JP5915321B2 - Laminated body for pressure vessel liner, pressure vessel and method for producing the same - Google Patents

Description

  The present invention relates to a laminate for a pressure vessel liner, a pressure vessel, and a method for producing the same, and more specifically, a hollow vessel formed of a synthetic resin liner material, a reinforcing material on an outer surface, and an adhesive strength are improved. Winding displacement of the reinforcing yarn to be formed can be prevented, and the pressure vessel liner laminate in which the shape retention at the time of molding is dramatically improved, and the pressure vessel using the laminate The present invention relates to a method for manufacturing the pressure vessel.

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

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

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

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

The present applicant, in Patent Document 2 , previously 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 base member, in which the hollow vessel and the reinforcing material layer are bonded or welded via an adhesive layer provided on the outer layer of the hollow vessel. . And, there has been proposed a pressure vessel in which the adhesive force between the inner wall of the hollow container formed of a synthetic resin liner material and the base member is improved, and the hermetic sealing property is improved, but the performance is further improved. Things are sought.
In particular, Patent Document 2 discloses a polyolefin-based resin containing a functional group or a composition thereof as an adhesive for forming an adhesive layer, and is particularly excellent in adhesion between a liner material and a reinforcing material, It cannot be said that disclosure or suggestion regarding a material suitable for retaining the liner shape at the time of winding the reinforcing material is necessarily made.

  The recent demands for strict quality control of products, higher pressure gas filling, or the conventional pressure vessel, especially for natural gas with relatively high molecular weight, etc. Is difficult to maintain sufficient hydrogen gas permeation resistance, and there is a demand for producing a higher-performance adhesive performance and a higher-quality product at a lower cost and with a simple manufacturing process.

Japanese Patent Laid-Open No. 7-305798 JP 2008-164131 A

The object of the present invention is to reinforce the formation of a reinforcing material layer by remarkably improving the adhesive strength with the reinforcing material on the outer surface of a hollow container formed of a synthetic resin liner material in view of the above-mentioned problems of the prior art. A pressure vessel liner laminate capable of producing a pressure vessel having a beautiful and strong reinforcing layer, preventing winding slippage when winding the yarn, and a pressure vessel using the pressure vessel and production of the pressure vessel It is to provide a method.
Another object of the present invention is to significantly improve the shape retention of the synthetic resin liner material during molding of the pressure vessel, particularly excellent in shape retention during winding of the reinforcing material to the hollow vessel, and at high temperatures. Another object of the present invention is to provide a pressure vessel liner laminate capable of producing a pressure vessel in which deformation of the pressure hardly occurs, a pressure vessel using the same, and a method for producing the pressure vessel.

  As a result of intensive studies in order to solve the above problems, the inventors of the present invention can maintain the shape of the synthetic resin liner material by using a laminate for a pressure vessel liner having specific properties, characteristics, and specific layer configurations. The shape of the molding material can be greatly improved, the adhesive strength between the synthetic resin liner material and the reinforcing material can be greatly improved, and the winding of the reinforcing yarn forming the reinforcing material can be prevented from slipping. The inventors have found that the retentivity can be dramatically improved and have completed the present invention.

That is, according to the first invention of the present invention, the thermoplastic resin layer (I) having the following characteristics (1) to (3) and the polyethylene layer (II) having the following characteristics (i) to (iii): A pressure vessel liner laminate comprising:
The thermoplastic resin layer (I) comprises at least one copolymer selected from the group consisting of an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-vinyl acetate copolymer. Including
A laminate for a pressure vessel liner is provided in which the thickness ratio of the thermoplastic resin layer (I) is 1 to 90% and the thickness ratio of the polyethylene layer (II) is 99 to 10%.
Characteristic (1): Density is 0.900 to 0.970 g / cm ³ Characteristic (2): Melt flow rate (MFR) measured at a temperature of 190 ° C. and a load of 2.16 kg is 0.01 to 100 g / 10 Characteristic (3): The amount of polar groups is 4 to 32% by weight Characteristic (i): Density is 0.900 to 0.970 g / cm ³ Characteristic (ii): Temperature 190 ° C., load 2 Melt flow rate (MFR) measured at .16 kg is 0.01 to 100 g / 10 min. Characteristic (iii): High temperature side melting point peak measured by DSC is 120 ° C. or higher.

Further, according to the second invention of the present invention, it has a hollow container formed of a liner material and a reinforcing material layer formed of a reinforcing material provided on an outer layer of the hollow container, and at least one A pressure vessel having a base member, wherein the liner material is a laminate according to the first invention is provided.

According to a third aspect of the present invention, there is provided the pressure vessel according to the second aspect, wherein the thermoplastic resin layer (I) of the liner material is disposed so as to contact the reinforcing material. Is done.

According to a fourth aspect of the present invention, there is provided the pressure vessel according to the second or third aspect , wherein the reinforcing material is a fiber reinforcing material.

Further, according to the fifth invention of the present invention, the hollow container formed by the pressure vessel liner laminate according to the first invention and the reinforcing material formed by the reinforcing material provided in the outer layer of the hollow container. A pressure vessel having at least one cap member, wherein a reinforcing material layer is provided on the outer layer of the hollow vessel, and the reinforcing material is bonded or welded to the thermoplastic resin layer (I). A method of manufacturing a pressure vessel is provided.

According to the laminate for a pressure vessel liner of the present invention, it is possible to remarkably improve the adhesive strength with the reinforcing material on the outer surface of the hollow container formed of the synthetic resin liner material, and to form a reinforcing material layer. Winding of the yarn can be prevented from slipping, and a pressure vessel having a beautiful and strong reinforcing layer can be manufactured.
Further, according to the laminate for a pressure vessel liner of the present invention, the shape retainability of the synthetic resin liner material is remarkably improved, particularly excellent in shape retainability during winding of the reinforcing material to the hollow container, and at a high temperature. It is possible to provide a pressure vessel in which the deformation of is difficult to occur.

The laminate for a pressure vessel liner of the present invention comprises a thermoplastic resin layer (I) having the above-described characteristics (1) to (3), and a polyethylene layer (II) having the above-described characteristics (i) to (iii). The thickness ratio of the thermoplastic resin layer (I) is 1 to 90%, and the thickness ratio of the polyethylene layer (II) is 99 to 10%.
Below, this invention is demonstrated in detail for every item.

1. Structure of Pressure Vessel The pressure vessel of the present invention has basically the same structure as that disclosed in, for example, Japanese Patent Application Laid-Open No. 2008-164131.
The pressure vessel according to the present invention is formed of a hollow container (inner wall) formed of a synthetic resin liner material (inner layer is a polyethylene layer and outer layer is a thermoplastic resin layer), and a reinforcing material on the outer layer of the hollow container. A reinforcing member layer (outer wall), and at least one end of the hollow container has a base member for attaching a nozzle for filling and discharging a high-pressure gas. The hollow container and the reinforcing member Is bonded or welded.

2. Materials for Pressure Vessel Constituent Materials The raw materials used in the present invention are specifically described in detail below.
(1) Liner material The liner material which forms a hollow container accommodates the high pressure gas with which the pressure container was filled. The liner material preferably has a gas barrier property that prevents the filled gas from leaking. Further, the liner material is preferably one having a high shape retaining property, and is preferably composed of a laminated material.

(1-1) Thermoplastic resin layer (I)
The thermoplastic resin layer (I) constituting the laminate for a pressure vessel liner of the present invention is formed from a thermoplastic resin having the following characteristics (1) to (3). In addition, when 25 to 75 weight% of polyethylene is contained in a thermoplastic resin, it is preferable to have the following characteristic (4).
Characteristic (1): Density is 0.900 to 0.970 g / cm ³ Characteristic (2): Melt flow rate (MFR) measured at a temperature of 190 ° C. and a load of 2.16 kg is 0.01 to 100 g / 10 Characteristic (3): The amount of polar group is 2 to 40% by weight. Characteristic (4): The proportion of insoluble components at 100 ° C. or higher measured by DSC is 20 to 75%. The technical significance of the above characteristics (1) to (4) will be described.
1. Characteristics (1)
The thermoplastic resin of the present invention, density of 0.900~0.970g / cm ^3, preferably, 0.905~0.965g / cm ^3, more preferably, 0.910~0.960g / cm A range of ³ is desirable for maintaining the shape of the container. The density is measured according to JIS K7112.
The density of the thermoplastic resin can be appropriately selected according to the performance of the target pressure vessel. However, if the density is less than 0.900 g / cm ³ , the rigidity is insufficient and the rigidity of the tank mouth portion is insufficient. In addition, if the density exceeds 0.970 g / cm ³ , the durability may decrease.

2. Characteristics (2)
The thermoplastic resin of the present invention has a melt flow rate (MFR) measured at a temperature of 190 ° C. and a load of 2.16 kg of 0.01 to 100 g / 10 minutes, preferably 0.02 to 80 g / 10 minutes. More preferably, it is 0.05 to 50 g / 10 min from the viewpoint of moldability of the hollow container. The MFR is measured according to JIS K6922-1 (temperature 190 ° C., load 2.16 kg).
The MFR of the thermoplastic resin can be appropriately selected according to the molding method of the target pressure vessel. However, if the MFR is less than 0.01 g / 10 min, the fluidity is low and the molding becomes difficult, and the molding resin Pressure rises and extrusion characteristics decrease. If it exceeds 100 g / 10 minutes, impact properties and durability may be reduced.

3. Characteristic (3)
The thermoplastic resin of the present invention has a polar group content of 2 to 40% by weight, preferably 3 to 36% by weight, and more preferably 4 to 32% by weight.
When the amount of the polar group is less than 2% by weight, the adhesion between the liner material and the reinforcing material becomes insufficient, and when it exceeds 40% by weight, the durability tends to decrease.
In the present invention, the polar group means an electrically polar substituent, and preferably (a) a carboxyl group, (b) a carboxylic acid anhydride group, (c) an alkoxycarbonyl group, and (d) At least one substituent selected from the group consisting of acyloxy groups is preferable from the viewpoints of adhesion to a reinforcing material, durability as a pressure vessel, and the like.

(A) A carboxyl group is a characteristic group of carboxylic acid and is —COOH.
(B) A carboxylic acid anhydride group is a group having a chemical structure in which one molecule of water is lost from two carboxyls of a carboxylic acid, and two acyl groups share one oxygen atom, and —CO—O Means -CO-.
(C) The alkoxycarbonyl group means —COOR, and in the present invention, R means C _n H _{2n + 1} — (n is 1 to 6), and n is preferably 1 to 4. Specific examples include a methoxycarbonyl group and an ethoxycarbonyl group.
(D) The acyloxy group means —OCOR ^1, and in the present invention, R ¹ means C _n H _{2n + 1} — (n is 1 to 6), and n is preferably 1 to 4, more preferably 1 It is. Specifically, an acetyloxy group (also referred to as an acetoxy group or an acetoxyl group) can be given.
The amount of the polar group can be determined from the amount of the radical polymerizable acid comonomer, acrylic acid ester comonomer, methacrylic acid ester comonomer, carboxylic acid vinyl ester comonomer, etc. used in producing the thermoplastic resin, IR and It can be measured by NMR analysis or the like.

4). Characteristic (4)
In the thermoplastic resin layer (I), a thermoplastic resin having no polar group can be mixed and used if necessary. As long as the effects of the present invention are not impaired, the polyethylene can be contained in an amount of 25 to 75% by weight. When the thermoplastic resin of the thermoplastic resin layer (I) contains 25 to 75% by weight of polyethylene, it preferably has the following characteristic (4).
The thermoplastic resin of the present invention has a shape retention property and heat resistance of the container of 20 to 75%, preferably 21 to 70% of the insoluble component at 100 ° C. or higher as measured by DSC. From the viewpoint, particularly from the viewpoint of shape retention during winding of the reinforcing material to the hollow container.
The ratio of the infusible component at 100 ° C. or higher measured by DSC is an index of the amount of the crystalline component contained in the thermoplastic resin, and the molded product shape is sufficiently retained by being within the range of the ratio. However, outside the range, it tends to be difficult to maintain the shape of the molded product.

DSC means differential scanning calorimetry, which is measured using a differential scanning calorimeter to measure crystallization temperature, crystallinity, and the like. DSC is a measurement based on a method that records the energy required to keep the temperature difference between the two to zero while the sample and reference material are adjusted under heating or cooling under equal conditions. Is done.
In the DSC measurement, the sample is put in a flat metal container, and precisely weighed to determine the amount of the sample. Then, the sample is covered with a lid, placed in a measuring device, and the amount of change in heat (ΔH) is determined over time.
In the present invention, the ratio of the infusible component at 100 ° C. or higher is the amount of change in calorie (ΔHw) of the DSC of the thermoplastic resin composition sample at 100 ° C. or higher, and the DSC heat amount change of the sample of polyethylene alone as the component of the composition The amount (ΔHa) is measured and determined as a ratio (percentage) of ΔHw / ΔHa.

5. Copolymer (B)
The thermoplastic resin forming the thermoplastic resin layer (I) of the present invention is preferably selected from the group consisting of ethylene and a radical polymerizable acid comonomer, an acrylate ester comonomer, a methacrylic acid ester comonomer, and a carboxylic acid vinyl ester comonomer. Preferred is a copolymer (B) with at least one comonomer.
The copolymer (B) is a specific ethylene-polar comonomer copolymer, and the use of this specific copolymer is also one of the features of the present invention.

Specific examples of the radical polymerizable acid comonomer of the copolymer (B) include α, β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, and itaconic acid, or anhydrides thereof, acrylic acid, Examples thereof include unsaturated monocarboxylic acids such as methacrylic acid, crotonic acid, vinyl acetic acid and pentenoic acid, among which maleic anhydride, acrylic acid and methacrylic acid are preferred.
Specific examples of the acrylate ester comonomer of the copolymer (B) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and the like. Among them, methyl acrylate and ethyl acrylate are preferable.
Specific examples of the methacrylate ester comonomer of the copolymer (B) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and the like, and among them, methyl methacrylate and ethyl methacrylate are preferable.
Specific examples of the vinyl carboxylate comonomer of the copolymer (B) include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate and the like, and among these, vinyl acetate is preferable.

Specific examples of the copolymer (B) include binary copolymers such as ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-maleic anhydride copolymer, ethylene- Examples thereof include a methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, an ethylene-ethyl methacrylate copolymer, and an ethylene-vinyl acetate copolymer.
Examples of terpolymers include ethylene-acrylic acid-methyl acrylate copolymer, ethylene-acrylic acid-ethyl acrylate copolymer, ethylene-acrylic acid-vinyl acetate copolymer, ethylene-methacrylic acid- Methyl methacrylate copolymer, ethylene-methacrylic acid-ethyl methacrylate copolymer, ethylene-methacrylic acid-vinyl acetate copolymer, ethylene-maleic anhydride-methyl acrylate copolymer, ethylene-maleic anhydride-acrylic Examples include ethyl acetate copolymer, ethylene-maleic anhydride-methyl methacrylate copolymer, ethylene-maleic anhydride-ethyl methacrylate copolymer, and ethylene-maleic anhydride-vinyl acetate copolymer.
Furthermore, the multi-component copolymer which combined said comonomer is also mentioned.
Among the above copolymers, in particular, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-maleic anhydride- A methyl acrylate copolymer, an ethylene-maleic anhydride-ethyl acrylate copolymer, an ethylene-maleic anhydride-methyl methacrylate copolymer, and an ethylene-maleic anhydride-ethyl methacrylate copolymer are preferred.

The content of the above-mentioned comonomer is preferably such that the amount of the polar group is 5 to 40% by weight. When the amount of the polar group is less than 5% by weight, the adhesion between the liner material and the reinforcing material becomes insufficient, and when it exceeds 40% by weight, the durability tends to decrease.
The copolymer (B) can be produced by a high-pressure radical polymerization method using a tubular reactor, an autoclave reactor or the like, but may be produced by ionic polymerization. Specifically, it can be produced according to the method for producing a copolymer described in Examples such as JP-A-60-240705 and JP-A-8-11680.

The copolymer (B) of the present invention preferably has a melt flow rate (MFR) of 0.01 to 100 g / 10 min measured at a temperature of 190 ° C. and a load of 2.16 kg, more preferably 0.02. From the viewpoint of moldability of the hollow container, it is desirable that it is ˜80 g / 10 minutes, more preferably 0.05 to 50 g / 10 minutes.
The MFR can be appropriately selected according to the molding method of the target pressure vessel. However, if the MFR is less than 0.01 g / 10 min, the fluidity is low and molding becomes difficult, and the molding resin pressure increases. Extrusion properties are reduced. If it exceeds 100 g / 10 minutes, impact properties and durability may be reduced. The MFR is measured according to JIS K6922-2 (temperature 190 ° C., load 2.16 kg).

(1-2) Polyethylene layer (II)
The polyethylene layer (II) constituting the laminate for a pressure vessel liner of the present invention is formed from polyethylene (A) having the following characteristics (i) to (iii).
Characteristic (i): Density is 0.900 to 0.970 g / cm ³ Characteristic (ii): Melt flow rate (MFR) measured at a temperature of 190 ° C. and a load of 2.16 kg is 0.01 to 100 g / 10 Characteristic (iii): The melting point peak on the high temperature side measured by DSC is 120 ° C. or higher. The technical significance of the above characteristics (i) to (iii) will be described below.

1. Characteristic (i)
The polyethylene (A) of the present invention refers to an ethylene homopolymer or a copolymer of ethylene and α-olefin, and has a density of 0.900 to 0.970 g / cm ³ , preferably a density of 0.905 to 0. A range of .965 g / cm ³ , more preferably 0.910 to 0.960 g / cm ³ is desirable for maintaining the shape of the container.
The density of the polyethylene (A) can be set according to the performance of the target pressure vessel, but if the density is less than 0.900 g / cm ³ , the rigidity is insufficient and the rigidity of the tank mouth portion is insufficient. In addition, if the density exceeds 0.970 g / cm ³ , the durability may decrease. The density is measured according to JIS K7112.

2. Characteristic (ii)
The polyethylene (A) of the present invention has a melt flow rate (MFR) measured at a temperature of 190 ° C. and a load of 2.16 kg of 0.01 to 100 g / 10 minutes, preferably 0.02 to 80 g / 10 minutes. More preferably, it is 0.05 to 50 g / 10 min from the viewpoint of moldability of the hollow container.
The MFR of polyethylene (A) can be set according to the molding method of the target pressure vessel, but if the MFR is less than 0.01 g / 10 min, the fluidity is low and molding becomes difficult, and the molding resin Pressure rises and extrusion characteristics decrease. If it exceeds 100 g / 10 minutes, impact properties and durability may be reduced. The MFR is measured according to JIS K6922-1 (temperature 190 ° C., load 2.16 kg).

3. Characteristics (iii)
The polyethylene (A) of the present invention has a peak temperature on the high temperature side measured by differential scanning calorimetry (DSC) of 120 ° C. or higher, preferably 125 ° C. or higher. Satisfying this requirement is desirable from the viewpoint of shape retention and heat resistance of the container, particularly from the viewpoint of shape retention during winding of the reinforcing material to the hollow container.
The peak temperature on the high temperature side measured by DSC is an index of the crystallization temperature. By setting the peak temperature on the high temperature side to 120 ° C. or higher, the shape of the container at the time of molding can be reliably maintained. If it is less than 0 ° C., the container shape at the time of molding tends to be difficult to maintain sufficiently.
In order to set the peak temperature on the high temperature side of DSC to 120 ° C. or higher, it is important to select a material having a melting point of 120 ° C. or higher. Don't be.
DSC means differential scanning calorimetry, and is measured using a differential scanning calorimeter to measure crystallization temperature, crystallinity, and the like. DSC is a measurement based on a method that records the energy required to keep the temperature difference between the two to zero while the sample and reference material are adjusted under heating or cooling under equal conditions. Is done.
In the DSC measurement, the sample is placed in a flat metal container at the bottom, precisely weighed to obtain the sample amount, covered with a lid, installed in a measuring device, and the amount of heat change (ΔH) is measured over time. The peak temperature of is determined.

4). Polyethylene (A)
The polyethylene (A) of the present invention is an ethylene homopolymer or a copolymer of ethylene and an α-olefin.
The α-olefin of polyethylene (A) is preferably a linear or branched olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1- Examples include 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 polyethylene (A) of the present invention is not particularly limited to the production catalyst, process, etc. Non-patent document 1 (Critical book “Polyethylene Technology Reader” (written by Kazuo Matsuura and Naotaka Mikami, published by the Industrial Research Council, 2001) P. 123-160, p. 163-196, etc.). In other words, it can be manufactured with various polymerization reactors, polymerization conditions, and catalysts in each polymerization mode of Ziegler catalyst, chromium catalyst, single site catalyst, etc., slurry method, solution method, gas phase method. is there.

(1-3) Layer Configuration The synthetic resin liner material of the present invention includes the specific thermoplastic resin layer (I) and the specific polyethylene layer (II) described above. It is important that the thickness ratio of the plastic resin layer (I) is 1 to 90% and the thickness ratio of the polyethylene layer (II) is 99 to 10%. If the thickness ratio of the thermoplastic resin layer (I) is less than 1% and the thickness ratio of the polyethylene layer (II) exceeds 99%, there is a problem that it is difficult to maintain the layer configuration or the adhesive strength cannot be secured. On the other hand, if the thickness ratio of the thermoplastic resin layer (I) exceeds 90% and the thickness ratio of the polyethylene layer (II) is less than 10%, there is a problem that the shape at the time of winding cannot be maintained.

Moreover, the synthetic resin liner material of this invention may be comprised from the said composite material of the thermoplastic resin.
Examples of the composite material and the laminated material include composite materials in which engineering plastics, metal members, inorganic fillers, and the like are dispersed in the thermoplastic resin. The laminated material may be a laminated body having a multilayer structure including a thermoplastic resin layer / adhesive layer / barrier layer.
The engineering plastics include various polyamide (PA) resins such as nylon 6, nylon 6,6, nylon 11 and nylon 12, various hydroxyl group-containing resins such as ethylene-vinyl alcohol copolymer (EVOH) and polyvinyl alcohol (PVA). , Various polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-styrene copolymer resin (AS), polycarbonate (PC) resin, polyacetal (POM) resin, polyphenylene ether (PPE) resin, polyphenylene sulfide (PPS) resin, aromatic polyester resin (liquid crystal resin), and the like.
Moreover, as said metal member, metals, such as iron, aluminum, copper, tin, zinc, nickel, titanium, and various alloys containing these are mentioned.
In addition, examples of the inorganic filler include talc, silica, calcium carbonate, mica, and the like. When ensuring rigidity, fine powder talc having a plate-like crystal structure with an average particle size of 0.5 to 10 μm Fine powder mica is preferred.

As a synthetic resin liner material having a laminated structure, the thermoplastic resin layer (I) / polyethylene layer (II) / adhesive layer / barrier layer structure, thermoplastic resin layer (I) / polyethylene layer (II) / Structure of adhesive layer / barrier layer / adhesive layer / thermoplastic resin layer (I), thermoplastic resin layer (I) / polyethylene layer (II) / regrind layer / adhesive layer / barrier layer / adhesive layer / The structure of the thermoplastic resin layer (I) can also be applied to the pressure vessel.
Examples of the material suitably used for the barrier material layer include polyamide resin, polyester resin, ethylene-vinyl alcohol copolymer, polyvinyl alcohol resin, polyacrylonitrile resin, and the like.
As the adhesive layer used here, a known adhesive resin such as a thermosetting resin such as an epoxy resin or a polyurethane resin can be used, and an adhesive described in JP-A-2008-164131 is used. You can also.
When these synthetic resin liner materials are used as containers, they can be produced by a molding method such as a blow molding method, an injection molding method, a rotational molding method, or a compression molding method. Of these, the blow molding method is preferred.

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

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

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

(3) Base Member The base member of the present invention is installed for mounting a nozzle for filling and discharging high pressure gas. For example, one having a disk shape at one end is provided at least one end of a cylindrical container composed of a hollow container inside the pressure vessel and an outer pressure-resistant reinforcing material layer. In the hemispherical shoulder portion, the disc portion of the die member is inserted so as to be embedded, and preferably, the disc portion of the die member and the innermost layer adhesive of the hollow container, which has been subjected to roughening or ground treatment in advance. The layers can be brought into contact and bonded or welded.

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

3. Manufacturing method of pressure vessel The manufacturing method of the pressure vessel of the present invention will be specifically described in detail below.
The pressure vessel according to the present invention is formed of a hollow container (inner wall) formed of a synthetic resin liner material (inner layer is a polyethylene layer and outer layer is a thermoplastic resin layer), and a reinforcing material on the outer layer of the hollow container. A reinforcing member layer (outer wall), and at least one end of the hollow container has a cap member for attaching a nozzle for filling and discharging a high-pressure gas, and the thermoplastic resin of the hollow container And the reinforcing material are bonded or welded together.

An example of a preferred production method of the present invention is as follows.
Above and below the support part associated with the support for molding, a base member that is preferably surface-treated or ground-treated in advance is supported, and is composed of an inner layer of a polyethylene layer and an outer layer of a thermoplastic resin layer from a multilayer die of a blow molding machine A cylindrical parison formed of a synthetic resin liner material is extruded, and the parison is suspended so as to cover the disk portion of the die member between the molds. Next, the mold is closed while the parison is still sufficiently soft, the diameter of the parison is reduced, the neck portion of the base member is pinched simultaneously with the parison, and blown up to expand the parison and press it against the inner wall of the mold. To form a hollow container.
On the other hand, the synthetic resin liner material and the disk portion of the base member are pressed and brought into close contact with each other by internal pressure, and are bonded or fused to produce a hollow container with a base member. Next, the outer periphery of the hollow container is covered with carbon fiber yarns or bundles, fiber yarns such as glass fiber yarns or bundles, bundles, mats, etc. impregnated with a thermosetting resin such as epoxy resin or unsaturated polyester resin. Then, the pressure vessel is manufactured by forming a fiber reinforcing material (CFRP, GFRP, etc.) layer by curing.

  In the method for manufacturing a pressure vessel according to the present invention, the method for manufacturing a hollow container and an adhesive layer formed of a synthetic resin liner is not limited to the above blow molding method, but includes injection molding, rotational molding, compression molding, and the like. However, it is possible to integrate the base member at the same time as the formation of the hollow container and the adhesive layer at the time of manufacturing, the manufacturing process is simple, the manufacturing cost is low, and it is economical. It is also possible to do.

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 reinforcing material and the hollow container formed of the synthetic resin liner material and excellent airtightness.

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

1. Measurement method (1) Density: Measured according to JIS K7112 (unit: g / cm ³ ).
(2) Melt flow rate (MFR): Measured according to JIS K6922-1 (temperature 190 ° C., load 2.16 kg) (unit: g / 10 minutes).
(3) Peak temperature on the high temperature side measured by differential scanning calorimetry (DSC):
Measurement was performed using a differential scanning calorimeter. The sample and reference material were placed under equal conditions while being adjusted by heating or cooling, and the energy required to keep the temperature difference between the two at zero was measured based on the principle of recording against time or temperature. In the DSC measurement, the sample is placed in a flat metal container at the bottom, precisely weighed to obtain the sample amount, covered with a lid, installed in a measuring device, and the amount of heat change (ΔH) is measured over time. The peak temperature of was determined.
(4) Ratio of insoluble component at 100 ° C. or higher as measured by DSC:
In the DSC measurement, the sample was put in a flat metal container, and precisely weighed to determine the amount of the sample. Then, the sample was covered with a lid, installed in a measuring apparatus, and the amount of change in heat (ΔH) was determined over time. Measure the calorie change (ΔHw) of the DSC of the thermoplastic resin composition sample at 100 ° C. or more and the calorie change (ΔHa) of the DSC of the sample of only the polyethylene (A) as a component of the composition, It calculated | required as a ratio (percentage) of (DELTA) Hw / (DELTA) Ha.
(5) Amount of polar group:
It calculated | required from the quantity of the radically polymerizable acid comonomer, the acrylic ester comonomer, the methacrylic ester comonomer, the carboxylic acid vinyl ester comonomer, etc. which were used when manufacturing the thermoplastic resin.
(6) Adhesive strength:
Measured according to the cross-cut method of JIS K5600-5-6, classifications 0 to 2 (good and markedly superior) were marked with ◯, and classifications 3 to 5 were marked with x.
(7) Shape retention:
A small hollow container having a liner thickness of 1 mm and an internal volume of 500 ml is molded, and after the container is stored in an atmosphere of 100 ° C. for 1 hour, the container shape is not deformed (good and remarkably excellent) ) Was marked with ○, and the others were marked with ×.

2. Raw material used [Copolymer (B) of thermoplastic resin layer (I)]
CP (1): ethylene-methyl acrylate copolymer, density = 0.944 g / cm ³ , MFR (temperature 190 ° C., load 2.16 kg) = 2.0 g / 10 min, methyl acrylate content = 24 weight % (Methoxycarbonyl group content = 16.5% by weight)
CP (2): ethylene-ethyl acrylate copolymer, density = 0.934 g / cm ³ , MFR (temperature 190 ° C., load 2.16 kg) = 5.0 g / 10 min, ethyl acrylate content = 20 weight % (Ethoxycarbonyl group content = 14.6% by weight)
CP (3): ethylene-vinyl acetate copolymer, density = 0.938 g / cm ³ , MFR (temperature 190 ° C., load 2.16 kg) = 1.5 g / 10 min, vinyl acetate content = 15 wt% ( Meacetyloxy group content = 10.3 wt%)
CP (5): Composition in which CP (1) 25 wt% and PE (1) 75 wt% are mixed, density = 0.944 g / cm ³ , MFR (temperature 190 ° C., load 2.16 kg) = 0.1 g / 10 minutes, methyl acrylate content = 6% by weight (methoxycarbonyl group content = 4.1% by weight)
CP (6): Maleic anhydride-modified polyethylene, density = 0.933 g / cm ³ , MFR (temperature 190 ° C., load 2.16 kg) = 0.5 g / 10 minutes, maleic anhydride graft monomer amount = 0.5 weight % (Carboxylic anhydride group content = 0.34% by weight)
[Polyethylene layer (II) polyethylene (A)]
PE (1): ethylene / 1-hexene copolymer, density = 0.945 g / cm ³ , MFR (temperature 190 ° C., load 2.16 kg) = 0.03 g / 10 min PE (3): ethylene-propylene- 1-hexene copolymer, density = 0.901 g / cm ³ , MFR (temperature 190 ° C., load 2.16 kg) = 2.0 g / 10 min PE (4): ethylene-1-hexene copolymer, density = 0.918 g / cm ³ , MFR (temperature 190 ° C., load 2.16 kg) = 2.0 g / 10 min

(Examples 1-6, Comparative Examples 1-4)
Using the thermoplastic resin shown in Table 1, a small hollow container having a thickness of 1 mm and an internal volume of 500 ml was formed as a liner material. The evaluation results as a liner material are shown in Table 1.

(Example 7)
[Manufacture of pressure vessels]
Using the laminates of Examples 1 to 6 of the present application as a liner material, a pressure vessel was produced according to the method for producing a pressure vessel described in Examples of Japanese Patent Application Laid-Open No. 2008-164131 as described below. .
A base member coated with an adhesive on a part of the surface is inserted above and below the support part, the base member is installed, and using a NB150 continuous hollow molding machine manufactured by Nippon Steel Works, a molding temperature of 210 ° C. and a blow pressure of 1. A cylindrical parison formed of a thermoplastic resin layer is extruded from a die of a blow molding machine under conditions of 4 MPa, a mold temperature of 20 ° C., and a blowing time of 130 seconds, and drooped between the molds, and the parison is still sufficiently soft. The mold is closed, the diameter of the parison is reduced, the neck of the base part material is pinched simultaneously with the parison, and a gas such as air is blown to press the parison against the mold wall. A formed hollow container was formed. On the other hand, the shoulder portion of the liner material and the base member were pressed against the inner shoulder portion of the synthetic resin liner material by internal pressure and fused to produce a hollow container having a layer thickness of 0.3 mm and a volume of 30 liters. Next, the outer periphery of the hollow container was impregnated with a thermosetting resin epoxy resin, wound with a carbon fiber bundle, heated and pressed to impregnate the hollow container and the epoxy resin with a carbon fiber fiber reinforcement ( CFRP) was fused, the epoxy resin was cured to form a reinforcing material layer, and a pressure vessel was manufactured.
As a result, a pressure vessel having a good appearance was obtained.

As is clear from the results shown in Table 1, in Examples 1 to 6 in which the laminate satisfying the requirements of the present invention was used as the liner material, the adhesive strength with the reinforcing material was remarkably improved and the shape was maintained during molding. As a result, the pressure difference between the conventional reinforcing material and the fiber does not occur, and the fiber can be wound uniformly, so that not only the reinforcing effect is improved, but also a pressure vessel having a good appearance is obtained.
On the other hand, in Comparative Examples 1 to 4 in which a laminate that does not satisfy some or all of the requirements of the present invention was used as a liner material, a significant problem occurred in terms of shape retention and adhesive strength.

  According to the pressure vessel (pressure vessel) and the manufacturing method thereof of the present invention, the adhesive strength with the reinforcing material on the outer surface of the hollow container formed of the synthetic resin liner material can be remarkably improved, and the reinforcing material layer The pressure vessel having a beautiful and strong reinforcing layer can be provided. Therefore, the pressure vessel (pressure vessel) of the present invention is, for example, a domestic liquefied petroleum gas vessel, an automotive liquefied petroleum gas vessel, a compressed natural gas (CNG), an industrial pressure for storing oxygen, nitrogen, or the like. It is particularly suitable as a container, a hydrogen tank for a fuel cell, etc., and its industrial value is extremely large.

Claims (5)

A laminate for a pressure vessel liner comprising a thermoplastic resin layer (I) having the following characteristics (1) to (3) and a polyethylene layer (II) having the following characteristics (i) to (iii):
The thermoplastic resin layer (I) comprises at least one copolymer selected from the group consisting of an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-vinyl acetate copolymer. Including
A laminate for a pressure vessel liner, wherein the thermoplastic resin layer (I) has a thickness ratio of 1 to 90% and the polyethylene layer (II) has a thickness ratio of 99 to 10%.
Characteristic (1): Density is 0.900 to 0.970 g / cm ³ Characteristic (2): Melt flow rate (MFR) measured at a temperature of 190 ° C. and a load of 2.16 kg is 0.01 to 100 g / 10 Characteristic (3): The amount of polar groups is 4 to 32% by weight Characteristic (i): Density is 0.900 to 0.970 g / cm ³ Characteristic (ii): Temperature 190 ° C., load 2 Melt flow rate (MFR) measured at .16 kg is 0.01 to 100 g / 10 min. Characteristic (iii): High temperature side melting point peak measured by DSC is 120 ° C. or higher. A pressure vessel having a hollow container formed of a 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 pressure vessel according to claim 1 , wherein the liner material is the laminate according to claim 1 . The pressure vessel according to claim 2, wherein the thermoplastic resin layer (I) of the liner material is disposed so as to be in contact with the reinforcing material. The pressure vessel according to claim 2 or 3, wherein the reinforcing material is a fiber reinforcing material. A hollow container formed of the pressure vessel liner laminate according to claim 1, and a reinforcing material layer formed of a reinforcing material provided on an outer layer of the hollow container, and at least one cap member is A method for manufacturing a pressure vessel, comprising:
A method for producing a pressure vessel, comprising: providing a reinforcing material layer on an outer layer of the hollow container, and bonding or welding the reinforcing material to the thermoplastic resin layer (I).