JP2008164113A - Cap member, pressure vessel using the same, and manufacturing method thereof - Google Patents

Abstract

Provided are a base member capable of improving the adhesive force between a synthetic resin liner material constituting an inner wall of a pressure vessel and a base member and improving hermetic sealing, a pressure vessel using the base member, and a method for manufacturing the same.
A pressure vessel having a hollow container formed of a synthetic resin liner and a reinforcing material layer formed of a reinforcing material provided on an outer layer of the hollow container, and having at least one cap member. A base member used for the base member, in which the base member is treated with a specific base treatment agent, a pressure vessel using the base member, and a manufacturing method thereof.
[Selection] Figure 2

Description

  The present invention relates to a cap member used for a pressure vessel and the like, a pressure vessel using the same, and a method for manufacturing the same, and more specifically, an adhesive force between a liner member made of a synthetic resin that constitutes an inner wall of the pressure vessel and the cap member. It is related with the nozzle | cap | die member which improves this, and a hermetic seal property is improved, a pressure vessel using the same, and its 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 resin-made liner having gas barrier properties is covered with an outer shell made of pressure-resistant fiber reinforced plastic (FRP), and is essentially made of resin. It is lighter than metal ones and can be expected to improve fuel efficiency.

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

  In particular, since the pressure vessel is filled with a high-pressure gas of 25 MPa to 100 MPa, extremely high gas sealing properties are required. In these resin pressure vessels, as a technique for improving the gas sealability of the cap member, for example, in the pressure vessel described in Patent Document 2, the disc-shaped flange portion of the cap member is received by the upper and lower lips of the inner shell end portion. By adopting a structure, the gas sealability of the base member is improved, 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 the container is manufactured, the resin in the inner shell creeps and shrinks while the product container is used for a long time, and a gap occurs at the interface between the inner shell and the base member. There is a risk of gas leakage from the gaps at the interface.

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

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

Further, in Patent Document 8, in a pressure vessel having a gas barrier inner shell and a pressure outer shell, and a cap member attached to at least one end, the shoulder of the liner material of the inner shell and one end There has been proposed a pressure vessel in which a base member having a disk shape on the side is bonded via an adhesive resin layer and the sealing property at the interface between the liner material of the inner shell and the base member is excellent.
The adhesive resin layer in Patent Document 8 is preferably an unsaturated carboxylic acid-modified polyethylene resin, and has a density of 0.88 to 0.945 g / cm ³ and an MFR of 0.05 to 50 g / 10 min. It has been shown that polymers are used (see Patent Document 5, paragraph [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 low molecular weight, although it is airtight for natural gas with a relatively high molecular weight, especially in conventional pressure vessels, although demands for quality control of recent products, demand for higher-pressure gas filling, and particularly in conventional pressure vessels It is difficult to say that sufficient hydrogen gas permeation resistance is maintained, and higher adhesion 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 pressure vessel in which the adhesive force between a synthetic resin liner material constituting the inner wall of the pressure vessel and the base member is improved, and the hermetic sealing property is improved in view of the above-mentioned problems of the prior art. An object of the present invention is to provide a cap member that can be used, a pressure vessel using the cap member, and a manufacturing method thereof.

As a result of intensive studies in order to solve the above problems, the present inventors have determined that a hollow container formed of a synthetic resin liner material and a reinforcing material formed of a reinforcing material provided on the outer layer of the hollow container A pressure vessel having at least one base member, and a hollow formed by a base member and a synthetic resin liner material dramatically by treating the base member with a base treatment agent. The present inventors have found that a base member capable of improving the adhesive strength with the container, a pressure container using the base member with an improved hermetic seal, and a method for producing the same can be provided, and the present invention has been completed.

That is, according to the first invention of the present invention, it has a hollow container formed of a synthetic resin liner, and a reinforcing material layer formed of a reinforcing material provided on the outer layer of the hollow container, and There is provided a cap member used for a pressure vessel having at least one cap member, wherein the cap member is treated with the following surface treatment agent.
[Pretreatment agent]
One or more chitosans selected from the group consisting of chitosan and chitosan derivatives and selected from the group consisting of Ti, Hf, Mo, W, Se, Ce, Fe, Cu, Zn, V and trivalent Cr A surface treatment agent comprising a metal compound containing one or more kinds of metals obtained

According to a second aspect of the present invention, there is provided a die member according to the first aspect, further comprising an adhesive layer made of an adhesive on the treated surface treated with the base treatment agent. .

According to a third invention of the present invention, in the second invention, the adhesive is a polyolefin-based resin containing at least one functional group of the following (a) to (e) or a composition thereof. A base member that is an adhesive is provided.
[Functional group]
(A) carboxylic acid group or carboxylic anhydride group (b) epoxy group (c) hydroxyl group (d) amino group (e) silyl group

According to a fourth invention of the present invention, in the third invention, the adhesive contains the following (A) to (D), which contains at least one functional group of (a) to (e). 0.5 to 100% by weight of one type of polyethylene resin (X) selected from: and at least one type of unmodified polyethylene resin (Y) selected from the following (A) to (E): 0 to 99. There is provided a die member made of an adhesive resin (Z) consisting of 5% by weight (z1) density 0.86 to 0.97 g / cm ³ and (z2) melt flow rate 0.01 to 100 g / 10 min.
(A): (a1) Density 0.94 to 0.97 g / cm ³ , (a2) High density polyethylene resin having a melt flow rate 0.01 to 100 g / 10 min (B): (b1) Density 0.90 ˜0.94 g / cm ³ , (b2) linear low density polyethylene resin (C) having a melt flow rate of 0.01 to 100 g / 10 min (C): (c1) high pressure having a melt flow rate of 0.01 to 100 g / 10 min Radical method polyethylene resin (D): (d1) Ultra low density polyethylene resin (E) with a density of 0.86 to less than 0.90 g / cm ³ and (d2) a melt flow rate of 0.01 to 100 g / 10 min (E): Heat Plastic elastomer

  According to a fifth aspect of the present invention, there is provided the cap member according to the fourth aspect, wherein (A), (B) or (D) is a polyethylene resin produced with a single site catalyst. Is done.

  According to a sixth invention of the present invention, in the fourth or fifth invention, the adhesive resin (Z) is a functional group-containing polyethylene resin (X) of 5 to 95% by weight, and an unmodified polyethylene resin. (Y) A base member composed of 5 to 95% by weight is provided.

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

  According to the eighth invention of the present invention, in any one of the second to seventh inventions, there is provided a base member in which the adhesive layer is provided by powder coating.

  According to the ninth aspect of the present invention, in the eighth aspect, the powder used for the powder coating has a median particle size of 90 to 150 mesh and a bulk specific gravity of 0.2 to 0. A base member having a thickness of 0.5 g / cc and a static friction coefficient of 0.7 to 0.9 is provided.

  According to a tenth aspect of the present invention, there is provided the base member according to the eighth or ninth aspect, wherein the adhesive layer provided by the powder coating has a thickness of 10 μm to 2 mm.

  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 pressure vessel having at least one cap member, wherein the cap member is the cap member according to any one of claims 1 to 10.

  Further, according to the twelfth 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 It is a manufacturing method of the pressure vessel which has at least 1 nozzle | cap | die member, Comprising: This hollow container is formed by blow molding of a synthetic resin liner material, and this nozzle | cap | die member is any one of Claims 1-10. The manufacturing method of the pressure vessel using the nozzle | cap | die member as described in 1 is provided.

ADVANTAGE OF THE INVENTION According to this invention, the adhesive force of the inner side wall formed with a synthetic resin liner material and a nozzle | cap | die member is improved, and the pressure vessel with which airtight sealing property was improved is obtained. This is a resin that can be used as liquefied petroleum gas containers for home use, liquefied petroleum gas containers for automobiles, compressed natural gas (CNG), industrial pressure vessels for storing oxygen, nitrogen, etc., hydrogen tanks for fuel cells, etc. The pressure vessel made. That is, according to the present invention, a base member having a strong adhesive force can be obtained by previously applying a base treatment agent to the base member and then providing an adhesive on the surface to which the base treatment agent has been applied. In particular, by using such a specific ground treatment agent and a specific adhesive in combination, the adhesive force is synergistically improved. In addition, since the film can be uniformly formed by applying an adhesive by powder coating such as electrostatic coating, the adhesive force between the inner surface of the liner material and the base member can be strengthened even if it is relatively thin, The hermetic sealability is also improved.
Therefore, by using such a cap member, a higher pressure vessel can be provided, and 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. is there.
Further, according to the present invention, since the base member can be integrated by blow molding or the like, the manufacturing process is simple, the manufacturing cost is low, and it is economical.

  As described above, the present invention comprises a hollow container formed of a synthetic resin liner material and a reinforcing material layer formed of a reinforcing material provided on the outer surface of the hollow container, and at least A base member used in a pressure vessel having one base member, the base member used in a pressure vessel having at least one base member, and a disk portion formed at one end of the base member, One or more chitosans selected from the group consisting of chitosan and chitosan derivatives and selected from the group consisting of Ti, Hf, Mo, W, Se, Ce, Fe, Cu, Zn, V and trivalent Cr It is a die member obtained by treating a base treatment agent containing a metal compound containing one or two or more kinds of metals, and particularly preferably an adhesive layer on the treated surface of the ground treatment agent, Above all A cap member that the adhesive is provided comprising a polyolefin resin containing at least one functional group of the below (a) ~ (e) as Chakuzai.

The surface treatment agent of the present invention contains chitosans and one or more metals selected from the group consisting of Ti, Hf, Mo, W, Se, Ce, Fe, Cu, Zn, V, and trivalent Cr. Contains metal compounds.
Chitosan is a deacetylated product obtained by heating chitin with a concentrated alkaline solution, has a polymer structure of β-1,4-poly-D-glucosamine, and has a molecular formula (C ₆ H ₁₁ NO ₄ ) _n It is the compound shown. Chitosan can be obtained, for example, by deacetylating natural high-molecular chitin extracted from crustaceans such as crabs and shrimps. Chitin can be prepared from crustacean shells such as crabs and shrimps by treatment with hydrochloric acid at room temperature, and is a kind of mucopolysaccharide, a compound represented by the molecular formula (C ₈ H ₁₃ NO ₅ ) _n (average polymerization) Degree 850).
A chitosan derivative is a compound obtained by, for example, carboxylation, glycolation, tosylation, sulfation, phosphorylation, etherification, alkylation, etc., on a hydroxyl group and / or amino group present in chitosan. Among them, 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 metal compound contains 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 the metal compounds, 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.

  In addition to the chitosans and the metal compound, the surface treatment agent of the present invention preferably further contains an organic compound having at least one carboxyl group in the molecule. By including such an organic compound, the solubility of chitosans can be improved, and the degree of metal crosslinking of chitosans can be improved (high molecular weight).

  The organic compound having at least one carboxyl group in the molecule is not particularly limited. Examples include acid, citric acid, butanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, ethylenediaminetetracarboxylic acid, trimellitic acid and the like.

  The ground treatment agent of the present invention may further contain a pH adjuster, various additives and the like as necessary.

  The concentration of chitosans in the surface treatment agent is preferably set in the range of 0.001 to 10% by mass, and more preferably in the range of 0.1 to 5% by mass. Moreover, it is preferable to set the density | concentration of the metal compound in the said surface treatment agent in the range of 0.001-10 mass%, and it is more preferable to set in the range of 0.1-5 mass% especially. Moreover, about the mixing ratio of both in the said surface treating agent, it is preferable to set it as 1-1000 mass parts of said metal compounds with respect to 100 mass parts of said chitosans, and it is more preferable to set it as 10-100 mass parts especially.

  As a processing method when the base member is processed with the base treatment agent, after applying the base treatment agent to the surface of the disk part of the base member, a coating treatment for heating or drying or a component in the base treatment agent is used. Examples include, but are not limited to, a chemical conversion treatment in which the metal surface is chemically reacted and then the surface is washed with water and dried. Examples of the coating method include a roll coating method, a spin coating method, a dipping method, and a spray method.

Thus, the dry adhesion amount of the chitosan to the surface of the die member is in the range of 1 to 500 mg / m ^{2 in} terms of chitosan, and the dry adhesion amount to the surface of the die member is 1 to 500 mg / in metal equivalent. A range of m ² is preferred. For example, when the die member is made of aluminum, it is particularly preferable that the adhesion amount of the chitosans to the aluminum surface when dried is in the range of 10 to 100 mg / m ^{2 in} terms of chitosan. The amount of the metal compound attached to the surface of the die member when dry is particularly preferably in the range of 5 to 50 mg / m ^{2 in} terms of metal.

A primer layer may be provided between the base treatment layer and the adhesive layer of the base member of the present invention as necessary. As the primer, an epoxy-based, urethane-based, epoxy-urethane-based, imine-based, titanate-based, polyester-based, or silane-based thermosetting primer can be used. Among these, an epoxy-based primer is preferable because of excellent adhesion and durability between the aluminum layer and the adhesive layer.
The base member of the present invention forms a base treatment layer by applying a base treatment, and laminates an adhesive on the base treatment layer, or coats a primer on the base treatment layer to form a primer layer, and further It can be manufactured by laminating an adhesive layer on the layer. When the primer layer is formed, it is preferable to heat and cure, then laminate the adhesive layer and fuse it by heating. However, after the primer is applied, the adhesive layer is laminated before curing, Curing may be performed using

Further, as described above, the present invention comprises a hollow container formed of a synthetic resin liner material, and a reinforcing material layer formed of a reinforcing material provided on the outer surface of the hollow container, And in the pressure vessel which has a nozzle | cap | die member in at least one edge part, it is a pressure vessel using said nozzle | cap | die member, and its manufacturing method.
Below, this invention is demonstrated in detail for every item.

1. Structure of Base Member and Pressure Vessel Hereinafter, the base member and the pressure vessel of the present invention will be described in detail based on the drawings.
FIG. 1 shows a partially cutaway cross-sectional view of an example of a base member of the present invention.
As shown in FIG. 1, the base member according to the present invention has a base treatment agent layer 4a provided on the disk portion 8 of the base member 3, and a base member provided with an adhesive layer 4b on the treated surface. It is.
FIG. 2 is 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 base member 3 provided with a base treatment agent layer 4a and preferably an adhesive layer 4b on a disk portion 8 of the base member 3 in advance, and a synthetic resin liner. A hollow container formed of a material and a reinforcing material layer formed of a reinforcing material provided on the outer surface of the hollow container, and is attached to at least one end of the hollow container, A pressure vessel 10 is formed by adhering or welding an inner shoulder portion of a hollow container 1 formed of a liner material and a disk portion 8 formed at one end of a cap member 3 via an adhesive layer 4b.

2. Base Member The raw materials used in the present invention will be specifically described below.
(1) Material of the cap member The cap member 3 of the present invention is installed for attaching a nozzle for filling and discharging a high pressure gas. As an example, one end of the cap member 3 has the shape of the disk portion 8. And at least one end of a cylindrical pressure vessel composed of a hollow vessel 1 formed of a synthetic resin liner inside the pressure vessel 10 and an outer pressure-resistant reinforcing material layer 2, and the synthetic resin of the vessel The die member 3 is inserted into the hemispherical shoulder inside the hollow container 1 made of the liner material so that the disc portion 8 of the die member 3 is embedded, and the base treatment agent layer 4a is applied in advance. On the disk part 8, the shoulder part of the hollow container 1 formed of a synthetic resin liner material and the disk part 8 of the base member 3 are brought into contact with each other via an adhesive 4 b to be bonded or welded.

  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, modified polyphenylene oxide, polyethersulfone, polyphenylene sulfide, polyarylate, polyetherimide, polyetheretherketone, polyimide , Polyamideimide, polyoxybenzylene, polysulfone and the like having high rigidity and excellent heat resistance. Among these, metal materials, particularly lightweight and relatively inexpensive aluminum, are preferable in terms of durability and durability.

The disk portion 8 of the base member 3 of the present invention is subjected to a surface treatment agent after performing a surface roughening treatment, a chemical conversion treatment, or the like, if desired, in order to increase the adhesive force with the adhesive 4b. Also good.
As a surface roughening treatment method, a rough surface having an arbitrary shape such as a corrugated 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.

(2) Ground treatment agent The ground treatment agent used in the present invention includes one or more chitosans selected from the group consisting of chitosan and chitosan derivatives, and Ti, Hf, Mo, W, Se, and Ce. , Fe, Cu, Zn, V, and a surface treatment agent containing a metal compound containing one or more metals selected from the group consisting of trivalent Cr, and in particular, a carboxyl group in the molecule. A base treatment agent containing at least one organic compound 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 them, as the chitosan, one or more chitosans selected from the group consisting of chitosan, carboxymethyl chitosan, cationized chitosan, hydroxyalkyl chitosan, and salts with these acids are used.

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

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

(3) Adhesive [Adhesive]
Examples of the adhesive used in the present invention include thermosetting resins such as epoxy resins, polyurethane resins, polyester resins, acrylic resins, or (a) carboxylic acid groups or carboxylic anhydride groups, (b) epoxy groups, A general adhesive for thermoplastic resins such as polyolefin resins containing at least one functional group such as (c) hydroxyl group, (d) amino group, and (e) silyl group can be used. In particular, when a polyolefin resin is selected as the synthetic resin liner, among these, a combination with a polyolefin resin containing a functional group is preferable.
The polyolefin-based resin containing a functional group of the present invention is a compound or monomer having the functional groups (a) to (e) (hereinafter also referred to as a functional group-containing compound) and an α-olefin having about 2 to 10 carbon atoms. And a modified polyolefin resin obtained by graft-modifying the functional group-containing compound on a polyolefin resin.
Hereinafter, the functional group-containing compounds (a) to (e) will be described in detail.

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

  As the compound for introducing the epoxy group of the functional group (b), glycidyl acrylate, glycidyl methacrylate, itaconic acid monoglycidyl ester, butenetricarboxylic acid monoglycidyl ester, butenetricarboxylic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester and Glycidyl esters such as α-chloroacrylic acid, maleic acid, crotonic acid, fumaric acid, etc. or glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, glycidyloxyethyl vinyl ether, styrene / p-glycidyl ether, p-glycidyl styrene, etc. Among them, particularly preferred are glycidyl methacrylate and allyl glycidyl ether.

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

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

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

As a specific method for introducing a functional group into a resin component of a polyolefin resin containing a functional group of the present invention, a method of introducing a modified polyolefin resin obtained by graft-modifying at least one functional group-containing compound or monomer. And a method in which a random copolymer of an olefin such as ethylene or propylene with a functional group and a functional group-containing compound is mixed and introduced into the resin component.
The content of the functional group is in the range of 0.001 to 30% by weight, in the case of a graft-modified polyolefin resin, in the range of 0.001 to 10% by weight, and in the case of a random copolymer, 1 to 1% by weight. Suitably it is in the range of 30% by weight. When the content of the functional group is less than 0.001% by weight, the adhesive strength is low, the object of the present invention cannot be achieved, and the functional group of the raw material to be prepared with the functional group content exceeding 30% by weight. It is difficult to obtain the polyolefin-containing resin and it is not economical.

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

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

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

Examples of polyolefin resins used for the grafting include high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, etc., and low-density polyethylene, ethylene- (meth) acrylic with Ziegler catalyst, Phillips catalyst, metallocene catalyst. Examples thereof include polyethylene resins such as acid copolymers and high-pressure radical polyethylene resins such as ethylene- (meth) acrylic acid alkyl copolymers, and polypropylene resins such as homopolypropylene and propylene-ethylene copolymers.
The functional group-containing olefin random copolymer and the grafted functional group-containing polyolefin resin are used alone or mixed with an unmodified polyolefin resin. In particular, it is preferable to use the functional group-containing polyolefin resin as a mixture with the unmodified polyolefin resin because the functional group content, MFR, density and the like can be easily adjusted. Among these, a polyethylene resin is preferable.

Hereinafter, the adhesive resin (Z) composed of a preferred polyethylene resin in the present invention will be described in detail.
[Adhesive resin (Z)]
(I) Materials of polyethylene-based resin (X) and unmodified polyethylene-based resin (Y) containing functional groups [high-density polyethylene resin (A)]
The high-density polyethylene resin (A) according to the present invention is a high-density polyethylene resin generally produced by ionic polymerization, and refers to an ethylene homopolymer or a copolymer of ethylene and an α-olefin. (A1) Density 0.94 to 0.97 g / cm ³ , preferably 0.945 to 0.965 g / cm ³ , more preferably 0.95 to 0.96 g / cm ^3. . (A2) The melt flow rate (MFR) is in the range of 0.01 to 100 g / 10 minutes, preferably 0.05 to 50 g / 10 minutes, more preferably 0.1 to 30 g / 10 minutes. Within such a range, the performance with excellent long-term life (durability) such as adhesive strength, rigidity and creep resistance is easily exhibited.
The density was measured based on the test method of JIS K6922-1 (1997).
Moreover, in this invention, melt flow rate (MFR) is measured on condition D (temperature 190 degreeC, load 21.18N) based on the test method of JISK6922-1 (1997).

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

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

The high-density polyethylene resin (A) or linear low-density polyethylene resin (B) produced by the ionic polymerization is not particularly limited to the production catalyst, process, etc. It can be produced by the method described in “Polyethylene Technology Reader” (edited by Kazuo Matsuura and Naotaka Mikami, published by Industrial Research Institute, p. 123-160, p. 163-196, etc.). . That is, it can be produced by various polymerization reactors, polymerization conditions, and catalysts in each polymerization mode of Ziegler catalyst, single site catalyst, etc., slurry method, solution method, gas phase method.
As polyethylene-based resins produced with single-site catalysts, product names manufactured by Nippon Polyethylene Co., Ltd .: Harmolex, product names: Kernel, products manufactured by Nippon Evolue Co., Ltd .: Evolue, Dow Chemical Co., Ltd. ) Product name: Engage etc.

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

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

(Ii) Configuration of functional group-containing polyethylene resin (X) The functional group-containing polyethylene resin (X) of the present invention includes the functional group-containing ethylene random copolymer and the grafted functional group-containing polyethylene resin, As the raw material of the grafted functional group-containing polyethylene resin, each of the component (A), the component (B), the component (C) and the component (D) may contain at least one functional group. , (A) + (B), (B) + (C), (A) + (C), (A) + (D) or (A) + (B) + (C), (A) + ( Any one of B) + (D), (A) + (C) + (D), (B) + (C) + (D) and (A) + (B) + (C) + (D) A functional group can also be contained as a seed polyethylene resin composition. These compositions may be dry blended when functional groups are contained, or may be preliminarily mixed with a known mixer such as a kneader or a Henschel mixer to contain functional groups.
Moreover, when at least one of (A) to (D) does not satisfy the above-described conditions, the adhesive strength is lowered, and there is a concern that desired adhesive strength cannot be obtained.
In addition, it is preferable that at least one of (A), (B) and (D) is produced with a single site catalyst because of a good balance between adhesive strength and mechanical strength.
Moreover, as a structure of functional group containing polyethylene-type resin (X), it is preferable from economical efficiency, workability | operativity, etc. to use it as a mixture of 2 or more types rather than using (A)-(D) independently. A particularly preferable combination is a functional group-containing product of the component (B), and a functional group-containing product having a linear low density polyethylene resin as a main component by a single site catalyst is desirable.

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

(Iv) Radical initiator In the present invention, as a radical initiator used when grafting a functional group onto a polyethylene resin, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl is used. -2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (t -Butylperoxy) hexane, lauroyl peroxide, t-butylperoxybenzoate, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, t-butylcumyl peroxide, α, α ' -Bis (t-butylperoxy-m-isopropyl) benzene, di-t-butyldiperoxy Isophthalate, n-butyl-4,4-bis (t-butylperoxy) valerate, t-butylperoxybenzoate, t-butylperoxyacetate, cyclohexanone peroxide, t-butylperoxylaurate, acetyl peroxide And organic peroxides.
Among these, those having a decomposition temperature for obtaining a half-life of 1 minute are preferably 160 to 200 ° C. If the decomposition temperature is too low, the decomposition reaction will start before the raw polyethylene resin is sufficiently plasticized in the extruder, so the reaction rate will be low and more gels and fish eyes will be generated. Conversely, if the decomposition temperature is too high The reaction is not completed in the extruder or the like, and the amount of the unreacted unsaturated carboxylic acid and its derivative increases.
The compounding amount of the radical initiator is usually 0.005 to 0.5 parts by weight, preferably 0.01 to 0.3 parts by weight based on 100 parts by weight of the total resin component including the polyethylene resin at the time of primary modification. Parts, more preferably 0.01 to 0.1 parts by weight. If it is less than 0.005 parts by weight, the grafting reaction is not sufficiently carried out and unreacted monomers increase, which is not preferable. On the other hand, when the amount is more than 0.5 parts by weight, gels and fish eyes may occur frequently.

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

(V) Production method of functional group-containing polyethylene resin (X) The production method of functional group-containing polyethylene resin (X) is at least one of resins (A), (B), (C) and (D). At least one functional group-containing monomer selected from the group consisting of an unsaturated carboxylic acid or a derivative thereof in 100 parts by weight of a polyethylene resin and a composition thereof (hereinafter referred to as a polyethylene resin or the like) 0.05 to 2.0 By adding 0.005 to 0.5 parts by weight of a radical initiator and a radical initiator, and melt-kneading or modifying in a solvent using a single-screw extruder and / or a twin-screw extruder or one or a plurality of reactors Achieved.
Specific examples include a melt-kneading method using an extruder, a Banbury mixer, a kneader, a solution method in which the solution is dissolved in an appropriate solvent, a slurry method in which the suspension is suspended in an appropriate solvent, or a so-called gas phase grafting method.
The treatment temperature is appropriately selected in consideration of (A) to (D) deterioration of at least one polyethylene resin, decomposition of unsaturated carboxylic acid and derivatives thereof, decomposition temperature of peroxide used, and the like. However, taking the melt kneading method as an example, it is usually 190 to 350 ° C., and 200 to 300 ° C. is particularly preferable.
In producing the functional group-containing polyethylene resin (X) according to the present invention, for the purpose of improving its performance, as described in JP-A-62-10107, an already known method, for example, the graft modification or A method of treating with an epoxy compound or a polyfunctional compound containing an amino group or a hydroxyl group after modification, and a method of removing unreacted monomers (unsaturated carboxylic acid and derivatives thereof) and various by-products by heating or washing. Can be adopted.
The higher the graft amount of at least one monomer selected from the group consisting of the unsaturated carboxylic acid and its derivative, the better, but generally it is in the range of 0.001 to 10% by weight (measurement method of graft amount: infrared spectroscopy). By a photometer).

Using the above radical initiator, the reaction to polyethylene-based resin, etc., grafting reaction and polyethylene micro-crosslinking occur simultaneously in parallel, but by setting the resin temperature during melt-kneading to 250 ° C. or higher, grafting The reaction takes place preferentially to achieve a high monomer addition rate. On the other hand, when the resin temperature is less than 250 ° C., the fine crosslinking of the polyethylene resin or the like occurs preferentially, resulting in an increase in gel and resin burn, 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 performed at such a high temperature, it is necessary to suppress air from entering the inside of the extruder or the reactor as much as possible. In melt-kneading, it is necessary to avoid the resin from staying in the extruder for a long time. I must. For this reason, it is extremely preferable to perform nitrogen feed in the vicinity of the raw material resin inlet.

In the production of the functional group-containing polyethylene-based resin (X) of the present invention, it is preferable to modify the polyolefin-based resin material over a plurality of orders, and thereby from a relatively expensive monomer, an unsaturated carboxylic acid and a derivative thereof. The modification rate of at least one modification monomer selected from the group is sufficiently increased to improve economy, and a high modification rate can be achieved with a relatively small amount of modification monomer. It is possible to produce a high-quality modified polyolefin resin (X) that is excellent in that no unreacted modified monomer remains and no gel or resin burn occurs.
Graft modification rate (measurement method: by infrared spectrophotometer) obtained by such a melt-kneading modification method is generally in the range of about 0.2 to 2.5% by weight. The upper limit of the graft modification rate of the resin (A) is preferably as high as possible, but is generally in the range of 0.55 to 3% by weight. However, it is not particularly limited to this range, and a higher modification rate is desirable.

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

The above component (A), component (B), component (C), component (D) and component (E) may be the same as the resin used in the functional group-containing polyethylene resin (X). A + B), (A + C), (A + D), (A + E), (B + C), (B + D), (B + E), (C + D), (D + E), (A + B + C), (A + B + D), (A + B + E), (A + C + D) , (A + C + E), (B + C + D), (B + C + E), (B + D + E), (C + D + E), (A + B + C + D), (A + B + C + E), (A + C + D + E), (B + C + D + E), (B + C + D + E), (A + B + C + D + E) unmodified polyethylene, etc. You may mix resin and its composition.
The component (Y) is not essential. However, when the component (X) is used alone, there is a concern that it may cause an adverse effect that excessive resin deterioration or gel may occur during molding. It is preferable to use the component (Y) because it is easy to adjust the functions such as density, heat resistance, mechanical properties, rigidity, and flexibility, or is economical.
In addition, at least one of (A), (B) and (D) used for the functional group-containing polyethylene resin (X) or unmodified polyethylene resin is produced with a single site catalyst. However, it is also preferable from the fact that there are few low molecular weight components and the resin deterioration and the generation of gel when containing functional groups are suppressed, and the performance such as mechanical strength and adhesive strength is improved.

(Vii) Adjustment of Adhesive Resin (Z) The adhesive resin (Z) of the present invention is a disc part formed at the inner shoulder part of the hollow container 1 formed of a synthetic resin liner and at one end of the cap member 3. 8 is bonded or welded with this adhesive resin (Z) in order to suppress gas leakage, and contains at least one functional group of (a) to (e) below (A) 0.5 to 100% by weight of at least one functional group-containing polyethylene resin (X) selected from (D) and at least one unmodified polyethylene resin selected from the following (A) to (E) (Z) is an adhesive resin (Z) having a density of 0.86 to 0.97 g / cm ³ and (z2) a melt flow rate of 0.01 to 100 g / 10 min. .
(A): (a1) density 0.94 to 0.97 g / cm ³ , (a2) high density polyethylene resin having a melt flow rate 0.01 to 100 g / 10 min (B): (b1) density 0.90 Less than 0.94 g / cm ³ , (b2) linear low density polyethylene resin (C) having a melt flow rate of 0.01 to 100 g / 10 min: (c1) high pressure radical method having a melt flow rate of 0.01 to 100 g / 10 min Polyethylene resin (D): (d1) Ultra low density polyethylene resin (E) having a density of 0.86 to less than 0.90 g / cm ³ and (d2) melt flow rate of 0.01 to 100 g / 10 min (E): thermoplastic elastomer

More specifically, a resin selected from one of (A), (B), (C) and (D) of the functional group-containing polyethylene resin (X) or a resin composition thereof, for example, (A) + (B), (B) + (C), (A) + (C), (A) + (D) or (A) + (B) + (C), (A) + (B) + ( D), (A) + (C) + (D), (B) + (C) + (D) and (A) + (B) + (C) + (D) Containing polyethylene-based resin composition (X ′) and one or more of unmodified polyethylene-based resin (Y) (A) to (E) or at least one unmodified polyethylene resin composition (Y ′) It is characterized by being mixed.
Among these, preferred are the functional group-containing linear low-density polyethylene resin (X) alone or the functional group-containing (B) component from the viewpoints of adhesiveness, heat resistance, strength, and easy moldability. And a mixture of the unmodified polyethylene resin composition (Y) with the unmodified high density polyethylene resin (A) and the unmodified linear low density polyethylene resin (B). The preferred blending ratio is 10 to 30% by weight of the functional group-containing polyethylene resin (X) of the component (B) and the unmodified polyethylene resin composition (Y) component (A / B = 5 to 40/95 to 60). 90 to 70% by weight.

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

The (z1) density of the adhesive resin (Z) is 0.86 to 0.97 g / cm ³ , preferably 0.90 to 0.96 g / cm ³ , more preferably 0.92 to 0.95. is there. If the density is less than 0.86 g / cm ³ , the adhesive strength may be lowered. If the density is more than 0.97 g / cm ³ , industrial mass production is difficult, and durability may be lowered. Occurs.
(Z2) The melt flow rate is in the range of 0.01 to 100 g / 10 min, preferably 0.05 to 50 g / 10 min, more preferably 0.1 to 30 g / 10 min. When the MFR is less than 0.01 g / 10 min, there is a difficulty in moldability, and when it exceeds 100 g / 10 min, the strength such as impact strength may be lowered.

  The adhesive of the present invention satisfies the above-mentioned properties, and the inner synthetic resin liner material shrinks and expands when the initial adhesive strength and high-pressure gas are filled and discharged, and the temperature changes. It is excellent in durability, such as compatibility, change with the passage of time, resistance to contents, and the like, and it is important that these adhesives are directly blended into the synthetic resin liner material 1. In particular, blow molding is efficient because it is produced in one step using an extrusion die, production speed is improved, a uniform coating film is formed, and performance such as adhesive strength is exhibited. Therefore, it is preferable.

The adhesive 4 of the present invention is preferably a polyolefin resin containing the above-described functional group, and more preferably an adhesive resin (Z). With such an adhesive, the initial adhesive strength, the inner synthetic resin liner material 1 when the high-pressure gas is filled and discharged, the response to shrinkage and expansion, temperature change, and the like are repeated. Durability such as resistance to changes over time and resistance to contents is excellent, and the adhesive of the present invention is a film, sheet, powder coating, etc., in a disk part previously formed at one end of the base member. An adhesive layer is formed. In particular, it is preferable to form a coating film by powder coating because a solvent is unnecessary, a uniform coating film is formed, and performance such as adhesive strength is exhibited with a relatively thin coating film. Further, when the adhesive is coated on the disk part of the base member in advance, a part or the entire surface of the disk part of the base member is subjected to a roughening treatment as desired, and the surface treatment is performed by the above-described base agent treatment. It is important to keep going.
As another embodiment, an adhesive layer is formed on the outer layer and / or the innermost layer of the synthetic resin liner material by a multilayer blow molding method or the like using a base member pretreated with a base treatment agent, and the adhesive layer A method of adhering or welding a synthetic resin liner material and a base member with a base treatment agent via a wire, or applying a base treatment agent by providing a line and / or groove on the base member, and then applying the base treatment line A method of forming an adhesive resin layer by burying an adhesive in the groove and / or groove, and bonding or welding the synthetic resin liner material and the die member through the adhesive resin layer by a blow molding method or an injection molding method Further, a method of directly blending the above-mentioned adhesive into a synthetic resin liner material and bonding or welding the synthetic resin liner material and a base member with a base treatment agent may be mentioned.

  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 adhesive powder used for the powder coating desirably has a density of 0.90 to 0.97 g / cm ³ , preferably 0.91 to 0.96 g / cm ³ , and more preferably 0.92 to 0.95. Range. If the density is less than 0.90 g / cm ³ , the adhesive strength may decrease, and if it exceeds 0.97 g / cm ³ , the durability may decrease.
Moreover, a melt flow rate is 0.01-100 g / 10min, Preferably it is 0.05-50 g / 10min, More preferably, it is the range of 0.1-40 g / 10min. If the MFR is less than 0.01 g / 10 min, there may be a problem in molding processability, and if it exceeds 100 g / 10 min, the strength such as impact strength may be lowered.

The median particle size of the powder is desirably 90 to 150 mesh (standard sieve: JIS Z8801), preferably 100 to 140 mesh, more preferably 110 to 130 mesh, bulk specific gravity (according to JIS K8721) 0.20 to 0. .50 g / cc, preferably 0.25 to 0.40, more preferably 0.30 to 0.35.
Moreover, the static friction coefficient (conforming to JIS K8721) of the powder is in the range of 0.7 to 0.9, and preferably in the range of 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.

Moreover, the thickness of the adhesive layer of the present invention is such that the thickness of the coating film 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. desirable. If the thickness is less than 10 μm, the adhesive strength is not sufficient, and there is a concern that gas leakage will occur due to repeated contraction motion, etc., and if it is 2 mm or more, there is a high possibility that problems such as generation of bubbles will occur. There is a concern that gas leakage may occur starting from the adhesive layer.
However, the thickness of the adhesive layer provided on the film, sheet, or liner material other than powder coating is selected in the range of about 10 to 5 mm. If the thickness of the adhesive layer is less than 10 μm, the adhesive force is insufficient as in the case of powder coating, and even if the thickness is 5 mm or more, the adhesive effect is not improved, resulting in an increase in cost and a loss of economy.

3. Pressure vessel The pressure vessel of the present invention is specifically described below.
As described above, the pressure vessel according to the present invention includes a hollow container 1 (inner wall) formed of an outer reinforcing material layer 2 (outer wall) and an inner synthetic resin liner, as shown in FIG. A base member for mounting a nozzle for filling and discharging a high-pressure gas, wherein a base treatment agent 4a and an adhesive 4b satisfying specific properties are applied in advance to at least one end of the pressure vessel. In order to suppress gas leakage, the shoulder portion on the inner side of the hollow container 1 formed by the synthetic resin liner material of the pressure vessel and the disc portion 8 formed at one end of the base member 3 are mounted. The pressure vessel 10 is bonded or welded via the adhesive 4b.

(1) The synthetic resin liner material forming the hollow container 1 inside the synthetic resin liner material needs to contain a high-pressure gas filled in the pressure vessel 10 and have a gas barrier property that does not leak, Specific examples include 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. 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. Stick, and the like.
Among the synthetic resin liner materials, polyethylene resins are 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 0.8. A range of 940 to 0.950 g / cm ³ is desirable.
When the density is less than 0.920 g / cm ³ , the rigidity is insufficient and the rigidity of the tank mouth portion is insufficient, and when the density exceeds 0.970 g / cm ³ , the durability may be lowered.
In the polyethylene resin, the high load melt flow rate: HLMFR (JIS K6922-1 (1997), condition D (measured at a temperature of 190 ° C. and a load of 211.8 N)) is 2 to 70 g / 10 minutes, preferably 3 to 60 g / 10 min, more preferably 4 to 50 g / 10 min is desirable, and within such a range, the synthetic resin liner material and the adhesive may be pressed simultaneously, particularly by multilayer blow molding. It is preferable because there is no layer disturbance when taking out and the surface layer is improved.
When the HLMFR is less than 2 g / 10 minutes, the resin pressure increases and the extrusion characteristics deteriorate, and when it exceeds 70 g / 10 minutes, there is a possibility that the impact properties and durability are insufficient.
These synthetic resin liner materials may be composed of a single layer body, a multilayer body, and a composite material of the thermoplastic resin. For example, it may be formed of a single layer of high-density polyethylene resin, or a composite material in which an engineering plastic, a metal member, and an inorganic filler are dispersed in the resin layer, or at least a thermoplastic resin layer / adhesive layer / It is good also as a laminated body which consists of a multilayer structure containing a barrier layer.

  The engineering plastics include various polyamide (PA) resins such as nylon 6, nylon 6,6, nylon 11 and nylon 12, various hydroxyl group-containing resins such as ethylene-vinyl alcohol copolymer (EVOH) and polyvinyl alcohol (PVA). , Various polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-styrene copolymer resin (AS), polycarbonate (PC) resin, polyacetal (POM) resin, polyphenylene ether (PPE) resin, polyphenylene sulfide (PPS) resin, 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 resin, three-layer structure, thermoplastic resin layer / adhesive layer / barrier layer / Adhesive layer / thermoplastic resin layer 3 type 5 layer structure, thermoplastic resin layer / regrind layer / adhesive layer / barrier layer / adhesive layer / thermoplastic resin layer 4 type 6 layer structure, etc. In addition, a laminate composed of two layers / two layers of thermoplastic layer / adhesive layer, two layers / three layers of adhesive layer / barrier layer / adhesive layer, and the like.
Examples of the material suitably used for the barrier material layer include polyamide resin, polyester resin, ethylene-vinyl alcohol copolymer, polyvinyl alcohol resin, polyacrylonitrile resin, and the like.
As the adhesive layer, general adhesives such as the adhesive 4 of the present invention and thermosetting resins such as epoxy resins and polyurethane resins can be used.
When these liner materials are used to form a hollow container, it 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 and the injection molding method are preferred.

(2) Outer reinforcing material The reinforcing material forming the outer reinforcing material layer 2 covers the hollow container 1 formed of the inner synthetic resin liner material and plays a role of improving the pressure resistance of the pressure container 10. It may be made of a lightweight metal material such as aluminum, titanium, light alloy, etc. However, in consideration of molding processability, weight reduction, etc., fiber reinforced plastics (FRP: fiber reinforced plastics) or fiber reinforced It is preferable to use a metal reinforced metal (FRM). That is, in order to form the reinforcing material layer 2 made of FRP so as to cover the outer peripheral wall of the cylindrical hollow container 1 formed by blow molding or the like of the synthetic resin liner material constituting the inner wall, 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 of the cylindrical hollow container 1 by a filament winding method or a tape winding method, and then the resin The outer wall reinforcing material layer 2 can be formed by heating and melting or curing to form. The strength of the reinforcing material layer 2 is a suitable range suitable for the purpose by combining various types of reinforcing fiber forming the winding layer, winding form, winding thickness, resin type, resin thickness, etc. The reinforcing material layer 2 can be obtained. Further, it may be formed by other methods such as a prepreg method in which a continuous reinforcing material such as a fabric is impregnated with a thermosetting resin.

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

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

FIG. 3 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. 3, the base treatment agents 4a, 4a 'and the adhesive are bonded to the upper and lower sides of the support member 14 associated with the support base 15 of the base member 3 at least at one end of the blow molding apparatus having at least a mold and a base support base. A cylindrical parison that forms a hollow container 1 from a die 11 of a blow molding machine (not shown), in which a base member 3, 3 ′ in which an agent 4 b, 4 b ′ is coated on an upper disk of one end of the base member 1 is supported. 12 (a, b) is extruded, suspended between the molds 13 (a, b), and a disk part formed at one end of the base member 3 installed in the mold by the parison 12 (a, b) Next, the mold 13 (a, b) is closed while the parison is still sufficiently soft, the diameter of the parison 12 (a, b) is reduced, and the necks of the base members 3, 3 'are attached to the parison 12 Pinch at the same time as (a, b) and put gas into the sealed mold Then, the parison 12 (a, b) is pressed against the wall of the mold 13 (a, b) to form a container, and at the same time, the shoulder part inside the hollow container 1 and the disk part 8 of the base member 3, 3 ′. The hollow containers 1 are manufactured by fusing the adhesives 4b and 4b ′ on the pretreated base treatment surface by internal pressure. Next, the outer circumference of the synthetic resin liner material of the hollow container 1 is impregnated with a thermosetting resin such as an epoxy resin or an unsaturated polyester resin, a fiber yarn such as a carbon fiber yarn or a bundle, a fiber yarn such as a glass fiber yarn or a bundle, or a bundle. The pressure vessel 10 is manufactured by covering with a mat or the like and curing to form a fiber reinforcing material 2 (CFRP, GFRP, etc.) layer.

  In the method for producing a pressure vessel of the present invention, the method for producing a hollow container formed from a synthetic resin liner material is not limited to the blow molding method, and is produced by injection molding, rotational molding, compression molding, or the like. However, since the base member can be integrated at the time of manufacture, the manufacturing process is simple, the manufacturing cost is low, and it is economical, it is preferable to employ the blow molding method.

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

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

1. Measurement method (1) Melt flow rate: 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 (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) Adhesive layer thickness: Select any part (5 places) of the disk part of the base part coated with adhesive by electrostatic coating, and use the following thickness gauge (EX-V manufactured by Keyence Corporation) The coating film thickness was measured. The sheet thickness was also measured in the same manner (measured value is an average value of 5 points).
[Thickness gauge]
High-accuracy overcurrent type using a digital displacement sensor: As the distance between the object and the sensor head approaches, the overcurrent increases and the transmission amplitude decreases. This transmission amplitude is rectified to change the DC voltage. The rectified signal and the distance are substantially proportional to each other, and linearity is corrected by a linearize circuit to obtain a linear output proportional to the distance. The thickness is displayed digitally.
(7) Appearance of the adhesive layer: The surface smoothness and surface state of the adhesive layer formed with a coating film or sheet formed on the disk part of the base part coated with the adhesive by electrostatic coating were visually observed. .
(8) Adhesive strength: Only the resin layer on the flat part of the die is turned 10 mm wide and 3 cm long using a cutter. Tensilon is used to pull tensilon at a pulling 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 is allowed to stand at room temperature for 30 days. ○ is no gas leak, × is gas leak.

2. Examples Hereinafter, the present invention will be demonstrated by examples implemented by powder coating or the like.
<Example 1>
[Production of functional group-containing polyethylene resin (X1)]
High-density polyethylene resin (density: 0.958 g / cm ³ , MFR: 20 g / 10 min, brand: HS490P, manufactured by Nippon Polyethylene Co., Ltd., referred to as A1) and linear low-density polyethylene resin (density) : 0.921 g / cm ³ , MFR: 16 g / 10 min, Brand: UJ370G, manufactured by Nippon Polyethylene Co., Ltd. (referred to as B1) 20 parts by weight of powdered polyethylene resin mixture (A1 + B1) in 100 parts by weight Then, 0.8 parts of maleic anhydride and 0.02 parts of 2,5-dimethyl-di- (t-butylperoxy) hexane were added, mixed with a Henschel mixer, and then 50 mm single screw extrusion manufactured by Modern Machinery Co., Ltd. Machine, melt kneading under the conditions of a screw speed of 50 rpm and a resin temperature of 280 ° C., MFR 8 g / 10 min, density 0.950 g / c A functional group-containing polyethylene resin (X1) having m ³ and a graft monomer amount of 0.5% by weight was obtained.

[Manufacture of adhesive resin powder (Z1)]
Functional group-containing polyethylene resin (X1) 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 set with a 90 mesh sieve, and then smoothed to give an adhesive resin powder (Z1) having properties as shown in Table 1. Was made. The density and MFR as the adhesive (Z1) were values as shown in Table 1, respectively.

[Base treatment of base member]
The liquid which mixed 500 mass parts of water, 10 mass parts of glycerylated chitosan, and 10 mass parts of 1,2,3,4-butanetetracarboxylic acid was stirred for 4 hours, and the glycerylated chitosan was fully dissolved. 5 parts by mass of chromium fluoride (trivalent Cr) was added to the resulting solution to obtain a base treatment agent. Next, the surface treatment agent was applied to the disk portion of the aluminum base member with a roll coater, and then heated and dried at 200 ° C. for 30 seconds to form a surface treatment layer (film, 4b in FIG. 2).

[Electrostatic coating]
Using an electrostatic coating machine (manufactured by GEMA), the adhesive resin powder is applied to the disk part 8 of the base member having a disk part at one end as shown in FIG. After electrostatic coating to a coating thickness of 300 μm as shown in FIG. 1, it was placed in an oven at 200 ° C. for 30 minutes to obtain a coated base member. The results (adhesive strength, coated surface smoothness, etc.) are shown in Table 1.

[Manufacture of pressure vessels]
As shown in FIG. 3, the coated base member is inserted above and below the support portion 14 that is engaged with the support base 15, and the base members 3 and 3 ′ are installed. Using a multilayer hollow molding machine, a cylindrical parison 12 (a, b) is extruded from a die 11 of a blow molding machine (not shown) under the following conditions, and is suspended between the molds 13 (a, b). The mold 13 (a, b) is closed with a sufficiently soft parison, the diameter of the parison 12 (a, b) is reduced, and the necks of the base members 3, 3 'are pinched simultaneously with the parison 12, Air is blown to press the parison 12 against the wall of the mold 13 to form the hollow container 1 formed of a synthetic resin liner. On the other hand, the shoulder 7 of the hollow container 1 and the adhesive 4b on the base treatment agent 4a previously applied to the disk portion 8 of the base member 3 cause the base member 3 (rod) to be the shoulder of the hollow container 1 due to internal pressure. The hollow container 1 was produced by being pressed and fused to 7 and bonded to a cap part having a volume of 30 liters. Next, the outer periphery of the hollow container 1 is impregnated with an epoxy resin, which is a thermosetting resin, and coated with a carbon fiber bundle. After that, the epoxy resin is cured to form a carbon fiber fiber reinforcement (CFRP) layer 2. The 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 the change over time in the tank pressure after standing at 60 ° C. for 60 days or at room temperature for 30 days. The results are shown in Table 1 (◯ is no gas leak, × is gas leak).
Table 1 shows the physical properties of the raw materials, the evaluation results of the pressure vessel, and the like.

[Blow molding conditions]
High-density polyethylene layer / regrind layer / adhesive layer / gas barrier layer (EVOH layer) / adhesive from the outer layer side under the conditions of molding temperature 210 ° C., blow pressure 1.4 MPa, mold temperature 20 ° C. and blowing time 130 sec. 4 types / 6 layers (layer thickness: 0.7 mm (outermost layer) /2.0 mm / 0.1 mm / 0.15 mm / 0.1 mm / 2.0 mm (innermost layer)) ) Cylindrical hollow container was produced. 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 , melt flow rate (MFR: measurement temperature 190 ° C., load 21.18 N) = 0.04 g / 10 min, high load melt Float (HLMFR: measurement temperature 190 ° C., load 211.8 N) = 6 g / 10 min.
[Regrind material layer]
The composition ratios of the high-density polyethylene resin, the adhesive, and the ethylene-vinyl alcohol copolymer are 87.2% by weight, 6.5% by weight, and 6.3% by weight, respectively.
[Adhesive layer]
Product name: Adtex FT61AR3, manufactured by Nippon Polyethylene Co., Ltd., density 0.933 g / cm ³ , MFR 0.6 g / 10 min.
[Gas barrier layer]
Ethylene-vinyl alcohol copolymer layer (EVOH layer)
Product name: EVAL F101B (manufactured by Kuraray Co., Ltd.)

<Examples 2-3>
[Production of functional group-containing polyethylene resin (X2)]
Powdered 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 B2), 100 parts by weight of anhydrous maleic After adding 0.8 parts of acid and 0.02 part of 2,5-dimethyl-di- (t-butylperoxy) hexane and mixing with a Henschel mixer, a 50 mm single screw extruder manufactured by Modern Machinery Co., Ltd. was used. Then, melt-kneading under the conditions of a screw speed of 50 rpm and a resin temperature of 280 ° C. to obtain a functional group-containing polyethylene resin (X2) having an MFR of 4 g / 10 min, a density of 0.925 g / cm ³ and a graft monomer amount of 0.5 wt% It was.

[Production of adhesive resin powder (Z2)]
Functional group-containing polyethylene resin (X2) 20% by weight and linear low-density polyethylene resin (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Z50MG, manufactured by Nippon Polyethylene Co., Ltd. Y1 (B2 )) 80% by weight was pulverized using a mechanical pulverizer set with a 90 mesh sieve and smoothed to produce an adhesive resin powder (Z2) having the properties shown in Table 1. . The density and MFR as the adhesive resin powder (Z2) were values as shown in Table 1, respectively.
Using the adhesive resin powder (Z2), electrostatic coating is performed on the disk portion of the base member in the same manner as in Example 1 to produce two types of base members having a thickness of 300 μm and 800 μm, and the physical properties thereof are shown. It was shown in 1. 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 1.

<Example 4>
[Production of functional group-containing polyethylene resin (X3)]
[Production of functional group-containing polyethylene resin (X3)]
Powdery single-site linear low-density polyethylene resin (density: 0.930 g / cm ³ , MFR: 3 g / 10 minutes, brand: Harmolex LL NW584N, manufactured by Nippon Polyethylene Co., Ltd., referred to as B3) 100 After adding 0.6 parts of maleic anhydride and 0.02 parts of 2,5-dimethyl-di- (t-butylperoxy) hexane to parts by weight, mixing with a Henschel mixer, 50 mm manufactured by Modern Machinery Co., Ltd. Using a single screw extruder, melt-kneaded under the conditions of a screw speed of 50 rpm and a resin temperature of 280 ° C., MFR 2 g / 10 min, density 0.930 g / cm ³ , and functional group-containing polyethylene resin with a grafting rate of 0.4 wt% (X3) was obtained.

[Production of adhesive resin powder (Z3)]
Functional group-containing polyethylene resin (X3) 20% by weight and linear low-density polyethylene resin (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Z50MG, manufactured by Nippon Polyethylene Co., Ltd. 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 (Z3) having the properties shown in Table 1. The density and MFR as the adhesive resin powder (Z3) were values as shown in Table 1, respectively.
Using the adhesive resin powder (Z3), electrostatic coating was performed on the disk portion of the die member in the same manner as in Example 1 to produce a die member having a thickness of 300 μm. Table 1 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 1.

<Example 5>
[Production of adhesive resin powder (Z4)]
Functional group-containing polyethylene resin (X1) 20% by weight and high-density polyethylene resin (density: 0.963 g / cm ³ , MFR: 7.0 g / 10 min, brand: HM560N, manufactured by Nippon Polyethylene Co., Ltd., A2 ) After 80% by weight was pulverized using a mechanical pulverizer with a 90 mesh sieve set, it was smoothed to produce an adhesive resin powder (Z4) having the properties shown in Table 1. The density and MFR as the adhesive resin powder (Z4) were values as shown in Table 1, respectively.
Using the adhesive resin powder (Z4), electrostatic coating was performed on the disk portion of the die member in the same manner as in Example 1 to produce a die member having a thickness of 300 μm. Table 1 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 1.

<Examples 6 to 9>
[Production of functional group-containing polyethylene resins (X4) to (X7)]
80 parts by weight of a linear low density polyethylene resin (density: 0.921 g / cm ³ , MFR: 16 g / 10 min, brand: UJ370G, referred to as “B1” manufactured by Nippon Polyethylene Co., Ltd.) and a low density polyethylene resin (density: 100 parts by weight of a powdered polyethylene resin mixture (B1 + C1) comprising 0.919 g / cm ³ , MFR: 8.5 g / 10 min, brand: LC607A, Nippon Polyethylene Co., Ltd. (referred to as C1) 20 parts by weight After adding 0.8 parts of maleic anhydride and 0.02 parts of 2,5-dimethyl-di- (t-butylperoxy) hexane and mixing with a Henschel mixer, 50 mm uniaxial made by Modern Machinery Co., Ltd. Using an extruder, it was melt-kneaded under the conditions of a screw speed of 50 rpm and a resin temperature of 280 ° C. to obtain a functional group-containing polyethylene resin (X4).
In addition, the following raw resin A, B, C and D for functional group-containing polyethylene resin are blended in the proportions shown in Table 2, and the functional group-containing polyethylene is the same as the functional group-containing polyethylene resin (X4). Resins (X5) to (X7) were obtained.
Raw material resin:
A1: High density polyethylene resin (density: 0.958 g / cm ³ , MFR: 20 g / 10 minutes, brand: HS490P, manufactured by Nippon Polyethylene Co., Ltd. B1: linear low density polyethylene resin (density: 0.921 g / cm ³ , MFR: 16 g / 10 min, brand: UJ370G, manufactured by Nippon Polyethylene Co., Ltd. C1: low density polyethylene resin (density: 0.919 g / cm ³ , MFR: 8.5 g / 10 min, brand: LC607A, Nippon Polyethylene Co., Ltd. D1: Linear ultra-low density polyethylene (Density: 0.870 g / cm ³ , MFR: 5 g / 10 min, Brand: Engage 8200, manufactured by Dow Chemical Japan Co., Ltd.

[Production of Adhesive Resin Powders (Z5) to (Z8)]
20% by weight of each of functional group-containing polyethylene resins (X4) to (X7) and linear low-density polyethylene resin (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Z50MG, Nippon Polyethylene Co., Ltd. ) 80% by weight (made by company Y1 (B2)) after pulverization using a mechanical pulverizer with a 90 mesh sieve set, smoothing treatment and adhesive resin powder having the properties shown in Table 2 ( Z5) to (Z8) were prepared. The density and MFR of each of the adhesive resin powders (Z5) to (Z8) were values as shown in Table 2, respectively.
Using the above-mentioned adhesive resin powders (Z5) to (Z8), electrostatic coating was performed on the disk part of the base member in the same manner as in Example 1 to produce a base member having a thickness of 300 μm. It was shown to.
Moreover, the pressure vessel was manufactured using this base member in the same manner as in Example 1, and the evaluation results are shown in Table 2.

<Examples 10 to 12>
As adhesive resin powder (Z9), 20% by weight of the functional group-containing polyethylene resin (X1) used in Example 1, and low density polyethylene (density: 0.919 g / cm ³ ) as unmodified polyethylene resin (Y), MFR: 8.5 g / 10 min, Brand: LC607A, Nippon Polyethylene Co., Ltd. Y2 (C1) 80% by weight was melt-kneaded and pulverized using a mechanical pulverizer with a 90 mesh sieve set. Then, an adhesive resin powder (Z9) having properties as shown in Table 3 was produced by smooth treatment. Using the adhesive resin powder (Z9), electrostatic coating was performed on the disk portion of the die member in the same manner as in Example 1 to produce a die member having a thickness of 300 μm. Table 3 shows the physical properties.
For the adhesive resin powder (Z10), 50% by weight of the functional group-containing polyethylene resin (X1) used in Example 1 and linear ultra-low density polyethylene (density: 0.00) as the unmodified polyethylene (Y). 870 g / cm ³ , MFR: 5 g / 10 min, Brand: Engage 8200, manufactured by Dow Chemical Japan Co., Ltd., referred to as Y3 (D1)))) The adhesive resin powder (Z10) having properties as shown in Table 3 was used.
Furthermore, for the adhesive resin powder (Z11), 50% by weight of the functional group-containing polyethylene resin (X1) used in Example 1, thermoplastic elastomer (density: 0.870 g / cm ³ , MFR: 5 g / 10). Min., Brand: Toughmer P-0180, manufactured by Mitsui Chemicals, Inc.) 50 wt% Y4 (E1)) is pulverized using a mechanical pulverizer with a 90 mesh sieve set and smoothed. An adhesive resin powder (Z11) having properties as shown in FIG.
Using the adhesive resin powders (Z9) to (Z11), electrostatic coating was performed on the disk portion of the die member in the same manner as in Example 1 to produce a die member having a thickness of 300 μm. It was shown to.
Table 3 shows the results of manufacturing and evaluating pressure vessels using these cap members in the same manner as in Example 1.

<Example 13>
Random terpolymer of ethylene-maleic anhydride (MAH) -methyl acrylate (MA) as the functional group-containing polyethylene resin (X) (density = 0.94 g / cm ³ , MFR = 8, MAH = 3 wt% MA = 10 wt%, manufactured by Nippon Polyethylene Co., Ltd., called ET, 20 wt% and linear low density polyethylene resin (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Z50MG) 80% by weight (referred to as Y1 (B2), manufactured by Nippon Polyethylene Co., Ltd.) was pulverized using a mechanical pulverizer in which a 90 mesh sieve was set, and then subjected to a smooth treatment, and the properties shown in Table 3 were obtained. An adhesive resin powder (Z12) was produced.
Using the adhesive resin powder (Z12), electrostatic coating was performed on the disk portion of the die member in the same manner as in Example 1 to produce a die member having a thickness of 300 μm. Table 3 shows the physical properties.
Moreover, the pressure vessel was manufactured in the same manner as in Example 1 using this base member, and the evaluation results are shown in Table 3.

<Example 14>
Modified polyethylene resin (X1) 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 melt-kneaded at 200 ° C using a single-screw extruder, then a 500 µm sheet was prepared using a T-die molding machine, and pressure-bonded to a die preheated for 30 minutes in an oven at 200 ° C The adhesive strength of the base member produced by the above was the same as that of the powder coating of Example 1. As a result of producing and evaluating a pressure vessel in the same manner as in Example 1 for this base member, no gas leakage was confirmed. The evaluation results are shown in Table 3.

<Comparative Example 1>
[Production of resin powder (Z13)]
In the above Example 1, an unmodified linear low density polyethylene (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Z50MG, manufactured by Nippon Polyethylene Co., Ltd.) is used for the base member instead of the adhesive resin. Table 4 shows the results of producing and evaluating a pressure vessel in the same manner as in Example 1 except that the powder (called Y1 (B2)) (Z13) was used.

<Example 15>
[Manufacture of adhesive resin powder (Z13)]
20% by weight of functional group-containing polyethylene resin (X2) and linear ultra-low density polyethylene (density: 0.870 g / cm ³ , MFR: 5 g / 10 min, brand: engagement 8200, Dow as unmodified polyethylene (Y)・ Chemical Japan Co., Ltd. Y5 (D1) (80% by weight) was melt-kneaded or dry blended, then pulverized using a mechanical pulverizer with a 40 mesh sieve set, smoothed and shown in Table 4 An adhesive resin powder (Z14) having such properties was produced. The density and MFR as the adhesive resin powder (Z14) were values as shown in Table 4, respectively.
The base member was electrostatically coated in the same manner as in Example 1, and the adhesion strength and smoothness of the coating surface were shown in Table 4.
Moreover, the pressure vessel was manufactured similarly to Example 1 using the base member, and the evaluation results are shown in Table 4.

<Reference Examples 1 and 2>
The results of evaluating the powder properties in powder coating are shown below.
Functional group-containing polyethylene resin (X2) 20% by weight and unmodified linear low-density polyethylene (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Z50MG, Y1 manufactured by Nippon Polyethylene Co., Ltd. B2)) 80% by weight melt-kneaded or dry blended, pulverized using a mechanical pulverizer with a 60-mesh sieve set, smoothed, and adhesive resin powder having the properties shown in Table 5 A body (Z15) was produced.
Using the adhesive resin powder (Z15), a die member in which a 300 μm or 800 μm coating film was formed on the die member by electrostatic coating as in the method of Example 1 was produced. Table 5 shows the adhesive strength and smoothness of the coating surface.
Moreover, the pressure vessel was manufactured similarly to Example 1 using the base member, and the evaluation results are shown in Table 5.

<Reference Example 3>
Functional group-containing polyethylene resin (X2) 20% by weight and unmodified linear low-density polyethylene (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Z50MG, Y1 manufactured by Nippon Polyethylene Co., Ltd. B2)) After 80% by weight melt kneading or dry blending, an adhesive resin powder (Z16) having the properties shown in Table 5 was prepared using a mechanical pulverizer with a 90 mesh sieve set. . The density and MFR of the adhesive resin powder (Z16) were values as shown in Table 5, respectively.
Using the adhesive resin powder (Z16), a die member having a 2.3 mm coating film formed on the die member by electrostatic coating in the same manner as in Example 1 was produced. Table 5 shows the adhesive strength and smoothness of the coating surface.
Moreover, the pressure vessel was manufactured similarly to Example 1 using the base member, and the evaluation results are shown in Table 5.

<Reference Example 4>
Functional group-containing polyethylene resin (X2) 20% by weight and unmodified linear low-density polyethylene (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Z50MG, Y1 manufactured by Nippon Polyethylene Co., Ltd. B2)) 80% by weight after melt-kneading or dry blending, after pulverization using a mechanical pulverizer with a 90 mesh sieve set, and without smoothing treatment, the static friction coefficient as shown in Table 5 is obtained. An adhesive resin powder (Z16) was prepared. The density and MFR of the adhesive resin powder (Z17) were values as shown in Table 5, respectively.
Using the adhesive resin powder (Z17), a die member having a 300 μm coating film formed on the die member by electrostatic coating as in the method of Example 1 was produced. Table 5 shows the adhesive strength and smoothness of the coating surface.
Moreover, the pressure vessel was manufactured similarly to Example 1 using the base member, and the evaluation results are shown in Table 5.

<Reference Example 5>
Functional group-containing polyethylene resin (X2) 20% by weight and unmodified linear low-density polyethylene (density: 0.924 g / cm ³ , MFR: 9 g / 10 min, brand: Z50MG, Y1 manufactured by Nippon Polyethylene Co., Ltd. B2)) After melt-kneading or dry blending 80% by weight, a cutter clearance of a mechanical pulverizer with a 90 mesh sieve set was prepared, and an adhesive resin powder (Z18) having a bulk specific gravity as shown in Table 5 was prepared. ) Was produced. The density and MFR of the adhesive resin powder (Z18) were values as shown in Table 5, respectively.
Using the adhesive resin powder (Z18), a die member having a 300 μm coating film formed thereon was produced by electrostatic coating on the die member in the same manner as in the method of Example 1. Table 5 shows the adhesive strength and smoothness of the coating surface.
Moreover, the pressure vessel was manufactured similarly to Example 1 using the base member, and the evaluation results are shown in Table 5.

3. Evaluation results As shown in Examples 1 to 14 of Tables 1 to 3, by applying the base treatment in advance and using the base part uniformly applied with an adhesive such as powder coating, Thus, a pressure vessel having improved adhesive strength, no gas leakage, and significantly improved hermetic sealing properties (pressure resistance), durability, and the like is provided.
Further, as shown in Comparative Example 1 in Table 4, the adhesive strength was low and the hermetic sealability was poor outside the scope of the present invention without the adhesive resin. Further, when the density of Example 15 was lowered, the adhesive layer became soft, and coating unevenness was somewhat produced, and in the gas leak test, leakage began to occur in 50 days. However, it can be used satisfactorily when the gas filling pressure is low.

  Moreover, as a result of evaluating the powder properties in powder coating, as shown in Reference Examples 1 and 2 in Table 5, the median particle size is 80 mesh, and the thickness of the adhesive layer is 2. When the coefficient of static friction is 0.95 as shown in Reference Example 4 and the bulk density of Reference Example 5 is 0.18 as shown in Reference Example 4, bubbles and uneven coating occur in each case, and a uniform coating layer is obtained. It was found that hermetic sealing properties (pressure resistance), durability, and the like deteriorated.

  According to the pressure vessel of the present invention and the manufacturing method thereof, a pressure vessel having an improved hermetic sealing property by improving the adhesive force between the inner wall of the hollow vessel formed of a synthetic resin liner material and the base member, and the pressure vessel Because it can provide a manufacturing method that can be economically manufactured in a simple process, it is for industrial use to store domestic liquefied petroleum gas containers, liquefied petroleum gas containers for automobiles, compressed natural gas (CNG), oxygen, nitrogen, etc. Since it can be particularly preferably used for a pressure vessel, a resin pressure vessel which can be used as a hydrogen tank for a fuel cell, etc., its industrial value is extremely large.

FIG. 1 is a partially cutaway sectional view of an example of a preferable base member of the present invention. FIG. 2 is a partially cutaway sectional view of an example of the pressure vessel of the present invention. FIG. 3 is a cross-sectional view of the main part of a blow molding method which is an example of a preferred production method of the present invention.

Explanation of symbols

1: Hollow container 1
2: Reinforcement material layer 3, 3 ': Base member 4a: Substrate treatment agent 4, 4', 4b: Adhesive 5: Outer base part 6: O-ring 7: Shoulder part of hollow container 8: Disk part of base 10: Pressure vessel 11: Extrusion die 12a: Parison a
12b: Parison b
13a: Mold a
13b: Mold b
14: support part 15: support stand

Claims (12)

A base used for 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 base member A base member in which the base member is treated with the following surface treatment agent.
[Pretreatment agent]
One or more chitosans selected from the group consisting of chitosan and chitosan derivatives and selected from the group consisting of Ti, Hf, Mo, W, Se, Ce, Fe, Cu, Zn, V and trivalent Cr A surface treatment agent comprising a metal compound containing one or more kinds of metals obtained   The base member according to claim 1, wherein an adhesive layer made of an adhesive is further provided on a treatment surface treated with the base treatment agent. The die member according to claim 2, wherein the adhesive is an adhesive made of a polyolefin resin containing at least one functional group of the following (a) to (e) or a composition thereof.
[Functional group]
(A) carboxylic acid group or carboxylic anhydride group (b) epoxy group (c) hydroxyl group (d) amino group (e) silyl group 1 type of polyethylene-type resin (X) selected from the following (A)-(D) in which the said adhesive agent contains the at least 1 sort (s) of functional group of said (a)-(e) 0.5-100 weight. % And at least one unmodified polyethylene resin (Y) selected from the following (A) to (E): 0 to 99.5% by weight, (z1) density 0.86 to 0.97 g / The base member according to claim ³ , comprising: cm ³ , (z2) 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 0.01 to 100 g / 10 min (B): (b1) Density 0.90 ˜0.94 g / cm ³ , (b2) linear low density polyethylene resin (C) having a melt flow rate of 0.01 to 100 g / 10 min (C): (c1) high pressure having a melt flow rate of 0.01 to 100 g / 10 min Radical method polyethylene resin (D): (d1) Ultra low density polyethylene resin (E) with a density of 0.86 to less than 0.90 g / cm ³ and (d2) a melt flow rate of 0.01 to 100 g / 10 min (E): Heat Plastic elastomer   The base member according to claim 4, wherein the (A), (B), or (D) is a polyethylene resin produced with a single site catalyst.   The base member according to claim 4 or 5, wherein the adhesive resin (Z) comprises 5 to 95% by weight of a functional group-containing polyethylene resin (X) and 5 to 95% by weight of an unmodified polyethylene resin (Y). .   The said adhesive agent contains 0.001-30 weight% of at least 1 sort (s) of functional group of said (a)-(e) on the basis of the weight of the whole adhesive agent. A base member according to the above.   The base member according to any one of claims 2 to 7, wherein the adhesive layer is provided by powder coating.   The powder used in the powder coating has a median particle size of 90 to 150 mesh, a bulk specific gravity of 0.2 to 0.5 g / cc, and a static friction coefficient of 0.7 to 0.9. The base member according to claim 8.   The base member according to claim 8 or 9, wherein a thickness of an adhesive layer provided by the powder coating is 10 µm to 2 mm.   A pressure vessel having a hollow container formed of a synthetic resin liner and a reinforcing material layer formed of a reinforcing material provided on an outer layer of the hollow container, and having at least one base member; The pressure vessel, wherein the base member is the base member according to any one of claims 1 to 10. 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 is formed by blow molding a synthetic resin liner material, and the base member uses the base member according to any one of claims 1 to 10. Container manufacturing method.

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