JP2020158780A - Tow prepreg and method for manufacturing composite material reinforced pressure container - Google Patents

Abstract

To provide a tow prepreg that is, due to the matrix resin composition that can be easily impregnated into the reinforcing fiber bundle, excellent in unwinding property from the spool, process passability in the FW process, and shape retention.SOLUTION: In the tow prepreg of the present invention, a matrix resin composition containing a component (A): an epoxy resin, a component (B): an epoxy resin curing agent, and a component (C): a particulate vinyl chloride-based copolymer is impregnated into a reinforced fiber bundle, in which the component (C) is not dissolved in the matrix resin composition containing the component (C).SELECTED DRAWING: None

Description

The present invention relates to a tow prepreg, a composite material reinforced pressure vessel and a method for manufacturing the same, and can be suitably used for, for example, a pressure vessel and general industrial applications such as sports equipment, automobiles, aircraft, and tension materials. It relates to a tow prepreg, a composite material reinforced pressure vessel and a method for manufacturing the same.

A pressure vessel in which a tank liner (hereinafter referred to as "liner") is reinforced with a fiber-reinforced composite material is used for a storage tank for compressed natural gas or hydrogen mounted on a moving body such as an automobile because of its light weight. Examples of the reinforcing fibers used in the fiber-reinforced composite material include glass fibers and carbon fibers. Among them, carbon fiber has a great merit of reducing the weight of the pressure vessel because of its high specific strength, and is particularly preferably used for a hydrogen storage tank which requires higher pressure resistance than a compressed natural gas storage tank.

A pressure vessel using a fiber-reinforced composite material (hereinafter, may be referred to as a “composite material-reinforced pressure vessel”) is generally manufactured by filament winding (FW) molding. In FW molding, a matrix resin composition is supplied to a bundle of reinforcing fibers in which one or a plurality of fibers are aligned, impregnated, wound around a mandrel such as a rotating liner at a predetermined tension and angle, and then the resin composition is wound. This is a molding method for curing a matrix resin composition. In many cases, the step of supplying the matrix resin composition to the reinforcing fiber bundle and impregnating it (impregnation step) is followed by a step of winding the matrix resin composition around a mandrel such as a rotating liner (FW step).

Further, immediately before the FW step, instead of supplying the reinforcing fiber bundle with the matrix resin composition and impregnating it, a tow prepreg in which the reinforcing fiber bundle is impregnated with the matrix resin composition is prepared in advance, and this is used in the FW step. It can also be used. In this case, the tow prepreg is wound around the rotating mandrel with a predetermined tension and angle.

Various advantages can be obtained by using toe prepreg in FW molding. For example, if a tow prepreg is used, the working environment can be improved because it is not necessary to handle the uncured matrix resin composition in the manufacturing process of the pressure vessel. In addition, since it does not have an impregnation step, the process speed of the FW step can be improved. Further, by using a tow prepreg in which the content of the matrix resin composition is controlled, a stable and high-performance molded product can be obtained.

Normally, the tow prepreg is wound on a bobbin such as a paper tube, and when used, it is unwound from the wound state. At this time, the tack (stickiness) of the toe prepreg must be weak in order to unravel at high speed. One of the methods for weakening the tack of the tow prepreg is a method of using a low-viscosity resin composition as the matrix resin composition to be impregnated in the reinforcing fiber bundle (Patent Document 1). Further, as a method of weakening the tack of the toe prepreg and maintaining the flexibility of the toe prepreg, there is a method of increasing the viscosity of the matrix resin composition to such an extent that it is not sticky at the operating environment temperature (usually room temperature) of the toe prepreg. (Patent Document 2).

Japanese Unexamined Patent Publication No. 9-087365 Japanese Unexamined Patent Publication No. 55-015870

The following characteristics are required in manufacturing products such as pressure vessels from tow prepreg. That is, the reinforcing fiber bundle is sufficiently impregnated with a predetermined amount of the matrix resin composition, it can be unwound at high speed from the state of being wound on the spool, and the toe prepreg is wound around the liner while being folded during the FW process. It is required to have excellent morphological retention so as not to cause problems such as being squeezed, and to have process passability in which the reinforcing fiber bundle does not get scratched when passing through a guard, a roll or the like in the FW process.

However, if the matrix resin composition having a low viscosity is simply used as in the technique described in Patent Document 1, the toe prepreg is folded by a guide roll or the like during the FW process, and its form is significantly changed. In some cases.

Normally, the toe prepreg is wound around a paper tube by applying a tension of several hundred g to 1 kg. At this time, the matrix resin composition is squeezed out from the toe prepreg, and the other side of the toe prepreg is located on the paper tube side. There is also a problem that the content of the matrix resin composition is higher in the toe prepreg located on the (outer peripheral side) (hereinafter, the phenomenon is referred to as "winding").

On the other hand, it is difficult to sufficiently impregnate the reinforcing fiber bundle with the high-viscosity matrix resin composition or the like described in Patent Document 2. In Patent Document 2, the matrix resin composition is dissolved in a solvent, impregnated into the reinforcing fiber bundle, and then heated and dried to remove the solvent. However, in this method, the solvent is small in the obtained tow prepreg. It will remain. The remaining solvent causes voids in the fiber-reinforced composite material produced by using the tow prepreg, which causes a great decrease in strength and quality.

The present invention has been made in view of the above background, and a matrix resin composition that can be easily impregnated into a reinforcing fiber bundle is used to provide unwindability from a spool, process passability in a FW process, and shape retention. The challenge is to obtain an excellent toe prepreg.

In order to solve the above problems, as a result of diligent studies, the present inventors have found that the above problems can be solved by using a tow prepreg that satisfies a specific condition, and have reached the present invention.

That is, the tow prepreg according to the present invention is obtained by impregnating a reinforcing fiber bundle with a matrix resin composition containing the following components (A), component (B) and component (C).
Component (A): Epoxy resin component (B): Epoxy resin curing agent component (C): Particulate vinyl chloride-based copolymer.

A composite material in which a reinforcing fiber bundle containing the following component (A), component (B) and component (C') is impregnated and the matrix resin composition is cured is used as a reinforcing layer. Reinforced pressure vessel.
Component (A): Epoxy resin component (B): Epoxy resin curing agent component (C'): Vinyl chloride-based copolymer.

Further, the method for producing a composite material reinforced pressure vessel according to the present invention includes an impregnation step of impregnating a reinforcing fiber bundle with a matrix resin composition containing the following components (A), components (B) and components (C), and a matrix resin. A filament winding process in which the reinforcing fiber bundle impregnated with the composition is wound around the liner, and a mat that heats the liner around which the reinforcing fiber bundle is wound and impregnates the reinforcing fiber bundle.
It includes a curing step of curing the Rix resin composition.
Component (A): Epoxy resin component (B): Epoxy resin curing agent component (C): Particulate vinyl chloride-based copolymer.

According to the present invention, the matrix resin composition that can be easily impregnated into the reinforcing fiber bundle has an effect that it is possible to provide a tow prepreg having excellent unwinding property from a spool, process passability in a FW process, and shape retention. Play.

It is a graph which showed the relationship between the heating temperature and the increase in viscosity in the form which adopted the paste vinyl chloride resin as a component (C).

<Toup prepreg>
The tow prepreg according to the present invention is obtained by impregnating a reinforcing fiber bundle with a matrix resin composition containing the following components (A), component (B) and component (C).
Component (A): Epoxy resin component (B): Epoxy resin curing agent component (C): Particulate vinyl chloride-based copolymer.

Component (C): The particulate vinyl chloride-based copolymer is present as particles in the matrix resin composition at room temperature. The particles have the effect of preventing the single fibers from being densely packed together. This makes it possible to increase the volume of the voids in the reinforcing fiber bundle and to include more matrix resin compositions in the reinforcing fiber bundle. Therefore, the reinforcing fiber bundle can be easily impregnated with a sufficient amount of the matrix resin composition.

Further, since it is possible to include a larger amount of the matrix resin composition in the reinforcing fiber bundle, the matrix resin composition exposed on the surface layer of the tow prepreg can be reduced. By reducing the matrix resin composition exposed on the surface layer of the toe prepreg, the tack of the toe prepreg can be suppressed. Since the tack is suppressed in this way, it is possible to provide a toe prepreg having excellent unwindability from the spool, process passability in the FW process, and morphological retention.

Toup prepreg is obtained by impregnating a reinforcing fiber bundle in which thousands to tens of thousands of reinforcing fiber filaments are arranged in one direction with a matrix resin composition, and then winding this on a bobbin such as a paper tube. It is a narrow intermediate base material to be used. In the present specification, the one wound around the bobbin or the one unwound after being wound is called "toup prepreg", and is simply a bundle of reinforcing fibers impregnated with a matrix resin composition. Is called a "resin-impregnated reinforcing fiber bundle". That is, the "resin-impregnated reinforcing fiber bundle" also includes the reinforcing fiber bundle unwound from the tow prepreg and impregnated with the matrix resin composition.

The tow prepreg according to the present invention can be obtained by impregnating a reinforcing fiber bundle with a matrix resin composition described later. The fiber diameter and the number of filaments constituting the reinforcing fiber bundle are not particularly limited, but the fiber diameter is preferably 3 μm or more, preferably 100 μm or less, and the number is 1,000 or more. It is preferable that the number is 70,000 or less. In addition, the "fiber diameter" in this specification is the diameter corresponding to the equivalent area circle of the cross section of each fiber.

Sufficient strength can be obtained if the fiber diameter is 3 μm or more. For example, in various processing processes, the filament moves laterally on the surface of a roll, bobbin, etc. (movement in a direction orthogonal to the fiber length direction. The same applies hereinafter). It is possible to prevent cutting and fluffing from occurring when the problem occurs. When the fiber diameter is 100 μm or less, the filament has flexibility and therefore has good flexibility.

The reinforcing fiber bundle in the present invention is used for ordinary fiber-reinforced composite materials such as glass fiber, carbon fiber (in the present invention, graphite fiber is also included in carbon fiber), aramid fiber, and boron fiber. Reinforcing fibers can be used. Of these, carbon fibers having a strand strength of 3500 MPa or more, more preferably carbon fibers having a strand strength of 4500 MPa or more, and even more preferably carbon fibers having a strand strength of 5000 MPa or more, in accordance with JIS R 7601. In particular, when used as a pressure vessel or a tensioning material, the stronger the strand strength of the carbon fiber bundle used, the more preferable.

When the reinforcing fiber bundle is a carbon fiber bundle, the fiber diameter of the filament is preferably 3 μm or more, and preferably 12 μm or less. The number is preferably 1,000 or more, and preferably 70,000 or less. Sufficient strength can be obtained when the fiber diameter is 3 μm or more, and for example, when the filament causes lateral movement on the surface of a roll, spool, etc. in various processing processes, it suppresses cutting or fluffing. it can. The upper limit is usually about 12 μm because carbon fibers can be easily produced.

Further, in the present specification, "epoxy resin" refers to a resin having one or more epoxy groups in the molecule.

<Unleashability of toe prepreg>
The method for producing the toe prepreg will be described later, but unlike the sheet-shaped prepreg, the toe prepreg is wound around a paper tube or the like as it is without being covered with a film or a release paper, like a glass fiber bundle or a carbon fiber bundle. You can take it and manufacture it. Then, the tow prepreg wrapped around a paper tube or the like may be unwound and used.

If the tack (stickiness) of the toe prepreg is too strong, there will be problems that the resistance at the time of unwinding is strong and it cannot be unraveled at high speed, or the single yarn of the reinforcing fiber bundle is taken and it cannot be unraveled well. The present invention can provide a toe prepreg with good tack.

<Morphological retention of toe prepreg>
Further, the tow prepreg is often wound around a paper tube while being reciprocated in the axial direction of the paper tube. Therefore, when unwinding, the position of the toe prepreg to be unwound moves in the axial direction of the paper tube, so it is necessary to use a guide for fixing the position of the toe prepreg. The shape of the guide used varies, but generally a roll or comb-like one having a groove in the circumferential direction on the surface and rotating freely is used. The unraveled toe prepreg is fixed in position by passing through the grooves on the roll surface or the teeth of the comb. The toe prepreg may fold when it comes in contact with the roll or comb, but if the toe prepreg has a strong tack, it will remain folded and will not open. Further, if the toe prepreg is too soft because the viscosity of the matrix resin composition is too low, the shape of the toe prepreg when it comes into contact with a roll or a comb may change. If the shape of the toe prepreg changes significantly, it may adversely affect the breaking pressure and pressure resistance cycle characteristics of the composite material reinforcing pressure vessel obtained by winding and curing the tow prepreg. However, according to the present invention, it is possible to provide a tow prepreg having excellent morphological retention. As used herein, the term "morphological retention" refers to the property of a toe prepreg to retain its morphology when it comes into contact with something else. For example, "excellent in morphology retention" means that the morphology does not easily collapse when in contact with another object, or that the morphology easily returns to the original morphology even if the morphology is deformed. "Inferior in retention" means that the form is liable to collapse when in contact with another object, or it is difficult to return to the original form after being deformed.

<Process passability of tow prepreg>
In the FW process, the toe prepreg is generally wound around the mandrel through a guide or some rolls. If the tack of the toe prepreg is too strong, the toe prepreg may be strongly rubbed on the roll surface or the like during the process, and the reinforcing fiber bundle may be damaged. If the reinforcing fiber bundle is flawed, it may adversely affect the fracture pressure and pressure resistance cycle characteristics of the composite material reinforcing pressure vessel produced by using the reinforcing fiber bundle. However, according to the present invention, it is possible to provide a tow prepreg having excellent process passability. As used herein, the term "process passability" refers to the property that the reinforcing fiber bundle is not easily damaged when passing through the apparatus used for the processing in the process of processing the tow prepreg. For example, "excellent in process passability" means that damage is unlikely to occur when passing through an apparatus for a process such as processing, and "poor in process passability" means a process such as processing. It means that damage is likely to occur when passing through the device for.

<Tack of tow prepreg>
The tack of the toe prepreg can be expressed by the average maximum stress value. The stress value means the tensile stress generated on the contact surface between the plunger and the sample, and the average maximum stress value is a value obtained by the tack test described below.

(Tack test)
Equipment: Tuck tester TA-500 (manufactured by UBM Co., Ltd.)
Contact area of the plunger with the sample: Approximately 3.1 cm ²
Plunger pressing time: 10 seconds Plunger pressing pressure: 90,000 Pa
Plunger rising speed: 1 mm / sec Measurement environment temperature: 23 ° C
Measurement environment humidity: 50% RH
procedure:
(1) Place the toe prepreg on the sample table and fix it. At this time, the surface of the toe prepreg that comes into contact with the plunger is the inner surface (that is, the surface on the paper tube side) when the toe prepreg is wound around the paper tube.
(2) Apply a pressure of 90,000 Pa to the plunger and press it against the toe prepreg for 10 seconds.
(3) Raise the plunger at 1 mm / sec.
(4) The maximum value of the stress value while raising the plunger is set as the maximum stress value, and the average value of the obtained maximum stress values is set as the average maximum stress value after measuring three times in total.

The average maximum stress value in the tow prepreg according to the present invention is preferably 2 kPa or more, more preferably 10 kPa or more, more preferably 65 kPa or less, and even more preferably 50 kPa or less. By making it larger than 2 kPa, it is possible to have an appropriate adhesiveness to the mandrel in the FW process, and it is possible to avoid problems such as slipping when winding the mandrel. Further, by making the average maximum stress value smaller than 65 kPa, high-speed unwinding from bobbin winding becomes possible, and it is possible to prevent the toe prepreg after unwinding from being wound around the liner while being folded.

<Viscosity of matrix resin composition at ambient temperature using toe prepreg>
A major factor that affects the strength of the tack of the tow prepreg is the viscosity of the matrix resin composition contained in the tow prepreg. In particular, the viscosity of the matrix resin composition at the ambient temperature at which the tow prepreg is used has a great influence on the tack of the tow prepreg. The viscosity of the matrix resin composition at 30 ° C. is preferably 3 Pa · sec or more in order to obtain a tow prepreg having excellent unwindability from the spool, process passability in the FW process, and morphological retention. -It is more preferably sec or more, more preferably 300 Pa · sec or less, and even more preferably 200 Pa · sec or less.

By setting the viscosity of the matrix resin composition at 30 ° C. to 300 Pa · sec or less, the tack of the tow prepreg does not become too strong. Further, since the tow prepreg has an appropriate drape property, it can be wound around the liner without forming a gap between adjacent toe prepregs. Further, by setting the viscosity of the matrix resin composition at 30 ° C. to 3 Pa · sec or more, the tow prepreg containing the matrix resin composition has an appropriate tack and can have an appropriate adhesiveness to the mandrel. Problems such as slipping during winding can be avoided. Further, since the toe prepreg does not become too soft, it is possible to prevent the shape of the toe prepreg from changing when passing through the guide in the FW process.

However, even if the viscosity of the matrix resin composition at 30 ° C. is 3 Pa · s or more and 300 Pa · s or less, if the matrix resin composition does not contain the component (C) particulate vinyl chloride copolymer. Since the influence of the surface tension of the matrix resin composition becomes large, the morphological retention property, process passability, and unraveling property of the above-mentioned tow prepreg are deteriorated.

<Contents of matrix resin composition>
Another major factor that affects the strength of the toe prepreg tack is the content of the matrix resin composition.

The content of the matrix resin composition in the tow prepreg according to the present invention is preferably 20% by mass or more, and preferably 40% by mass or less. When the content is 20% by mass or more, a sufficient amount of the matrix resin composition can be easily distributed in the reinforcing fiber bundle, and it is possible to prevent a large number of voids from being generated in the molded product. By setting the content of the matrix resin composition to 40% by mass or less, it is possible to prevent the tack from becoming too strong. Further, since the fiber-containing volume fraction of the fiber-reinforced composite material can be increased, desired mechanical properties can be effectively exhibited. The content of the matrix resin composition in the tow prepreg should be 20% by mass or more and 30% by mass or less in order to have better unresolvability, process passability, and morphological retention, and to more effectively exhibit mechanical properties. Is more preferable.

<Matrix resin composition>
The matrix resin composition contained in the tow prepreg according to the present invention and the matrix resin composition used in the method for producing a composite material reinforced pressure vessel according to the present invention described later contain the following components (A) to (C). ..

Component (A): Epoxy resin Component (B): Epoxy resin curing agent Component (C): Particulate vinyl chloride-based copolymer.

<Ingredient (A)>
The component (A) may be an epoxy resin.

Among the epoxy resins, it is preferable to mainly use a bifunctional epoxy resin having an aromatic ring in the molecule as the component (A). By using a bifunctional epoxy resin having an aromatic ring in the molecule, the viscosity of the matrix resin composition can be adjusted to an appropriate range, and the mechanical properties of the cured product can be adjusted to an appropriate range. be able to. In addition, "mainly" means that the amount is the largest, and here, the component (A) is a bifunctional epoxy resin alone, or when a plurality of types of epoxy resins are contained, a bifunctional epoxy. It means that it is preferable to use the largest amount of resin.

Further, in the present specification, the "bifunctional epoxy resin" means a compound having two epoxy groups in the molecule.

Examples of the aromatic ring in the bifunctional epoxy resin having an aromatic ring in the molecule include a benzene ring, a naphthalene ring, a fluorene ring and the like.

Examples of the bifunctional epoxy resin having an aromatic ring in the molecule include bisphenol A diglycidyl ether type epoxy resin, bisphenol F diglycidyl ether type epoxy resin, bisphenol S diglycidyl ether type epoxy resin, and resorcin diglycidyl ether type. Epoxy resin, hydroquinone diglycidyl ether type epoxy resin, terephthalic acid diglycidyl ester type epoxy resin, bisphenoloxyethanol full orange glycidyl ether type epoxy resin, bisphenol full orange glycidyl ether type epoxy resin, bisphenol full orange glycidyl ether type epoxy resin, Novorak Examples thereof include, but are not limited to, glycidyl ether type epoxy resin and hexahydrophthalic acid glycidyl ester. Further, only one type of epoxy resin may be used, or two or more types of epoxy resins may be used in combination.

Among bifunctional epoxy resins having an aromatic ring in the molecule, the viscosity of the matrix resin composition can be adjusted to an appropriate range, and the mechanical properties of the cured product can be adjusted to an appropriate range. From the point of view, a liquid bisphenol A diglycidyl ether type epoxy resin having an epoxy equivalent of 170 g / eq or more and 200 g / eq or less is particularly preferable.

In addition to the bisphenol A diglycidyl ether type epoxy resin, various epoxy resins can be used for the purpose of improving heat resistance and adjusting the viscosity. For example, a trifunctional or higher functional epoxy resin, an epoxy resin having an aliphatic skeleton, and the like can be mentioned.

Examples of the trifunctional epoxy resin include a triazine skeleton-containing epoxy resin, an aminophenol type epoxy resin, and an aminocresol type epoxy resin.

Examples of the tetrafunctional or higher functional epoxy resin include a cresol novolac type epoxy resin, a phenol novolac type epoxy resin, and an aromatic glycidylamine type epoxy resin.

Examples of the epoxy resin having an aliphatic skeleton include cyclohexanedimethanol diglycidyl ether, butanediol diglycidyl ether, and hexahydrophthalic acid diglycidyl ester.

<Ingredient (B)>
The component (B) may be an epoxy resin curing agent. The epoxy resin curing agent may generally have any structure as long as it can cure the epoxy resin. Examples thereof include amines, acid anhydrides (carboxylic acid anhydrides), phenols (novolak resins and the like), mercaptans, amine Lewis acid complexes, onium salts, imidazoles and the like. Among these, acid anhydrides and amine Lewis acid complexes are preferable because they can be uniformly compatible with the matrix resin composition and have excellent pot life.

Examples of the acid anhydride include hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride and the like.

Examples of the amine leasate complex include a boron halide amine complex, and specifically, for example, a boron trifluoride / piperidine complex, a boron trifluoride / monoethylamine complex, and a boron trifluoride / triethanol. Examples thereof include a boron trifluoride amine complex such as an amine complex and a boron trifluoride amine complex such as a boron trifluoride / octylamine complex. Among these amine ruisate complexes, the boron trichloride amine complex is particularly preferable in that it has excellent solubility in an epoxy resin, excellent pot life when used as a matrix resin composition, and excellent curability.

<Component (C)>
The component (C) may be a particulate vinyl chloride-based copolymer. The component (C) is not dissolved in the matrix resin composition containing the component (C), and remains in the reinforcing fiber bundle in the form of particles even after the reinforcing fiber bundle is impregnated with the matrix resin composition.

As the particulate vinyl chloride-based copolymer of the component (C), a so-called paste vinyl chloride resin in the form of particles is preferable. The paste vinyl chloride resin has a property of becoming a paste (vinyl chloride sol) when mixed with a plasticizer, a stabilizer, or the like. Examples of the method for producing the paste vinyl chloride resin include emulsion polymerization, microsuspension polymerization, or seed emulsion polymerization and seed microsuspension polymerization in which the particles obtained by the polymerization method are further enlarged as seed particles. Examples thereof include a method of producing by spray-drying the obtained vinyl chloride resin latex.

As described above, the paste vinyl chloride resin has the property of becoming a paste (vinyl chloride sol) when mixed with a plasticizer, stabilizer, etc., but it can also be heated by mixing with an epoxy resin to reduce its viscosity. Acts as a plasticizer and becomes a paste as well.

In the resin-impregnated reinforcing fiber bundle formed during the production of the tow prepreg and the composite material reinforced pressure vessel without using the toe prepreg, the paste vinyl chloride resin used as the particulate vinyl chloride-based copolymer of the component (C). Exists in the form of particles. By including the paste vinyl chloride resin existing as particles in the reinforcing fiber bundle, the effect of preventing the single fibers from being densely packed with each other can be obtained. This makes it possible to increase the volume of the voids in the reinforcing fiber bundle and to include more matrix resin compositions in the reinforcing fiber bundle. Therefore, the reinforcing fiber bundle can be easily impregnated with a sufficient amount of the matrix resin composition.

Further, if the reinforcing fiber bundle is impregnated with a sufficient amount of the matrix resin composition, the matrix resin composition exposed on the surface layer of the tow prepreg can be reduced. By reducing the matrix resin composition exposed on the surface layer of the toe prepreg, the tack of the toe prepreg can be suppressed. Since the tack is suppressed in this way, it is possible to provide a toe prepreg having excellent unwindability from a spool such as a paper tube, process passability in a processing process such as FW molding, and shape retention.

Further, the component (C) exists as particles at room temperature, and the matrix is present at a temperature higher than room temperature, more preferably at a temperature higher than the production temperature of the tow prepreg, and at a temperature lower than the curing temperature of the matrix resin composition. It is more preferable that the temperature is compatible with the component (A) in the resin composition. For example, the component (C) is swelled by the component (A) at such a temperature so that the component (C) and the component (A) are compatible with each other, or the component (C) is at such a temperature. It is more preferable that it is compatible with A). Further, it is more preferable that the substances are mixed more uniformly when they are compatible with each other. Since the component (A) and the component (C) can be cured in a sufficiently mixed state, a molded product can be satisfactorily produced. For example, it is possible to manufacture a composite material reinforced pressure vessel having stable quality and high breaking pressure. That is, as the tow prepreg according to the present invention, one that is compatible with the component (A) at a temperature higher than room temperature, more preferably higher than the production temperature of the tow prepreg and lower than the curing temperature of the matrix resin composition is used. Therefore, it is possible to use a tow prepreg having excellent unresolvability, process passability in the FW process, and morphological retention, and it is possible to provide an excellent composite material reinforced pressure vessel. Further, the above-mentioned paste vinyl chloride resin exists as particles at room temperature, but at a temperature higher than normal temperature, more preferably at a temperature higher than the production temperature of tow prepreg, the paste vinyl chloride resin is made of the epoxy resin of the component (A). Swells and becomes compatible with the epoxy resin of the component (A). The production temperature of the above-mentioned tow prepreg is, for example, the temperature at which the reinforcing fiber bundle is impregnated with the matrix resin composition, preferably 50 ° C. or higher and 150 ° C. or lower, and more preferably 80 ° C. or higher and 130 ° C. or lower. ..

The method for producing the tow prepreg and the method for producing the composite material reinforced pressure vessel will be described later, but when the matrix resin composition is supplied and impregnated into the reinforcing fiber bundle, it is added in order to lower the viscosity of the matrix resin composition. It is more preferable to warm it. When a paste vinyl chloride resin is used as the component (C), it is more preferable that the paste vinyl chloride resin does not form at the heating temperature. Specifically, 40 paste vinyl chloride resin-dispersed epoxy resins in which the paste vinyl chloride resin is uniformly dispersed in the liquid bisphenol A diglycidyl ether type epoxy resin having an epoxy equivalent of 170 g / eq or more and 200 g / eq or less. It is more preferable that the resin does not form a vinyl chloride sol even when heated in an environment of ° C. for 1 hour. By having this property, thickening of the matrix resin composition can be prevented during the production of the tow prepreg or the production of the composite material reinforcing pressure vessel, so that the matrix resin composition is supplied and impregnated into the reinforcing fiber bundle. It becomes easy.

Further, in order to obtain a desired molded product from the toe prepreg and the resin-impregnated reinforcing fiber bundle directly without going through the toe prepreg, for example, the matrix resin composition contained in the toe prepreg wound around the mandrel or the resin-impregnated reinforcing fiber bundle. Heat to cure. It is more preferable to confirm that the component (C) is compatible with the component (A) by this heating.

The method for confirming that the component (C) is compatible with the component (A) by heating is not particularly limited. For example, when a paste vinyl chloride resin is used as the component (C), the paste vinyl chloride resin is used. Whether or not it is compatible with the component (A) can be roughly determined by measuring the temperature-raising viscosity of the uncured matrix resin composition. Specifically, the temperature-increasing viscosity of the matrix resin composition is measured under the following conditions, and as shown in FIG. 1, the paste vinyl chloride resin is compatible with the component (A) until the viscosity increases due to the curing reaction. If the viscosity increases due to the above, it can be determined that the paste vinyl chloride resin is substantially compatible with the component (A) during heating and curing during molding.

[Measurement conditions for temperature rise viscosity of matrix resin composition]
Equipment: AR-G2 (manufactured by TA Instruments)
Plate used: 35 mmΦ Parallel plate Plate gap: 0.5 mm
Measurement frequency: 10 rad / sec Heating rate: 2 ° C / min Stress: 3000 dynes / cm ² .

Note that FIG. 1 is a graph showing the relationship between the heating temperature and the increase in viscosity in order to confirm that the paste vinyl chloride resin is used as the component (C) and is compatible with the component (A). is there. In FIG. 1, the solid line on the graph shows the relationship between the temperature and the viscosity of the matrix resin composition to which the paste PVC (vinyl chloride resin) is added as the component (C), and the broken line shows the matrix resin composition not containing the component (C). The relationship between the temperature and viscosity of an object is shown. As shown in FIG. 1, in the case of the matrix resin composition to which the paste PVC is added as the component (C), the paste vinyl chloride resin is at a temperature lower than the temperature at which the thickening occurs due to the curing reaction of the matrix resin composition. Causes an increase in viscosity due to the compatibility with the component (A).

The component (C) exists as particles at room temperature, and has a property of being compatible with the component (A) in the matrix resin composition at a temperature higher than room temperature and lower than the curing temperature of the matrix resin composition. If it is, it exists in the form of particles in the matrix resin composition at room temperature, that is, at a relatively low temperature. Therefore, the toe prepreg impregnated with the matrix resin composition does not have an excessively high surface tack, and as a result, a toe prepreg having excellent solvability and handleability can be obtained. Further, by producing the fiber-reinforced composite material using the material having the property as the component (C), the component (C) and the component (A) are sufficiently miscible, so that voids due to the presence of particles are produced. It is possible to obtain a high-strength molded product without the occurrence of. Therefore, the composite reinforced pressure vessel manufactured using the tow prepreg according to the present invention can also achieve a high breaking pressure.

As the component (C), as described above, a paste vinyl chloride resin is desirable, and among them, various factors such as the polymer composition, molecular weight, glass transition temperature, and solubility parameters of the paste vinyl chloride resin that can be preferably used are particularly limited. However, a paste vinyl chloride resin obtained by copolymerizing vinyl chloride and vinyl acetate is more preferable. Such a paste vinyl chloride resin can more easily realize compatibility with the component (A) due to swelling. Therefore, when the reaction between the component (A) and the component (B) proceeds from a relatively low temperature of 100 ° C. or higher and 120 ° C. or lower, the paste vinyl chloride resin obtained by copolymerization of vinyl chloride and vinyl acetate Can be used more preferably. Further, two or more kinds of paste vinyl chloride resins may be used in combination as the component (C).

The blending amount of the component (C) in the matrix resin composition is more preferably 1 part by mass or more, and more preferably 30 parts by mass or less with respect to 100 parts by mass of the component (A). The higher the content of the matrix resin composition contained in the tow prepreg and the higher the viscosity of the matrix resin composition contained in the tow prepreg, the more the tack of the tow prepreg is within the above-mentioned preferable range of the component (C). It is necessary to increase the blending amount of the particulate vinyl chloride copolymer. By setting the blending amount of the component (C) to 1 part by mass or more with respect to 100 parts by mass of the component (A), it is possible to prevent the tack of the tow prepreg from becoming too strong, and the amount should be 30 parts by mass or less. Therefore, it is possible to prevent the tack of the toe prepreg from becoming too weak, and it is possible to prevent a large amount of voids from being generated in the molded product produced by using the toe prepreg.

When the component (C) is kneaded with other components of the matrix resin composition, a known kneading device can be used. Examples of the known kneading device include a raker, an attritor, a planetary mixer, a dissolver, a triple roll, a ball mill and a bead mill. In addition, two or more of these can be used in combination.

When kneading to obtain the matrix resin composition contained in the tow prepreg according to the present invention, the component (C) is relatively concentrated in order to uniformly disperse the component (C) in the matrix resin composition. It is preferable to knead the mixture with a high concentration (low dilution ratio) to form a masterbatch, and then add other components later. Further, when the temperature in the system rises due to shearing heat generation due to kneading, it is preferable to perform an operation such as kneading while cooling so as not to raise the temperature during kneading.

The paste vinyl chloride resin that can be suitably used as the component (C) is a commercially available Kaneka stock such as PCH-72, PCH-12, PCH-843, PCH-175, PSL-31, PSL-275, PSL-290R. Examples thereof include pastes made by Tosoh Corporation such as PVC, R750, R751, R850, R950, and R650 manufactured by Tosoh Corporation.

<Arbitrary ingredient>
The matrix resin composition contained in the tow prepreg according to the present invention and the matrix resin composition used in the method for producing a composite material reinforced pressure vessel according to the present invention described later do not impair the effects of the present invention, if necessary. To the extent, various well-known additives may be included. Additives include thermoplastic elastomers, elastomer fine particles, core-shell elastomer fine particles, diluents, inorganic particles such as silica, carbonaceous components such as carbon nanotubes, flame retardants such as phosphorus compounds, and defoaming agents. Not exclusively.

Further, in order to improve the toughness of the matrix resin composition without lowering the heat resistance, it is preferable to add the core-shell type elastomer fine particles. Examples of commercially available core-shell elastomer fine particles include "Metabrene" (manufactured by Mitsubishi Rayon Co., Ltd.), "Stafyroid" (manufactured by Aica Kogyo Co., Ltd.), and "Paraloid" (manufactured by Dow Chemical Co., Ltd.). Be done. The core-shell type elastomer fine particles can also be obtained as a masterbatch type epoxy resin pre-dispersed in an epoxy resin, and such core-shell type elastomer-dispersed epoxy resin includes "Kaneace" (manufactured by Kaneka Corporation) and "Acrylic". "Set BP series" (manufactured by Nippon Kaneka Corporation) and the like can be mentioned. It is preferable to use a core-shell type elastomer-dispersed epoxy resin because not only the preparation time of the matrix resin composition can be shortened but also the dispersed state of the rubber particles in the matrix resin composition can be improved.

<Manufacturing method of tow prepreg>
The tow prepreg of the present invention can be produced by a known production method, but it is preferable to produce it through the following steps (1) to (4).
Step (1): Tension is applied to the reinforcing fiber bundle drawn from the spool, and the width is widened (heated as necessary).
Step (2): Quantify the matrix resin composition (heated as necessary) on at least one side of the widened reinforcing fiber bundle (so that the matrix resin composition becomes a predetermined amount per unit amount of the reinforcing fiber bundle). ) Supply.
Step (3): The supplied matrix resin composition is impregnated into the reinforcing fiber bundle to obtain a resin-impregnated reinforcing fiber bundle.
Step (4): The resin-impregnated reinforcing fiber bundle is wound around a bobbin such as a paper tube (cooled to about room temperature if necessary).

The reinforcing fiber bundle impregnated with the matrix resin composition is preferably widened and has a flat shape. If the reinforcing fiber bundle is widened and has a flat shape, the contact area with the matrix resin composition becomes wide.

Examples of the method of widening the reinforcing fiber bundle include a method of scraping with a cylindrical bar; a method of applying vibration; a method of crushing and the like. Further, when widening the reinforcing fiber bundle, it is preferable to heat it. The heating temperature depends on the type of sizing agent adhering to the carbon fibers, but is more preferably 50 ° C. or higher, and more preferably 150 ° C. or lower. Further, by heating the reinforcing fiber bundle at the time of widening, there is also an effect that the temperature of the matrix resin composition impregnated in the reinforcing fiber bundle does not decrease in the subsequent step (3). As the heating method, contact heating with a heating element and non-contact heating methods such as infrared heating and atmospheric heating can be used.

The widening of the reinforcing fiber bundle may be carried out in-line or offline. For example, a commercially available widened tape-like reinforcing fiber bundle is regarded as an offline widened reinforcing fiber bundle.

As a method of supplying the matrix resin composition to the reinforcing fiber bundle, the tow is passed through a resin bath to impregnate the matrix resin composition, and then the excess matrix resin composition is squeezed out by an orifice, a roll, or the like to obtain a resin content. "Resin bath method"; a transfer roll type impregnation method in which a matrix resin composition layer is formed on a rotating roll and transferred to a toe (for example, an impregnation method using a rotating drum having a doctor blade). "Rotary roll method"; "Paper transfer method" in which a matrix resin layer is formed on paper and transferred to a tow; JP-A-09-176346, JP-A-2005-335296, JP-A-2006-063173, etc. Examples thereof include the "nozzle dropping method"; the "resin contact and toe movement method" described in JP-A-08-073630, JP-A-09-031219, and the like.

Among these, the rotary roll method, the resin contact method, and the toe movement method are preferable as the method for supplying the matrix resin composition from the viewpoint of controlling the supply amount of the matrix resin composition and easiness of implementation. In addition, the width of the reinforcing fiber bundle is usually not stable, and the way it spreads varies. Therefore, as described in Japanese Patent Application Laid-Open No. 8-73630, it is effective to widen the reinforcing fiber bundle and then narrow the toe width to stabilize the matrix resin composition immediately before or at the time of contact. As a specific example, there is a method in which a groove having a predetermined width is provided at the resin discharge port portion, the coating portion, or a position immediately before the groove, and the reinforcing fiber bundle is allowed to run in the groove to narrow the width of the reinforcing fiber bundle. ..

As a method for impregnating the reinforcing fiber bundle with the matrix resin composition, a known impregnation method can be used. Among them, a method of rubbing against a heating element such as a heating roll or a hot plate; a method of allowing the reinforcing fiber bundle to which the matrix resin composition is supplied to run idle in a heating furnace, that is, in a heating atmosphere; by a non-contact heating means such as infrared heating. The method of heating; is preferable. To prevent the temperature of the reinforcing fiber bundle and the matrix resin composition from dropping between the time when the matrix resin composition is supplied to the reinforcing fiber bundle and the time when it is heated by the heating element, and between the heating element and the heating element. It is even more preferable to heat it by contact heating means.

Further, in the step of impregnating the reinforcing fiber bundle with the matrix resin composition, the cross-sectional shape of the reinforcing fiber bundle is changed by applying an external force to the reinforcing fiber bundle to laterally move the filament constituting the reinforcing fiber bundle on the roll surface. It is preferable to let it. By such an operation, the relative positions of the filaments can be changed to increase the chances of contact between the matrix resin composition and the filaments. As a result, a uniform impregnation effect that exceeds the impregnation effect due to simple pressurization or capillarity can be obtained.

Specific examples of the operation of changing the relative positions of the filaments include folding the reinforcing fiber bundle, widening the reinforcing fiber bundle, narrowing the reinforcing fiber bundle, and twisting the reinforcing fiber bundle. In these operations, the folding operation and the twisting operation tend to narrow the width of the reinforcing fiber bundle as in the narrowing operation. When the operation of narrowing the width of the reinforcing fiber bundle and the operation of expanding the width of the reinforcing fiber bundle are used in combination, the effect of uniform impregnation becomes higher. The twisting may be performed at the time of impregnation of the matrix resin composition, and if a state without twisting is required after impregnation, untwisting may be performed after impregnation. Further, if rubbing is applied at the same time as or immediately after twisting, the width of the reinforcing fiber bundle tends to widen, and the matrix resin composition moves in the thickness direction of the reinforcing fiber bundle, so that the uniformity of impregnation becomes high.

When the filament is laterally moved on the roll surface, it is useful to bring the reinforcing fiber bundle into contact with a roll rotating at a peripheral speed lower than the traveling speed of the reinforcing fiber bundle and scrape it from the viewpoint of preventing fluff accumulation and cleaning the roll. is there. If it is abraded, the reinforcing fiber bundle will not be entangled on the surface of the roll, and since the roll is rubbed by the reinforcing fiber bundle and is rotating, the surface in contact with the reinforcing fiber bundle is always cleaned. .. However, the peripheral speed of the roll is preferably 50% or more, more preferably 80% or more, more preferably 99% or less, and more preferably 95% or less of the traveling speed of the reinforcing fiber bundle. By setting the peripheral speed of the roll to 50% or more of the traveling speed of the reinforcing fiber bundle, the scraping force is weakened, so that fluffing of the reinforcing fiber bundle can be suppressed. Therefore, it is possible to suppress the occurrence of wrapping in the subsequent process and to satisfactorily unwind the tow prepreg wound on the bobbin.

When the reinforcing fiber bundle is uniformly impregnated with the matrix resin composition, the mechanical properties of the produced fiber-reinforced composite material are improved, and the effects of the present invention can be sufficiently obtained.

The reinforcing fiber bundle uniformly impregnated with the matrix resin composition is cooled to about room temperature by using known cooling means such as rubbing against a cooling body or non-contact cooling means before the winding process to the paper tube. It is preferable to keep it. By cooling, the matrix resin composition has a viscosity of a suitable height when it is wound on a bobbin such as a paper tube, so that it is prevented from slipping and the winding form is disturbed when it is wound, and it is wound well. Can be taken. In addition, by cooling, the shelf life of the tow prepreg can be extended for a long period of time. In the spool of the toe prepreg, the high temperature continues for a relatively long time, and the shelf life may be shortened due to the influence of the high temperature part on the surroundings, but if it is cooled, such a problem This is because it does not occur.

<Manufacturing method of composite material reinforced pressure vessel>
The method for producing a composite material reinforced pressure vessel according to the present invention includes an impregnation step of impregnating a reinforcing fiber bundle with the above-mentioned matrix resin composition and a filament winding step (FW) of winding the reinforcing fiber bundle impregnated with the matrix resin composition around a liner. A step) and a curing step of heating the liner around which the reinforcing fiber bundle is wound to cure the matrix resin composition impregnated in the reinforcing fiber bundle.

Further, the method for manufacturing a composite material reinforced pressure vessel according to the present invention includes a winding step of winding a resin-impregnated reinforcing fiber bundle impregnated with a matrix resin composition around a bobbin between an impregnation step and a FW step. You may. The resin-impregnated reinforced fiber bundle wound around the bobbin by the winding process is stored as a toe prepreg until it is wound around the liner.

If the method of manufacturing the composite reinforced pressure vessel does not have a winding step, the resin impregnated reinforced fiber bundle is wound around the liner without going through the toe prepreg. On the other hand, when the manufacturing method of the composite material reinforcing pressure vessel includes a winding step, the resin-impregnated reinforcing fiber bundle is wound around the liner as a toe prepreg.

(Immersion process)
The impregnation step is a step of impregnating the reinforcing fiber bundle with the matrix resin composition.

When the method for producing the composite material reinforcing pressure vessel does not include a winding step, the method for supplying the matrix resin composition to the reinforcing fiber bundle and the method for impregnating the composite material are not particularly limited, and examples thereof include the following methods. That is, a matrix resin composition having a certain thickness is applied to a columnar drum using a doctor blade or the like, a reinforcing fiber bundle is brought into contact with the matrix resin composition, and the matrix resin composition is supplied, and the matrix is supplied by a roller or the like. A method of impregnating the inside with the resin composition; a method of immersing the reinforcing fiber bundle in a container storing the matrix resin composition and then scraping off the unnecessary matrix resin composition with a bar or a guide; quantitatively with a dispenser or the like. A method of feeding the matrix resin composition and applying it to the reinforcing fiber bundle; and the like can be mentioned. The method using a drum or a dispenser is preferable in that the matrix resin composition can be applied to the reinforcing fiber bundle without supplying excess resin to the reinforcing fiber bundle and accurately controlling the impregnation amount to a target value.

On the other hand, even when the method for manufacturing the composite material reinforcing pressure vessel has a winding step, the method for supplying the matrix resin composition to the reinforcing fiber bundle and the method for impregnating the composite material are as described above as a case where the method does not have a winding step. Examples thereof include a method for supplying the composition and a method for impregnating the composition.

(Winding process)
The winding step is a step of winding a resin-impregnated reinforcing fiber bundle on a bobbin such as a paper tube. The method of winding the resin-impregnated reinforcing fiber bundle around the bobbin is not particularly limited. The resin-impregnated reinforcing fiber bundle wound around the bobbin is stored as a tow prepreg.

(FW process)
The FW step is a step of winding a resin-impregnated reinforcing fiber bundle (including a resin-impregnated reinforcing fiber bundle unwound from the tow prepreg) around a rotating liner. A product obtained by winding a resin-impregnated reinforcing fiber bundle around a liner may be referred to as a "pressure vessel intermediate".

As described above, in the FW step, the resin-impregnated reinforcing fiber bundle may be wound around the liner without passing through the tow prepreg, or the resin-impregnated reinforcing fiber bundle (tow prepreg) wound around the bobbin such as a paper tube may be wound on the bobbin. You may wrap it around the liner while pulling it out from.

As the filament winding machine (FW machine) used in the FW process, a conventionally known one can be used. When producing a composite material reinforcing pressure vessel, a resin-impregnated reinforcing fiber bundle is wound around the liner as a mandrel. The FW machine may be one in which one resin-impregnated reinforcing fiber bundle is wound around the mandrel, or a plurality of resin-impregnated reinforcing fiber bundles may be wound around the mandrel at the same time.

When winding the resin-impregnated reinforcing fiber bundle around the liner, it is preferable to wind the resin-impregnated reinforcing fiber bundle so as to have a laminated structure in which composite materials having different characteristics are laminated in order to take advantage of the characteristics of the resin-impregnated reinforcing fiber bundle as an anisotropic material. A layer made of a resin-impregnated reinforcing fiber bundle or a cured layer is called a composite material layer.

In the present invention, the composition and thickness of the composite material layer, the angle and tension for winding the resin-impregnated reinforcing fiber bundle around the liner can be freely selected depending on the use and shape of the container, the type of contents, and the like.

Hoop winding and helical winding are known as methods for winding the resin-impregnated reinforcing fiber bundle. Conventionally, the fiber-reinforced composite material layer that reinforces the mirror portion and the body portion is referred to as a "helical layer", and the fiber-reinforced composite material layer that reinforces the body portion is referred to as a "hoop layer".

(Curing process)
The curing step is a step of heating the pressure vessel intermediate to cure the matrix resin composition contained in the resin-impregnated reinforcing fiber bundle. The curing temperature and curing time are determined according to the compounding composition of the matrix resin composition. As a method of heating, a method of using a vacuum bag and a heater, a method of wrapping a wrapping tape to apply pressure and heating in an oven, a method of filling a pressure vessel with a pressurized substance and heating while applying internal pressure, etc. are used. ..

<Composite reinforcement pressure vessel>
The composite material reinforced pressure vessel obtained as described above is also within the scope of the present invention. That is, the composite material reinforcing pressure vessel according to the present invention includes a reinforcing fiber bundle, and the reinforcing fiber bundle is impregnated with a matrix resin composition containing the following components (A), component (B) and component (C'). The reinforcing fiber bundle in which the matrix resin composition is cured is used as the reinforcing layer.
Component (A): Epoxy resin component (B): Epoxy resin curing agent component (C'): Vinyl chloride-based copolymer component (C') is derived from the above-mentioned component (C) and is a composite material. The component (C), which was particulate when it was a part of the reinforcing pressure vessel, has become non-particulate by being dissolved, and is preferably compatible with the component (A).

[Additional notes]
As described above, in the tow prepreg according to the present invention, it is more preferable that the viscosity of the matrix resin composition at 30 ° C. is 3 Pa · s or more and 300 Pa · s or less.

Further, in the tow prepreg according to the present invention, it is more preferable that the component (B) is a boron trichloride amine complex.

Further, in the tow prepreg according to the present invention, the blending amount of the component (B) is 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the component (A), and the component (C). Is more preferably 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the component (A).

Further, in the tow prepreg according to the present invention, the component (C) is particulate at room temperature, is higher than room temperature, and is lower than the curing temperature of the matrix resin composition. It is more preferable that it is compatible with.

Further, in the tow prepreg according to the present invention, it is more preferable that the reinforcing fiber bundle is a carbon fiber bundle.

Further, in the composite material reinforced pressure vessel according to the present invention, it is more preferable that the cured tow prepreg is wound around a metal liner or a resin liner.

The raw materials, preparation methods, and methods for measuring each physical property of the resin composition used in each example are shown below. Tables 1 to 3 summarize the composition of each matrix resin composition and the measurement results of the physical properties. The numerical values of each component in Tables 1 to 3 represent the number of parts by mass of each component to be blended in the matrix resin composition. However, the scope of the present invention is not limited to the examples.

<Raw materials>
<Ingredient (A)>
・ JER828
"Product name" jER828
"Ingredients" Bisphenol A type epoxy resin (bifunctional epoxy resin; bisphenol A diglycidyl ether type epoxy resin)
(Epoxy equivalent: 189 g / eq)
"Supplier" Mitsubishi Chemical Corporation, CY184
"Product name" Araldite "Ingredients" Hexahydrophthalic acid diglycidyl ester (epoxy equivalent: 158 g / eq)
"Supplier" Huntsman Japan Co., Ltd.

<Masterbatch type rubber particle dispersion epoxy resin in which arbitrary components are dispersed in component (A)>
・ MX-257
"Product name" Kane Ace MX-257
"Component" Bisphenol A type epoxy resin (bifunctional epoxy resin. Epoxy equivalent: 189 g / eq): 63% by mass, and butadiene-based core-shell type rubber particles (volume average particle size: 200 nm): 37% by mass.
"Supplier" Kaneka Corporation.

<Ingredient (B)>
・ DY9577
"Product name" DY9577
"Ingredients" Boron trichloride amine complex "Supplier" Huntsman Japan Co., Ltd.

<Component (C)>
・ PSL-290R
"Product name" PSL-290R (paste PVC)
"Ingredients" Vinyl chloride polymer "Supplier" Kaneka Corporation PSL-675
"Product name" PSL-675 (paste PVC)
"Ingredients" Vinyl chloride polymer "Supplier" Kaneka Corporation PSH-24
"Product name" PSH-24 (paste PVC)
"Ingredients" Vinyl chloride polymer "Supplier" Kaneka Corporation PCH-72
"Product name" PCH-72 (paste PVC)
"Ingredients" Vinyl chloride / vinyl acetate copolymer "Supplier" Kaneka Corporation PCH-12
"Product name" PCH-12 (paste PVC)
"Ingredients" Vinyl chloride / vinyl acetate copolymer "Supplier" Kaneka Corporation PCH-843
"Product name" PCH-843 (paste PVC)
"Ingredients" Vinyl chloride / vinyl acetate copolymer "Supplier" Kaneka Corporation.

<Particles that do not correspond to component (C)>
・ 102A
"Product name" Polarite 102A
"Ingredients" Surface aminosilane treated kaolin "Supplier" Imeris Minerals Japan Co., Ltd.

<Arbitrary ingredient>
・ BYK-A506
"Product name" BYK-A506
"Ingredients" Foam-breaking polysiloxane solution "Supplier" Big Chemie Japan Co., Ltd.

[Examples and Comparative Examples]
<Example 1>
(Preparation of matrix resin composition)
5 parts by mass of paste vinyl chloride resin PCH-12 was mixed with 75 parts by mass of Kaneace MX-257. The mixture was further mixed using a three-roll mill to form a masterbatch. A masterbatch, 25 parts by mass of Araldite CY184, 10 parts by mass of DY9577, and 0.3 parts by mass of BYK-A506 are weighed in a glass flask and heated to about 40 ° C. to 50 ° C. using a water bath. While stirring until uniform, a matrix resin composition was obtained.

(Making tow prepreg)
As a reinforcing fiber bundle, a tow prepreg was prepared using a carbon fiber "37-800WD" having 30,000 filaments (manufactured by Mitsubishi Rayon Carbon Fiber and Composits Co., Ltd., tensile strength 5520 MPa, tensile elastic modulus 255 GPa).

The specific production method is shown below. The reinforcing fiber bundle was sent out from the creel, and the width was widened from 10 mm to 15 mm through an opening bar whose surface temperature was heated to about 100 ° C. The widened reinforcing fiber bundle was brought into contact with a touch roll coated with the matrix resin composition heated to about 40 ° C., and the matrix resin composition was supplied to the reinforcing fiber bundle. The reinforcing fiber bundle to which the matrix resin composition is supplied is rubbed against an impregnated roll heated to about 50 to 60 ° C. to impregnate the inside of the reinforcing fiber bundle with the matrix resin composition, and then paper is used with a winder. A tow prepreg was obtained by winding it on a tube. By adjusting the clearance between the doctor blade and the touch roll, the amount of resin adhered to the reinforcing fiber bundle (that is, the resin content of the tow prepreg) was adjusted to about 24% by mass.

(Manufacturing of composite material reinforced pressure vessel)
Using a FW device, the obtained tow prepreg was applied to an aluminum liner with a capacity of 9 liters (total length: 540 mm, body length: 415 mm, body outer diameter: 163 mm, wall thickness at the center of the body: 3 mm). Wrapped around. The aluminum liner used is made of a material obtained by heat-treating the aluminum material specified in JIS H 4040 A6061-T6.

The tow prepreg was unwound from the paper tube, adjusted in position via the guide roll, and then wound around the liner as follows.

First, as the first layer in contact with the body of the liner, a toe prepreg was wound around the body so as to form 88.6 ° with respect to the rotation axis direction of the liner. After that, the tow prepreg was wound at an angle of 11.0 ° with respect to the rotation axis direction of the liner, and a helical layer for reinforcing the mirror portion of the liner was laminated, and thereafter, described in "Laminate Nos. 3 to 8" shown in Table 4. A pressure vessel intermediate was prepared by winding the toe prepreg sequence around the liner at the angle of.

The obtained pressure vessel intermediate was removed from the FW device, suspended in a heating furnace, the temperature inside the furnace was raised to 110 ° C. at 2 ° C./min, and then held at 110 ° C. for 2 hours for curing. Then, the temperature in the furnace was cooled to 60 ° C. at 1 ° C./min to obtain a composite material reinforcing pressure vessel.

(Evaluation of toe prepreg unresolvability, morphological retention, and process passability)
When manufacturing a composite material reinforced pressure vessel as described above, if the composite material reinforced pressure vessel can be manufactured without any problems in the unresolvability, shape retention, and process passability of the tow prepreg, "○" Although there were some problems, it was evaluated as "Δ" when the composite material reinforced pressure vessel could be manufactured in a stable manner, and as "x" when any obvious problem occurred. The results are shown in Table 2.

(Breaking pressure measurement test of composite material reinforced pressure vessel)
After setting the composite material reinforced pressure vessel in the hydraulic failure tester and filling the composite material reinforced pressure vessel with water, the composite material reinforced pressure vessel is loaded with water pressure at a pressurization rate of 15 MPa / min to make the composite material reinforced pressure vessel. The water pressure at the time of rupture was recorded and used as the breaking pressure of the composite material reinforced pressure vessel. The results are shown in Table 3.

(Tack test)
The tack of the toe prepreg was measured by the following tack test.

Equipment: Tuck tester TA-500 (manufactured by UBM Co., Ltd.)
Contact area of the plunger with the sample (toe prepreg to be measured): 3.131 cm ²
Plunger pressing time: 10 seconds Plunger pressing pressure: 90,000 Pa
Plunger rising speed: 1 mm / sec Measurement temperature: 23 ° C
Measured humidity: 50% RH
procedure:
(1) Place the toe prepreg on the sample table and fix it. At this time, the surface of the toe prepreg that comes into contact with the plunger is the surface that was not visible when the toe prepreg was wound around the paper tube (that is, the surface on the paper tube side).
(2) The plunger is pressed against the toe prepreg with a pressure of 90,000 Pa for 10 seconds.
(3) Raise the plunger at 1 mm / sec.
(4) The maximum value of the stress value while raising the plunger was defined as the maximum stress value, and the average value of the maximum stress values obtained by measuring a total of 5 times was defined as the average maximum stress value. The results are shown in Tables 1, 2 and 3.

<Example 2>
A matrix resin composition was prepared in the same manner as in Example 1 except that the amount of the paste vinyl chloride resin PCH-12 used in Example 1 was 10 parts by mass, preparation of a tow prepreg, and production of a composite material reinforced pressure vessel. , Evaluation of unresolvability, morphological retention, and process passability of toe prepreg, and tack test were performed. The results are shown in Tables 1 and 2.

<Example 3>
A matrix resin composition was prepared in the same manner as in Example 1 except that the amount of the paste vinyl chloride resin PCH-12 used in Example 1 was 15 parts by mass, and a tow prepreg was prepared and a tack test was carried out. The results are shown in Table 1.

<Example 4>
(Preparation of matrix resin composition)
jER828 and the paste vinyl chloride resin PCH-72 were mixed in a ratio of 1: 1. The mixture was further mixed using a three-roll mill to form a masterbatch. Weigh the masterbatch, jER828, DY9577, and BYK-A506 into a glass flask to the amounts shown in Table 2, and stir with a water bath while heating to about 40 ° C. to 50 ° C. until uniform. A matrix resin composition was obtained.

(Manufacture of tow prepreg, manufacture of composite material reinforced pressure vessel, evaluation of toe prepreg unresolvability, morphological retention, process passability, fracture pressure measurement test, tack test)
This was done in the same manner as in Example 1. The results are shown in Tables 1, 2 and 3.

<Example 5>
(Preparation of matrix resin composition)
jER828 and the paste vinyl chloride resin PCH-72 were mixed in a ratio of 1: 1. The mixture was further mixed using a three-roll mill to form a masterbatch. Weigh the masterbatch, jER828, CY184, DY9577, and BYK-A506 into a glass flask to the amounts shown in Table 2, and stir until uniform while heating to about 40 ° C to 50 ° C using a water bath. Then, a matrix resin composition was obtained.

(Manufacture of tow prepreg, manufacture of composite material reinforced pressure vessel, unfoldability, morphological retention, process passability evaluation of tow prepreg, tack test)
This was done in the same manner as in Example 1. The results are shown in Table 2.

<Example 6>
(Preparation of matrix resin composition)
10 parts by mass of the paste vinyl chloride resin PCH-72 was mixed with 75 parts by mass of Kaneace MX-257. The mixture was further mixed using a three-roll mill to form a masterbatch. Weigh the masterbatch, CY184, DY9577, and BYK-A506 into a glass flask to the amounts shown in Table 2, and stir with a water bath while heating to about 40 ° C. to 50 ° C. until uniform. A matrix resin composition was obtained.

(Manufacture of tow prepreg, manufacture of composite material reinforced pressure vessel, unfoldability, morphological retention, process passability evaluation of tow prepreg, tack test)
This was done in the same manner as in Example 1. The results are shown in Table 2.

<Example 7>
(Preparation of matrix resin composition)
5 parts by mass of the paste vinyl chloride resin PCH-843 was mixed with 75 parts by mass of Kaneace MX-257. The mixture was further mixed using a three-roll mill to form a masterbatch. Weigh the masterbatch, CY184, DY9577, and BYK-A506 into a glass flask to the amounts shown in Table 2, and stir with a water bath while heating to about 40 ° C. to 50 ° C. until uniform. A matrix resin composition was obtained.

(Manufacture of tow prepreg, manufacture of composite material reinforced pressure vessel, evaluation of toe prepreg unresolvability, morphological retention, process passability, fracture pressure measurement test, tack test)
This was done in the same manner as in Example 1. The results are shown in Tables 2 and 3.

<Example 8>
(Preparation of matrix resin composition)
10 parts by mass of the paste vinyl chloride resin PCH-843 was mixed with 75 parts by mass of Kaneace MX-257. The mixture was further mixed using a three-roll mill to form a masterbatch. Weigh the masterbatch, CY184, DY9577, and BYK-A506 into a glass flask to the amounts shown in Table 2, and stir with a water bath while heating to about 40 ° C. to 50 ° C. until uniform. A matrix resin composition was obtained.

(Manufacture of tow prepreg, manufacture of composite material reinforced pressure vessel, unfoldability, morphological retention, process passability evaluation of tow prepreg, tack test)
This was done in the same manner as in Example 1. The results are shown in Table 2.

<Example 9>
(Preparation of matrix resin composition)
10 parts by mass of paste vinyl chloride resin PSL-290R was mixed with 75 parts by mass of Kaneace MX-257. The mixture was further mixed using a three-roll mill to form a masterbatch. Weigh the masterbatch, CY184, DY9577, and BYK-A506 into a glass flask to the amounts shown in Table 2, and stir with a water bath while heating to about 40 ° C. to 50 ° C. until uniform. A matrix resin composition was obtained.

(Manufacture of tow prepreg, manufacture of composite material reinforced pressure vessel, unfoldability, morphological retention, process passability evaluation of tow prepreg, tack test)
This was done in the same manner as in Example 1. The results are shown in Table 2.

<Example 10>
(Preparation of matrix resin composition)
10 parts by mass of the paste vinyl chloride resin PSL-675 was mixed with 75 parts by mass of Kaneace MX-257. The mixture was further mixed using a three-roll mill to form a masterbatch. Weigh the masterbatch, CY184, DY9577, and BYK-A506 into a glass flask to the amounts shown in Table 2, and stir with a water bath while heating to about 40 ° C. to 50 ° C. until uniform. A matrix resin composition was obtained.

(Manufacture of tow prepreg, manufacture of composite material reinforced pressure vessel, unfoldability, morphological retention, process passability evaluation of tow prepreg, tack test)
This was done in the same manner as in Example 1. The results are shown in Table 2.

<Example 11>
(Preparation of matrix resin composition)
10 parts by mass of paste vinyl chloride resin PSH-24 was mixed with 75 parts by mass of Kaneace MX-257. The mixture was further mixed using a three-roll mill to form a masterbatch. Weigh the masterbatch, CY184, DY9577, and BYK-A506 into a glass flask to the amounts shown in Table 2, and stir with a water bath while heating to about 40 ° C. to 50 ° C. until uniform. A matrix resin composition was obtained.

(Manufacture of tow prepreg, manufacture of composite material reinforced pressure vessel, unfoldability, morphological retention, process passability evaluation of tow prepreg, tack test)
This was done in the same manner as in Example 1. The results are shown in Table 2.

<Comparative example 1>
(Preparation of matrix resin composition)
Weigh Kaneace MX-257, CY184, DY9577, and BYK-A506 in a glass flask to the amounts shown in Table 2, and stir while heating to about 40 ° C to 50 ° C using a water bath until uniform. Then, a matrix resin composition was obtained.

(Manufacture of tow prepreg, manufacture of composite material reinforced pressure vessel, unfoldability, morphological retention, process passability evaluation of tow prepreg, tack test)
This was done in the same manner as in Example 1. The results are shown in Table 2.

<Comparative example 2>
(Preparation of matrix resin composition)
Weigh jER828, DY9577, and BYK-A506 into a glass flask to the amounts shown in Table 2, and stir with a water bath while heating to about 40 ° C. to 50 ° C. until uniform, and the matrix resin composition. I got something.

(Manufacture of tow prepreg, manufacture of composite material reinforced pressure vessel, unfoldability, morphological retention, process passability evaluation of tow prepreg, tack test)
This was done in the same manner as in Example 1. The results are shown in Table 2.

<Comparative example 3>
(Preparation of matrix resin composition)
5 parts by mass of Polarite 102A was mixed with 75 parts by mass of Kaneace MX-257. The mixture was further mixed using a three-roll mill to form a masterbatch. Weigh the masterbatch, CY184, DY9577, and BYK-A506 into a glass flask to the amounts shown in Table 3, and stir until uniform while heating to about 40 ° C. to 50 ° C. using a water bath. A matrix resin composition was obtained.

(Manufacture of tow prepreg, manufacture of composite material reinforced pressure vessel, evaluation of toe prepreg unresolvability, morphological retention, process passability, fracture pressure measurement test, tack test)
This was done in the same manner as in Example 1. The results are shown in Table 3.

From Table 1, as the amount of the component (C) added to the matrix resin composition increased, the average maximum stress value (tack) of the tow prepreg decreased, and the addition of the component (C) to the matrix resin composition. It can be seen that the average maximum stress value (tack) of the toe prepreg can be adjusted within an appropriate range.

From Table 2, when the viscosity of the matrix resin composition at 30 ° C. and the average maximum stress value (tack) of the tow prepreg are within the above-mentioned preferable ranges, the tow prepreg's unfoldability, morphological retention, and steps It can be seen that the passability is in a preferable state. In Comparative Example 1, since the matrix resin composition did not contain the component (C), the tack was strong, and there were major problems in morphological retention and process passability, such as the toe being folded and not opened during the FW process. Further, in Comparative Example 2, since the viscosity of the matrix resin composition at 30 ° C. was too low, the prepared tow prepreg was very soft, and since it did not contain the component (C), the average maximum stress value (tack) of the toe prepreg was obtained. However, when the tow prepreg is folded or tensioned during the FW stroke, the toe becomes very thin due to the influence of the surface tension of the matrix resin composition, and the shape retention property, And there was a big problem in process passability. Furthermore, the above-mentioned winding-drawing phenomenon was also observed in the toe prepreg of Comparative Example 2.

From Table 3, it can be seen that the composite material reinforced pressure vessel according to the present invention exhibits excellent breaking pressure because of its high quality. In Comparative Example 3, inorganic particles Polarite 102A were used as particles not contained in the component (C). It can be seen that the inorganic particles have the same effects as the component (C) in terms of optimizing the unfoldability, morphological retention, and process passability of the tow prepreg. However, unlike the component (C), the inorganic particle Polarite 102A maintains its particle shape even after the composite material reinforcing pressure vessel is molded, and a large number of voids resulting from this are present in the composite material reinforcing pressure vessel of Comparative Example 3. Is occurring in. Since the void becomes the starting point of fracture when the internal pressure is applied to the composite material reinforcing pressure vessel, the breaking pressure of the composite material reinforcing pressure vessel is remarkably lowered. In fact, the breaking pressure of the composite material reinforcing pressure vessel of Comparative Example 3 was low.

In any of the examples, the reinforcing fiber bundle could be sufficiently impregnated with the matrix resin composition by the above-mentioned method.

The tow prepreg, composite material reinforced pressure vessel and its manufacturing method according to the present invention can be used for a pressure vessel, and can also be used for general industrial applications such as sports equipment, automobiles, aircraft, and tension materials. ..

Claims (4)

Contains a matrix resin composition
The matrix resin composition contains the following component (A), component (B) and component (C).
The component (C) is not dissolved in the matrix resin composition containing the component (C).
Tow prepreg.
Component (A): Epoxy resin Component (B): Epoxy resin curing agent Component (C): Particulate vinyl chloride-based copolymer The blending amount of the component (B) is 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the component (A), and the blending amount of the component (C) is the component (A). The tow prepreg according to claim 1, wherein the amount is 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass. An impregnation step of impregnating a reinforcing fiber bundle with a matrix resin composition containing the following components (A), component (B) and component (C), and
A filament winding process in which a bundle of reinforcing fibers impregnated with a matrix resin composition is wound around a liner,
It includes a curing step of heating the liner around which the reinforcing fiber bundle is wound and curing the matrix resin composition impregnated in the reinforcing fiber bundle.
A method for producing a composite material reinforced pressure vessel in which the component (C) is not dissolved in a matrix resin composition containing the component (C).
Component (A): Epoxy resin Component (B): Epoxy resin curing agent Component (C): Particulate vinyl chloride-based copolymer
The blending amount of the component (B) is 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the component (A), and the blending amount of the component (C) is the component (A). The method for manufacturing a composite material reinforced pressure vessel according to claim 3, wherein the amount is 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass.

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