperoxyisophthalate, n- Organic peroxidation such as butyl-4,4-bis (t-butylperoxy) valerate, t-butylperoxybenzoate, t-butylperoxyacetate, cyclohexanone peroxide, t-butylperoxylaurate, acetyl peroxide Things.
Among these, a decomposition temperature for obtaining a half-life of 1 minute is preferably 160 to 200 ° C. When the decomposition temperature is too low, the decomposition reaction starts before the raw polyethylene resin is sufficiently plasticized in the extruder, so the reaction rate is low and more gels and fish eyes are added. Conversely, if the decomposition temperature is too high, The reaction is not completed in the extruder or the like, and the amount of functional group-containing compounds such as 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. Used in the range of 2 parts by weight. If the amount is less than 0.005 parts by weight, the grafting reaction is not sufficiently performed and the amount of unreacted monomers increases, 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 functional group-containing compound such as an unsaturated carboxylic acid or its derivative compound and 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.

(Iv) Method for producing functional group-modified polyethylene resin (X) The method for producing functional group-modified polyethylene resin (X) comprises at least one of the above resins (a) and (ii) + (b), 0.05 to 2.0 at least one functional group-containing compound (also referred to as a monomer) selected from the group consisting of an unsaturated carboxylic acid or a derivative thereof in 100 parts by weight of a composition (hereinafter referred to as a polyethylene resin or the like) Add 0.005 to 0.5 parts by weight of a radical initiator and a radical initiator, and use a single-screw extruder and / or a twin-screw extruder, one or a plurality of reactors, and the like to contain a functional group in a melt kneading or 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 deterioration of at least one polyethylene resin (a) or (b), decomposition of unsaturated carboxylic acid or its derivative, decomposition temperature of peroxide used, and the like. However, taking the above-described 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 (method for measuring the 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 burnt, and the quality of the resulting functional group-containing polyethylene resin (X) 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. .
Graft functional group content (measurement method: by infrared spectrophotometer) obtained by the functional group-containing method in such melt kneading is generally in the range of about 0.2 to 2.5% by weight. Although the upper limit in the graft functional group content of the next functional group-containing polyethylene resin (A) is desirable, it 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.

II Unmodified polyethylene resin (Y)
(I) Configuration of Unmodified Polyethylene Resin (Y) The unmodified polyethylene resin or thermoplastic elastomer (Y) used in the present invention (hereinafter also simply referred to as unmodified polyethylene resin (Y)) is (a1) Density 0.94 to 0.97 g / cm ³ , (a2) high density polyethylene resin (A) having a melt flow rate of 0.01 to 100 g / 10 min, (b1) density 0.90 to 0.94 g / cm ³ (B2) linear low density polyethylene (B) having a melt flow rate of 0.01 to 100 g / 10 min, (c1) high-pressure radical polyethylene resin (C) having a melt flow rate of 0.01 to 100 g / 10 min ) and, (d1) density 0.86~0.89g / cm less than ^3, (d2) a melt flow rate 0.01 to 100 g / 10 min ultra low density polyethylene (D At least one unmodified polyethylene resin or a thermoplastic elastomer selected from a thermoplastic elastomer (E).

The above component (A), component (B), component (C), component (D) and (E) may be the same as the resin used in (b) of the modified polyethylene resin, but (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 a plastic elastomer and its composition.
The component (Y) is not essential, but when the modified polyethylene resin (X) is used alone, there is a concern that there may be an adverse effect that excessive resin deterioration or gel may occur during molding. It is preferable to use the component (Y) because it can easily adjust the functions such as MFR, density adjustment, heat resistance, mechanical properties, rigidity, flexibility, etc., or is economical. .
Further, at least one of (A), (B), and (D) used for the modified or unmodified resin is produced by a single site catalyst, so that the low molecular weight component is small and the resin is deteriorated. It is also preferable because it suppresses the generation of gel and is excellent in mechanical performance.

(Ii) Unmodified polyethylene resin (Y) material [high density polyethylene resin (A)]
The high-density polyethylene resin (A) according to the present invention is a high-density polyethylene resin generally produced by ionic polymerization, and refers to an ethylene homopolymer or a copolymer of ethylene and α-olefin. (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).
In the present invention, the melt flow rate (MFR) is measured under the condition D (temperature 190 ° C., load 21.18 N) based on the test method of JIS K6922-1 (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 comprises a copolymer of ethylene and an α-olefin. It is intended to refer, (b1) density 0.90~0.94g / cm ^3, preferably a density 0.91~0.935g / cm ^3, more preferably in the range of 0.92~0.93g / cm ³ is there. (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, the process, etc. It can be produced by the method described in “Technology Reader” (edited by Kazuo Matsuura and Naotaka Mikami, published by Industrial Research Institute, 2001), p. 123-160, p. 163-196, etc.). 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's product name: Harmolex, Product name: Kernel, Nippon Evolue Co., Ltd. product 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).
Moreover, 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. ) 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 ethylene (co) polymer (C)]
The high-pressure radical ethylene (co) polymer (C) of the present invention is (c1) an ethylene homopolymer (low-density polyethylene resin) 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, etc., and these low-density polyethylene resins are produced by a known high-pressure radical polymerization method, You may manufacture by any method of a tubular method and an autoclave 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. Is done.

  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 is (d1) a density of 0.86 to less than 0.90 g / cm ³ , preferably 0.87 to 0.89 g / cm ³ , (d2) An ethylene / α-olefin copolymer having an MFR of 0.01 to 100 g / 10 minutes, preferably 0.1 to 50 g / 10 minutes, and an ethylene-carbon 3-12 α-olefin copolymer having crystallinity. 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 polyolefin elastomers include ethylene / α-olefin copolymer rubbers such as ethylene-propylene copolymer rubber (EPR) and ethylene-propylene-diene copolymer rubber (EPDM). It can also be obtained by dynamic partial crosslinking or complete crosslinking in the presence of polypropylene resin and EPR, EPDM, polyethylene resin such as ultra-low density polyethylene resin or linear low density polyethylene resin, or oil and crosslinking agent as required. Including polyolefin-based elastomers (TPO).

  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.

III Adhesive resin (Z)
The adhesive resin (Z) of the present invention is formed by using the adhesive resin (Z) in order to suppress gas leakage between the inner shoulder portion of the synthetic resin liner material and the disk portion formed at one end of the base member. In particular, by making the modified polyethylene resin (X1) containing a specific high-density polyethylene resin essential, the adhesive strength can be remarkably improved. Is.
That is, the adhesive resin (Z) of the present invention comprises (a1) a density of 0.94 to 0.97 g / cm ³ and (a2) a high density polyethylene resin having a melt flow rate of 0.01 to 30 g / 10 min. 30 to 100 parts by weight, (b1) density 0.90 to 0.97 g / cm ³ , (b2) polyethylene resin (b) 0 to 70 parts by weight of melt flow rate 0.01 to 30 g / 10 minutes, 0.5 to 100 wt% of a modified polyethylene resin (X) graft-modified with at least one compound having functional groups (a) to (e);
(A1) a density of 0.94 to 0.97 g / cm ³ , (a2) a high density polyethylene resin (A) having a melt flow rate of 0.01 to 100 g / 10 min,
(B1) a density of 0.90 to less than 0.94 g / cm ³ , (b2) a linear low density polyethylene resin (B) having a melt flow rate of 0.01 to 100 g / 10 min,
(C1) High pressure radical ethylene (co) polymer (C) having a melt flow rate of 0.01 to 100 g / 10 min,
(D1) a density of 0.86 to less than 0.90 g / cm ³ , (d2) an ultra-low density polyethylene-based resin (D) having a melt flow rate of 0.01 to 100 g / 10 minutes,
And (z1) density 0.86 to 0.97 g / cm ³ , comprising at least one unmodified polyethylene-based resin (Y) selected from thermoplastic elastomer (E) and 0 to 99.5% by weight ( z2) An adhesive resin (Z) having a melt flow rate of 0.01 to 100 g / 10 min.

More specifically, it is a mixture of a modified polyethylene resin (X) and a resin or thermoplastic elastomer selected from one of (A) to (E) of an unmodified polyethylene resin (Y).
The density (Z1) of the adhesive resin (Z) is 0.86 to 0.97 g / cm ³ , preferably 0.90 to 0.96 g / cm ³ , more preferably 0.91 to 0.95 g / cm ³ . It is a range.
When the density is less than 0.86 g / cm ³ , the adhesive strength is lowered, and when it exceeds 0.97 g / cm ³ , mass production is difficult industrially, and durability is lowered. ) May cause a decrease in performance.
The (z2) melt flow rate 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. When the MFR is less than 0.01 g / 10 minutes, there are difficulties in moldability, and when it exceeds 100 g / 10 minutes, the impact strength of the hollow container of the product may be reduced.

In the adhesive resin (Z) of the present invention, the modified polyethylene (X) may be used alone. It is desirable to use it blended with a resin.
The blending ratio (X) / (Y) of the modified polyethylene resin (X) and the unmodified polyethylene resin (Y) is 100 to 0.5 / 0 to 99.5% by weight, preferably 95 to 5 / It is desirable to select in the range of 5 to 95% by weight, more preferably 90 to 10/10 to 90% by weight. If the modified polyethylene resin (X) is less than 0.5% by weight, the desired adhesive strength cannot be exhibited.

The adhesive resin (Z) satisfies the above-mentioned specific properties, and the inner synthetic resin liner material shrinks and expands when filling and discharging the initial adhesive strength and high-pressure gas, and the temperature. It is excellent in durability such as adaptability to changes, changes over time when these are repeated, resistance to contents, and resistance to contents. These adhesive resins (Z) are preliminarily used in films, sheets, powder coatings, etc. It is used by forming a coating film layer (adhesive resin layer) on a disk part formed at one end of the base member. In particular, forming a coating film by powder coating and melting it in a heating furnace to provide an adhesive resin layer eliminates the need for a solvent, forms a uniform coating film, and provides performance such as adhesive strength with a relatively thin coating film. Is preferable.
Further, the adhesive resin (Z) of the present invention comprises (1) an adhesive resin (Z) layer formed on the outer layer and / or the innermost layer of the synthetic resin liner material, and the synthetic resin liner material via the adhesive resin layer. And (2) a hollow container formed of a synthetic resin liner material, and a reinforcing material provided on the outer layer of the hollow container, and at least one cap member is A pressure vessel having a line engraving and / or a groove, and an adhesive resin layer is formed by burying an adhesive resin in the line engraving and / or the groove. A method of bonding or welding the synthetic resin liner material and the die member; (3) directly bonding the adhesive resin (Z) to the synthetic resin liner material and bonding or bonding the synthetic resin liner material and the die member; Seeds such as welding method It can be applied in ways.
In addition, when the adhesive resin (Z) is coated, laminated, and bonded to the disk portion of the base member in advance, a surface treatment such as the above-described roughening treatment is performed on a part or the entire surface of the disk portion of the base member. It is desirable to do.

  Examples of the powder coating generally include an electrostatic powder coating method, a fluid immersion method, a thermal 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.

The powder of the adhesive resin used for the powder coating has a median particle size of 90 to 150 mesh (standard sieve: JIS Z8801), preferably 100 to 140 mesh, more preferably 110 to 130 mesh, and bulk specific gravity (JIS K8721). In the range of 0.20 to 0.50 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, when used for the thickness of the adhesive resin (Z) of the present invention, film, sheet, inner and outer layers of a liner material, etc., it is 10 μm or more, preferably 10 μm to 5 mm, more preferably 50 μm to 3 mm, still more preferably. Is selected in the range of about 100 μm to 1 mm.
If the thickness is less than 10 μm, the adhesive strength is not sufficient, and there is a concern that gas leakage may occur due to repeated contraction motions. On the other hand, when the thickness exceeds 5 mm, the adhesive strength is not further improved, and the economy is impaired.
The thickness of the adhesive resin (Z) in the case of the above powder coating is in the range of 10 μm to 2 mm, preferably 50 μm to 1.5 mm, more preferably 300 μm to 1 mm. In powder coating, if it is 2 mm or more, it is too thick, and the number of coatings is repeated. This is impractical, and in some cases, bubbles are generated, and there is a risk of tank destruction starting from the adhesive resin layer.

3. As described above, the pressure vessel according to the present invention includes a hollow container 1 (inner wall) formed of an inner synthetic resin liner material and an outer reinforcing material layer, as shown in FIG. 2 (outer wall), and a cap member 3 for attaching a nozzle for filling and discharging high-pressure gas is attached to at least one end of the container, and is formed of a synthetic resin liner material of the container In order to suppress gas leakage, the inner shoulder portion 7 of the hollow container 1 and the disc portion 8 formed at one end of the cap member 3 are bonded via an adhesive resin (Z) 4 that satisfies specific properties. The pressure vessel 10 is bonded or welded.

In the pressure vessel manufacturing method of the present invention, the synthetic resin liner manufacturing method is not limited to the blow molding method, and may be manufactured by injection molding, rotational molding, compression molding, or the like. Since the members can be integrated, the manufacturing process is simple, the manufacturing cost is low, and it is economical, it is preferable to employ a blow molding method.
As a manufacturing method by blow molding, a synthetic resin liner material is molded into a cylindrical shape by blow molding, and then a die member in which an adhesive resin (Z) film is formed in advance on a disk-like end portion of the die member, The synthetic resin liner material is inserted into at least one end portion of the synthetic resin liner material, and the end portion of the synthetic resin liner material is reduced in diameter by closing the mold, so that the disc-shaped end portion of the cap member and the synthetic resin of the container A method of welding the inner shoulder portion of the liner material through the adhesive resin (Z) is preferable from the viewpoint of airtightness.

Below, an example of the manufacturing method of the pressure vessel of this invention is explained in full detail.
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 adhesive resin 4, 4 ′ is coated on the disk portion 8 at one end of the base member 3 in advance by powder coating or the like using a blow molding apparatus having at least a mold, a base support member, and a support base. After the base members 3 and 3 'are installed above and below the support portion 14 associated with the support base 15, a cylindrical parison 12 (a , B) is extruded, suspended between the molds 13 (a, b), and a disk portion formed at one end of the cap member 3, 3 'installed in the mold by the parison 12 (a, b). 8, and then the mold 13 (a, b) is closed while the parison parison 12 (a, b) is still sufficiently soft, the diameter of the parison 12 (a, b) is reduced, and the base member 3 3 'neck is pinched simultaneously with parison 12 (a, b) and sealed mold A gas such as air is blown to press the parison 12 (a, b) against the wall of the mold 13 (a, b) to form a hollow container. At the same time, the inner shoulder portion of the synthetic resin liner 1 and the base Adhesive resins 4 and 4 ′ previously applied to the disk-shaped portions of the members 3 and 3 ′ are fused by internal pressure, and a hollow container having a cap member attached thereto is manufactured. Next, the outer periphery of the hollow container 1 formed of a synthetic resin liner material is impregnated with a thermosetting resin such as an epoxy resin or an unsaturated polyester resin, and a fiber yarn such as a carbon fiber yarn or a bundle, a glass fiber yarn or a bundle. The pressure vessel 10 is manufactured by coating with a bundle, mat, or the like and curing to form a fiber reinforcing material (CFRP, GFRP, etc.) layer 2.

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 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 MFR (unit: g / 10 min): Measured according to JIS K6922-1 (1997), condition D (temperature 190 ° C., load 21.18 N).
(2) 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).
(3) Medium particle size: measured in accordance with JIS Z8801 (standard sieve).
(4) Bulk specific gravity: Measured according to JIS K8721.
(5) Coefficient of static friction: measured in accordance with JIS K8721.
(6) Coating film thickness: Select any part (5 places) of the disk-shaped part of the base member coated with adhesive resin by electrostatic coating, and use the following thickness gauge (EX-V manufactured by Keyence Corporation) The coating film 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 in a substantially proportional relationship, and linearity is corrected by a linearize circuit to obtain a linear output proportional to the distance. The thickness is displayed digitally.
(7) Paintability: The surface smoothness and surface state of the coating film formed on the disk-shaped part of the base member coated with the adhesive resin by electrostatic coating were visually observed.
(8) Adhesive strength: Only the resin layer on the flat part of the die is turned about 10 mm wide and 3 cm long using a cutter, and Tensilon is used to pull the tensile speed of 50 mm / min, 5 cm long, 180 degrees The adhesive strength was measured by peeling (measured value is an average value of 5 points).
(9) Gas leak test: The pressure vessel 10 is filled with 30 MPa of hydrogen gas, and the pressure in the tank is changed with time after being left at 60 ° C. for 60 days. ○ is no gas leak, × is gas leak.

2. Example <Materials Used>
The high density polyethylene resin described in Table 1 was used.

The method of deriving the viscosity curve index FCI of the present invention was obtained by verifying and plotting the adhesive strength of an adhesive resin using a sample of a high-density polyethylene resin polymerized by the method described in JP-B-55-14084. Examples of the preferred FCI formula (2) of the present invention are shown in Table 2 and FIG.
Y = −00547X + 1.08 (2)

<Example 1>
[Production of Modified Polyethylene Resin (X1)]
High-density polyethylene resin (density: 0.956 g / cm ³ , MFR: 0.8 g / 10 min, Mw / Mn: 5.5, FCI: 1.09, referred to as A1 manufactured by Nippon Polyethylene Co., Ltd.) 80 weight Part and linear low density polyethylene resin (density: 0.926 g / cm ³ , MFR: 0.8 g / 10 min, referred to as “B1” manufactured by Nippon Polyethylene Co., Ltd.) 20 parts by weight of powdered polyethylene resin To 100 parts by weight of (A1 + B1), 0.8 part of maleic anhydride and 0.02 part of 2,5-dimethyl-di- (t-butylperoxy) hexane are added and mixed with a Henschel mixer. using Ltd.) 50mm single screw extruder, a screw speed of 50 rpm, and melt-kneaded at a resin temperature of 280 ℃, MFR0.2g / 10 min, density 0.950 g / cm ³ To obtain a graft monomer content 0.5 wt.% Of modified polyethylene resin (X1).

[Manufacture of adhesive resin powder (Z1)]
Modified polyethylene-based resin (X1) 20% by weight and linear low-density polyethylene-based resin (density: 0.924 g / cm ³ , MFR: 9 g / 10 minutes, brand: Z50MG, referred to as Y1 manufactured by Nippon Polyethylene Co., Ltd.) Using a mechanical pulverizer in which 80% by weight of a 90-mesh sieve was set, the mixture was pulverized and smoothed to produce an adhesive resin powder (Z1) having properties as shown in Table 3. The density and MFR as the adhesive resin (Z1) were values as shown in Table 3, respectively.

[Electrostatic coating]
Using an electrostatic coating machine (manufactured by GEMA), the adhesive resin powder is applied to the disk-shaped part of the die having a disk-shaped part at one end as shown in FIG. After electrostatic coating to a coating thickness of 300 μm as shown in FIG. 3, it was placed in an oven at 200 ° C. for 30 minutes to obtain a coated die. The results (adhesive strength, coated surface smoothness, etc.) are shown in Table 3.

[Manufacture of pressure vessels]
As shown in FIG. 2, the coated base is inserted into the support member 14 associated with the support base 15, and the base members 3 and 3 'are installed. The NB150 continuous multilayer hollow molding machine manufactured by Nippon Steel Works, Ltd. Is used to extrude a cylindrical parison 12 (a, b) from a die 11 of a blow molding machine (not shown) and hang down between the molds 13 (a, b), and the parison is still soft enough. In this state, the mold 13 (a, b) is closed, the diameter of the parison 12 (a, b) is reduced, the neck portion of the base member 3 is pinched simultaneously with the parison 12, and air is blown to parison 12 Is pressed against the wall of the mold 13 to form the hollow container 1 formed of a liner material. On the other hand, the base member 3 (rod) is pressed against the shoulder of the hollow container 1 by internal pressure between the shoulder 7 of the hollow container 1 and the adhesive resin 4 previously applied to the upper part 8 of the disk-shaped part of the base 3. Thus, a hollow container 1 was prepared which was fused and fitted with a cap member having a volume of 30 liters. Next, the outer periphery of the hollow container was impregnated with a thermosetting resin epoxy resin, and the carbon fiber bundle was coated and wound, and then the epoxy resin was cured to form a carbon fiber fiber reinforcing material 2 (CFRP) layer, A pressure vessel 10 was manufactured.
Using this pressure vessel 10, hydrogen gas of 30 MPa was filled, and the presence or absence of gas leakage was confirmed. The presence or absence of gas leakage was determined by changing the pressure in the tank with time after being left at 60 ° C. for 60 days. The results are shown in Table 3 (◯: no gas leak, x: gas leak).

[Blow molding conditions]
High-density polyethylene layer / rigline layer / adhesive layer / gas barrier layer (EVOH layer) / adhesive layer from the outer layer side under conditions of molding temperature 210 ° C., blow pressure 1.4 MPa, mold temperature 20 ° C., and blowing time 130 sec. / 4 types and 6 layers of high density polyethylene layer (innermost layer) (layer thickness: 0.7 mm (outermost layer) /2.0 mm / 0.1 mm / 0.15 mm / 0.1 mm / 2.0 mm (innermost layer)) A cylindrical hollow container was 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 , 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) Trade name: Eval F101B (Kuraray)
Table 3 shows the physical properties of the above raw materials, the evaluation results of the pressure vessel, and the like.

<Example 2>
[Production of Modified Polyethylene Resin (X2)]
High-density polyethylene resin (density: 0.956 g / cm ³ , MFR: 0.8 g / 10 min, MW / MN: 5.5, FCI: 1.09, referred to as “A1” manufactured by Nippon Polyethylene Co., Ltd.) 100 weight After adding 0.8 parts of maleic anhydride and 0.02 parts of 2,5-dimethyl-di- (t-butylperoxy) hexane to the parts, mixing with a Henschel mixer, 50 mm unit made by Modern Machinery Co., Ltd. Using a screw extruder, a melt-kneaded mixture under the conditions of a screw speed of 50 rpm and a resin temperature of 280 ° C., a modified polyethylene system having an MFR of 0.2 g / 10 minutes, a density of 0.956 g / cm ³ , and a graft monomer amount of 0.5% by weight. Resin (X2) was obtained.

[Manufacture of adhesive resin powder (Z2)]
Modified polyethylene-based resin (X2) 20% by weight and linear low-density polyethylene-based resin (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Z50MG, referred to as Y1 manufactured by Nippon Polyethylene Co., Ltd.) 80% by weight was pulverized using a mechanical pulverizer in which a 90 mesh sieve was set, and then smoothed to prepare an adhesive resin powder (Z2) having properties as shown in Table 3. The density and MFR as the adhesive resin (Z2) were values as shown in Table 3, respectively.
Using the adhesive resin powder (Z2), electrostatic coating was performed on the disk-shaped portion of the die member in the same manner as in Example 1 to produce a die member having a thickness of 300 μm, and the physical properties are shown in Table 3. . Next, using this base member, a pressure vessel was produced in the same manner as in Example 1, and the evaluation results are shown in Table 3.

<Example 3>
[Production of modified polyethylene resin (X3)]
High density polyethylene resin (density: 0.956 g / cm ³ , MFR: 0.8 g / 10 min, MW / MN: 5.5, FCI: 1.09, referred to as A1 manufactured by Nippon Polyethylene Co., Ltd.) 30 weight Part and linear low density polyethylene resin (density: 0.926 g / cm ³ , MFR: 0.8 g / 10 min, referred to as Nippon Polyethylene Co., Ltd. B1) 70 parts by weight of powdered polyethylene resin To 100 parts by weight of (A1 + B1), 0.8 part of maleic anhydride and 0.02 part of 2,5-dimethyl-di- (t-butylperoxy) hexane are added and mixed with a Henschel mixer. using Ltd.) 50mm single screw extruder, a screw speed of 50 rpm, and melt-kneaded at a resin temperature of 280 ℃, MFR0.2g / 10 min, density 0.935 g / cm ³ To obtain a graft monomer content 0.5 wt.% Of modified polyethylene resin (X3).

[Manufacture of adhesive resin powder (Z3)]
Modified polyethylene-based resin (X3) 20% by weight and linear low-density polyethylene-based resin (density: 0.924 g / cm ³ , MFR: 9 g / 10 minutes, brand: Z50MG, referred to as Y1 manufactured by Nippon Polyethylene Co., Ltd.) 80% by weight was pulverized using a mechanical pulverizer in which a 90 mesh sieve was set, and smoothed to produce an adhesive resin powder (Z3) having properties as shown in Table 3. The density and MFR as the adhesive resin (Z3) were values as shown in Table 3, respectively.
Using the above-mentioned adhesive resin powder (Z3), electrostatic coating was performed on the disk-shaped portion of the base member in the same manner as in Example 1 to produce a base member having a thickness of 300 μm, and the physical properties are shown in Table 3. . Next, using this base member, a pressure vessel was produced in the same manner as in Example 1, and the evaluation results are shown in Table 3.

<Example 4>
[Production of adhesive resin powder (Z4)]
The modified polyethylene resin (X1) 100% by weight was pulverized using a mechanical pulverizer with a 90 mesh sieve set and smoothed to obtain an adhesive resin powder (Z4) having the properties shown in Table 3. Produced. The density and MFR as the adhesive resin (Z4) were values as shown in Table 3, respectively.
Using the adhesive resin powder (Z4), electrostatic coating was performed on the disk-shaped portion of the base member in the same manner as in Example 1 to produce a base member having a thickness of 300 μm. Table 3 shows the physical properties. . Next, using this base member, a pressure vessel was produced in the same manner as in Example 1, and the evaluation results are shown in Table 3.

<Example 5>
[Manufacture of adhesive resin powder (Z5)]
Modified polyethylene-based resin (X1) 0.6% by weight and linear low-density polyethylene-based resin (density: 0.924 g / cm ³ , MFR: 9 g / 10 minutes, brand: Z50MG, manufactured by Nippon Polyethylene Co., Ltd., Y1 99.4% by weight was pulverized using a mechanical pulverizer in which a 90 mesh sieve was set, and smoothed to prepare an adhesive resin powder (Z5) having the properties shown in Table 3. The density and MFR as the adhesive resin (Z5) were values as shown in Table 3, respectively.
Using the above-mentioned adhesive resin powder (Z5), electrostatic coating was performed on the disk-shaped portion of the base member in the same manner as in Example 1 to produce a base member having a thickness of 300 μm, and the physical properties are shown in Table 3. . Next, using this base member, a pressure vessel was produced in the same manner as in Example 1, and the evaluation results are shown in Table 3.

<Examples 6 to 8>
As adhesive resin powder (Z6), 20% by weight of the modified polyethylene resin (X1) used in Example 1, and low density polyethylene (density: 0.919 g / cm ³ , MFR: unmodified polyethylene (Y)): 8.5 g / 10 min, brand: LC607A, manufactured by Nippon Polyethylene Co., Ltd. Y2: C) 80% by weight was melt-kneaded, pulverized using a mechanical pulverizer equipped with a 90 mesh sieve, and smoothed. Thus, an adhesive resin powder (Z6) having properties as shown in Table 4 was prepared. Using the adhesive resin powder (Z6), electrostatic coating was performed on the disk-shaped portion of the die member in the same manner as in Example 1 to produce a die member having a thickness of 300 μm, and the physical properties are shown in Table 4. .
For the adhesive resin powder (Z7), 50% by weight of the modified polyethylene resin (X1) used in Example 1 and linear ultra-low density polyethylene (density: 0.870 g) as unmodified polyethylene (Y). / Cm ³ , MFR: 5 g / 10 min, Brand: Engage 8200, Dow Chemical Japan Co., Ltd. Y3: D) 50% by weight using a mechanical grinder set with a 90 mesh sieve, Table 4 An adhesive resin powder (Z7) having the properties as shown was produced.
Furthermore, for the adhesive resin powder (Z8), 50% by weight of the modified polyethylene resin (X1) used in Example 1, an elastomer (density: 0.870 g / cm ³ , MFR: 5 g / 10 min, : Tuffmer P-0180, manufactured by Mitsui Chemicals Co., Ltd.) 50 wt% Y4 (E)) was pulverized using a mechanical pulverizer in which a 90 mesh sieve was set, and smoothed and shown in Table 4. An adhesive resin powder (Z8) having such properties was produced.
Using the above adhesive resin powders (Z6) to (Z8), electrostatic coating is performed on the disk-shaped portion of the die member in the same manner as in Example 1 to produce a die member having a thickness of 300 μm, and its physical properties are expressed. This is shown in FIG.
Table 4 shows the results of manufacturing and evaluating pressure vessels using these cap members in the same manner as in Example 1.

<Example 9>
20% by weight of modified polyethylene resin (X1) 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. Y1 B2) ) After melt-kneading 80% by weight using a single screw extruder at 200 ° C., making a 500 um sheet with a T-die molding machine and pressing it onto a preheated base for 30 minutes in an oven at 200 ° C. The adhesive strength of the produced base member was the same as that of the powder coating of Example 1. The thickness of the adhesive layer after pressure bonding was 300 μm. As a result of manufacturing and evaluating a pressure vessel for this member in the same manner as in Example 1, no gas leakage was confirmed. The evaluation results are shown in Table 4.

<Comparative Example 1>
[Production of Modified Polyethylene Resin (X4)]
High-density polyethylene resin (density: 0.956 g / cm ³ , MFR: 0.8 g / 10 minutes, Mw / Mn: 5.5, FCI: 1.09, referred to as A1 manufactured by Nippon Polyethylene Co., Ltd.) 20 weight Part and linear low-density polyethylene resin (density: 0.926 g / cm ³ , MFR: 0.8 g / 10 min, referred to as “B1” manufactured by Nippon Polyethylene Co., Ltd.) To 100 parts by weight of (A1 + B1), 0.8 part of maleic anhydride and 0.02 part of 2,5-dimethyl-di- (t-butylperoxy) hexane are added and mixed with a Henschel mixer. using Ltd.) 50mm single screw extruder, a screw speed of 50 rpm, and melt-kneaded at a resin temperature of 280 ℃, MFR0.2g / 10 min, density 0.932 g / cm ³ To obtain a graft monomer content 0.5 wt.% Of modified polyethylene resin (X4).

[Production of Adhesive Resin Powder (Z9)]
Modified polyethylene-based resin (X4) 20% by weight and linear low-density polyethylene-based resin (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Z50MG, manufactured by Nippon Polyethylene Co., Ltd. (Y1: B2 )) 80% by weight was pulverized using a mechanical pulverizer with a 90-mesh sieve set and smoothed to prepare an adhesive resin powder (Z9) having the properties shown in Table 5. The density and MFR as the adhesive resin (Z9) were values as shown in Table 5, respectively.
Using the adhesive resin powder (Z9), electrostatic coating was performed on the disk-shaped portion of the base member in the same manner as in Example 1 to produce a base member having a thickness of 300 μm. Table 5 shows the physical properties. . Next, using this base member, a pressure vessel was produced in the same manner as in Example 1, and the evaluation results are shown in Table 5.

<Comparative Example 2>
[Production of modified polyethylene resin (X5)]
High-density polyethylene resin (density: 0.956 g / cm ³ , MFR: 0.8 g / 10 min, MW / MN: 7.5, FCI: 1.15, referred to as A2 manufactured by Nippon Polyethylene Co., Ltd.) 80 weight Part and linear low density polyethylene resin (density: 0.926 g / cm ³ , MFR: 0.8 g / 10 min, referred to as “B1” manufactured by Nippon Polyethylene Co., Ltd.) 20 parts by weight of powdered polyethylene resin (A + B) To 100 parts by weight, 0.8 parts of maleic anhydride and 0.02 parts of 2,5-dimethyl-di- (t-butylperoxy) hexane are added and mixed with a Henschel mixer. using Ltd.) 50mm single screw extruder, a screw speed of 50 rpm, and melt-kneaded at a resin temperature of 280 ℃, MFR0.2g / 10 min, density 0.950 g / cm ^3, grayed It was obtained Futomonoma amount 0.5 wt% of modified polyethylene resin (X5).

[Production of Adhesive Resin Powder (Z10)]
Modified polyethylene resin (X5) 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. (Y1: B2 )) 80% by weight was pulverized using a mechanical pulverizer in which a 90 mesh sieve was set, and then smoothed to prepare an adhesive resin powder (Z10) having the properties shown in Table 5. The density and MFR as the adhesive resin (Z10) were values as shown in Table 5, respectively.
Using the adhesive resin powder (Z10), electrostatic coating was performed on the disk-shaped portion of the base member in the same manner as in Example 1 to produce a base member having a thickness of 300 μm, and the physical properties are shown in Table 5. . Next, using this base member, a pressure vessel was produced in the same manner as in Example 1, and the evaluation results are shown in Table 5.

<Comparative Examples 3 and 4>
[Production of Modified Polyethylene Resin (X6)]
Powdered polyethylene resin (B: LLDPE) made of linear low density polyethylene resin (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Z50MG, referred to as B2 manufactured by Nippon Polyethylene Co., Ltd.) ) To 100 parts by weight, 0.8 parts of maleic anhydride and 0.02 parts of 2,5-dimethyl-di- (t-butylperoxy) hexane were added and mixed with a Henschel mixer, then Modern Machinery Co., Ltd. using Ltd. 50mm single screw extruder, a screw speed of 50 rpm, and melt-kneaded at a resin temperature of 280 ℃, MFR4g / 10min, density 0.925 g / cm ^3, the graft monomer content of 0.5% by weight of functional groups The contained polyethylene resin (X2) was obtained.

[Production of Adhesive Resin Powder (Z11)]
Modified polyethylene resin (X6) 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. (referred to as Y1: B2) )) 80% by weight was pulverized using a mechanical pulverizer with a 90-mesh sieve set and smoothed to produce an adhesive resin powder (Z11) having the properties shown in Table 5. The density and MFR as the adhesive (Z11) were values as shown in Table 5, respectively.
Using the adhesive resin powder (Z11), electrostatic coating was performed on the disk part of the base part in the same manner as in Example 3 to produce a base member having a thickness of 300 μm. Table 5 shows the physical properties. Next, using this base member, a pressure vessel was produced in the same manner as in Example 1, and the evaluation results are shown in Table 5.
Moreover, the comparative example 4 is the content as shown in Table 5, and produced the pressure vessel similarly to Example 1, and showed the result of having evaluated in Table 5.

3. Evaluation Results In Examples 1 to 8 of the present invention, the adhesive resin layer according to the present invention was formed on the die member by the electrostatic coating method, and Example 9 was formed of a sheet. Met.
On the other hand, Comparative Example 1 is a gas leak test in which the adhesive strength does not increase and the molecular weight distribution and the FCI are deviated when the amount of high density polyethylene used as the raw material of the modified polyethylene (X) is outside the scope of the present invention. Failed. Comparative Example 3 is a modified linear low density polyethylene resin alone, and Comparative Example 4 is that the amount of the modified polyethylene (X) used is outside the scope of the present invention, and neither has any adhesive strength or gas leak test. It was a pass.

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. FIG. 3 is an example of a plot for deriving a formula of a preferred viscosity curve index FCI of the present invention in Examples and Comparative Examples.

Explanation of symbols

1 Hollow container (inner wall) formed from a synthetic resin liner
2 Outer pressure resistant reinforcement (outer wall)
3, 3 'base member 4, 4' adhesive resin 5 outer base member 6 O-ring 7 shoulder portion of liner material 8 disc portion 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 (13)

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 hollow container and the base member satisfy 30-100 parts by weight of a high-density polyethylene resin (A) that satisfies the following characteristics (a1) to (a3) and the following characteristics (b1) and (b2): And (b) 0 to 70 parts by weight of a different polyethylene resin (b) are grafted with at least one compound selected from compounds having functional groups (a) to (e) below: (X1) Adhesion containing a graft-modified polyethylene resin (X) having a density of 0.91 to 0.97 g / cm ³ and (x2) a melt flow rate of 0.01 to 30 g / 10 min. Through resin (Z) Pressure vessel bonded or welded together.
[Characteristic]
(A1) Density 0.94 g / cm ^{3 to} 0.97 g / cm ³ ,
(A2) Melt flow rate (JIS K6922-1 (1997) Condition D (measured at a temperature of 190 ° C. and a load of 21.18 N)) 0.01 to 30 g / 10 minutes,
(A3) Molecular weight distribution (Mw / Mn) is 7 or less (b1) Density 0.90 to 0.97 g / cm ³ ,
(B2) Melt flow rate 0.01-30 g / 10 min [functional group]
(A) carboxylic acid group or carboxylic acid anhydride group (b) epoxy group (c) hydroxyl group (d) amino group (e) silyl group The pressure vessel according to claim 1, wherein a viscosity curve index (FCI) and a melt flow rate (MFR) of the high-density polyethylene resin (a) further satisfy the following formula (1).
FCI ≦ −0.063 × log (MFR) +1.10 (1) The adhesive resin (Z) is 0.5 to 100% by weight of the modified polyethylene resin (X) and at least one unmodified polyethylene resin or thermoplastic elastomer (Y selected from the following (A) to (E): And (z1) an adhesive resin (Z) having a density of 0.86 to 0.97 g / cm ³ and (z2) a melt flow rate of 0.01 to 100 g / 10 min. Item 3. The pressure vessel according to Item 1 or 2.
(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 to less than 0.94 g / cm ³ (b2) linear low density polyethylene resin (C1): (c1) melt flow rate 0.01 to 100 g / 10 min High-pressure radical ethylene (co) polymer (D): minutes: (d1) density: 0.86 to less than 0.90 g / cm ³ , (d2) ultra low density polyethylene with a melt flow rate of 0.01 to 100 g / 10 minutes Resin (E): Thermoplastic elastomer   4. The resin according to any one of claims 1 to 3, wherein the resin (a), (b), (A), (B) or (D) is a polyethylene resin produced with a single site catalyst. Pressure vessel.   The adhesive resin (Z) is composed of 5 to 95% by weight of a functional group-containing polyethylene resin (X) and 5 to 95% by weight of an unmodified polyethylene resin or a thermoplastic elastomer (Y). Item 1 is a pressure vessel.   The adhesive resin (Z) contains 0.001 to 10 wt% of at least one functional group (a) to (e) based on the weight of the entire adhesive resin (Z). The pressure vessel according to any one of 5. The pressure vessel according to any one of claims 1 to 6, wherein the synthetic resin liner material is a synthetic resin material including at least a polyethylene-based resin having a density of 0.920 to 0.970 g / cm ³ .   The pressure vessel according to any one of claims 1 to 7, 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 8, wherein the synthetic resin liner material is composed of a laminate including at least a thermoplastic resin layer / adhesive layer / barrier layer.   The pressure vessel according to any one of claims 1 to 9, 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 hollow container and the base member are made of 30 to 100 parts by weight of a high-density polyethylene resin (A) that satisfies the following characteristics (a1) to (a3), and the following (b1) and (b2): Polyethylene resin (b) 0 to 70 parts by weight that satisfies the characteristics and is different from (a) by at least one compound selected from compounds having functional groups (a) to (e) below Graft-modified polyethylene resin (X) having (x1) density of 0.91 to 0.97 g / cm ³ and (x2) melt flow rate of 0.01 to 30 g / 10 min. Adhesive resin containing ( A process for producing a pressure vessel which is bonded or welded via Z).
[Characteristic]
(A1) Density 0.94 g / cm ^{3 to} 0.97 g / cm ³ ,
(A2) Melt flow rate (JIS K6922-1 (1997) Condition D (measured at a temperature of 190 ° C. and a load of 21.18 N)) 0.01 to 30 g / 10 minutes,
(A3) Molecular weight distribution (Mw / Mn) is 7 or less (b1) Density 0.90 to 0.97 g / cm ³ ,
(B2) Melt flow rate 0.01-30 g / 10 min [functional group]
(A) carboxylic acid group or carboxylic acid anhydride group (b) epoxy group (c) hydroxyl group (d) amino group (e) silyl group   The hollow container is formed by blow molding of a synthetic resin liner material, an adhesive layer made of the adhesive resin (Z) is formed on the base member by powder coating, and the hollow container and the base member are formed through the adhesive layer. The manufacturing method of the pressure vessel of Claim 11 which adhere | attaches or welds.   The method for manufacturing a pressure vessel according to claim 11 or 12, wherein the base member is previously treated with a base treatment agent.

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