JP6503683B2 - Tow prepreg - Google Patents

Description

  The present invention is a tow prepreg excellent in unwinding ability from a paper tube, processability, and form retention. The tow prepreg can be used in general industrial applications such as sports goods, automobiles, pressure vessels, aircraft, tendons and the like.

  A pressure vessel in which a tank liner is reinforced with a reinforced fiber composite material is used as a natural gas or hydrogen gas storage tank mounted on a mobile body such as an automobile because of its lightness. Glass fibers, carbon fibers and the like are used as reinforcing fibers. Among them, carbon fiber is high in specific strength and large in the merit of weight reduction in pressure vessel, and is suitably used in a storage tank of hydrogen gas which requires higher pressure resistance performance than a storage tank of natural gas.

  A pressure vessel reinforced with a reinforcing fiber composite material is generally produced by filament winding molding (FW molding). That is, it is a molding method in which a reinforcing fiber bundle is wound in a desired tension and angle around a rotating tank liner while supplying and impregnating a matrix resin composition in a single or plural aligning process.

  Instead of winding while impregnating in the process, it is also possible to use a tow prepreg in which a reinforcing fiber bundle is impregnated with a resin composition in advance. In this case, the matrix resin composition is not supplied or impregnated in the process, but is wound around the rotating tank liner at a desired tension and angle without performing impregnation. In addition, various advantages can be obtained by using a tow prepreg in FW molding. That is, since it is not necessary to handle the uncured resin composition in the process, the working environment can be improved, and the process speed can be improved because there is no need to supply and impregnate the matrix resin composition to the reinforcing fiber bundle in the process. It is possible to obtain molded articles having high quality and high performance by using a tow prepreg in which the content of the matrix resin composition is controlled.

  That is, the desired amount of matrix resin composition in the tow prepreg is sufficiently impregnated into the reinforcing fiber bundle, that the tow prepreg can be unwound at high speed, and the form of the tow prepreg does not change significantly during FW forming. Is required.

  The tow prepreg is usually wound on a paper tube and unwound from the paper tube when used. At this time, in order to unwind the tow prepreg at high speed, the tack (stickiness) of the tow prepreg must be weak. One of the methods of weakening the tack of tow prepreg is a method of reducing the viscosity of a matrix resin composition to be impregnated into a reinforcing fiber bundle (Patent Document 1).

  Also, as a method to weaken the tack of tow prepreg and keep the form retention of tow prepreg good, the viscosity of the matrix resin composition to be impregnated into the reinforcing fiber bundle is not sticky at the operating temperature (usually room temperature) of tow prepreg. There is a method to make it as high as possible (patent document 2).

Japanese Patent Application Laid-Open No. 9-087365 Japanese Patent Application Laid-Open No. 55-015870

  However, as in the technique disclosed in Patent Document 1, when the viscosity of the matrix resin composition is too low, the form retention of the tow prepreg is weak, and the tow prepreg is folded by a guide roll or the like during FW forming and the form largely changes. Resulting in. Furthermore, although a tow prepreg is normally wound on a paper tube under a tension of several hundreds of grams to 1 kg, there is a problem that the amount of the matrix resin composition changes, which is squeezed out of the matrix resin composition contained in the tow prepreg. It also happens.

  On the other hand, it is difficult to sufficiently impregnate the reinforcing fiber bundle with a high viscosity matrix resin composition as disclosed in Patent Document 2, and in Patent Document 2, the matrix resin composition is dissolved in a solvent and impregnated into the reinforcing fiber bundle. I am doing it. When the matrix resin composition is dissolved in a solvent, some of the solvent remains in the tow prepreg. The remaining solvent causes voids in the cured product produced using the tow prepreg, which causes the strength and the quality to be greatly reduced.

  In view of the above background, it is an object of the present invention to provide a tow prepreg excellent in the unwindability from a paper tube, the processability in the FW forming process, and the form retention.

MEANS TO SOLVE THE PROBLEM As a result of earnest examination, in order to solve the said subject, the present inventors discover that the said subject can be solved by using the tow prepreg which satisfy | fills specific conditions, and came to this invention. That is, the present invention relates to the following.
[1] A tow prepreg comprising a reinforcing fiber bundle impregnated with a matrix resin composition containing a particulate component, the tow prepreg having an average maximum stress value in the range of 5,000 to 55,000 Pa as a tack test result. .
[2] The tow prepreg according to the above [1], which has a viscosity of 5 to 300 Pa · s at 30 ° C. of the matrix resin composition.
[3] The tow prepreg according to [1] or [2], wherein the reinforcing fiber bundle is a carbon fiber bundle.
[4] The tow prepreg according to any one of [1] to [3], which has a resin content of 20 to 40% by mass.
[5] The matrix resin composition contains the following components (A) to (C), and the content of the component (B) is 5 to 20 parts by mass with respect to 100 parts by mass of the component (A), [1] to [4], wherein the content of the component (C) is 1 to 30 parts by mass with respect to 100 parts by mass of the specific organic compound component, and the primary particle diameter of the component (C) is 1 to 30 μm The tow prepreg according to any one of the above.

Component (A): Epoxy resin Component (B): Boron trichloride amine complex Component (C): Particulate thermoplastic resin The "specific organic compound component" in the present invention refers to the matrix resin composition of the present invention. It is a general term for the component (A), the component (B), the component (E) to be described later, and the “thermoplastic resin dissolved in epoxy resin” to be described later. In addition, for example, when the matrix resin composition of this invention contains only a component (A) among this "specific organic compound components", the "specific organic compound component" in the said matrix resin composition is a component (A When only the component (A), the component (B) and the “thermoplastic resin dissolved in an epoxy resin” are included, the “specific organic compound component” in the matrix resin composition is the component (A), The component (B) and "a thermoplastic resin dissolved in an epoxy resin" are all represented.
[6] The matrix resin composition contains the following component (A), component (C) and component (D), and the total content of the component (C) and component (D) is 100 mass of a specific organic compound component The tow prepreg according to any one of the above [1] to [4], which is 3 to 30 parts by mass with respect to 1 part and the primary particle diameter of the component (C) is 1 to 30 μm.

Component (A): Epoxy resin Component (C): particulate thermoplastic resin Component (D): particulate epoxy resin curing agent, or particulate epoxy resin curing agent and particulate epoxy resin curing assistant [7 The particulate epoxy resin curing agent in the component (D) is at least one selected from the group consisting of an epoxy resin imidazole adduct compound, an epoxy resin amine adduct compound, a modified aliphatic amine compound, a dicyandiamide and an aromatic polyamine The tow prepreg according to the above [6].
[8] The particulate epoxy resin curing aid in the component (D) is at least one selected from the group consisting of an epoxy resin imidazole adduct compound, an epoxy resin amine adduct compound, a modified aliphatic amine compound and a urea compound The tow prepreg according to the above [6] or [7], which is (but a compound different from the particulate epoxy resin curing agent used in combination as a part of the component (D)).
[9] The matrix resin composition further comprises the following component (E), and the content of the component (E) is 10 to 110 parts by mass with respect to 100 parts by mass of the component (A). The tow prepreg as described in any one of 5]-[8].

Component (E): Rubber particle [10] The tow prepreg according to the above [9], wherein the component (E) is a rubber particle containing butadiene rubber.

  By setting the average maximum stress value of the tack test result in the range of 5,000 Pa to 55,000 Pa, it is possible to obtain a tow prepreg excellent in the unwindability from a paper tube, the processability, and the form retention. The tow prepreg can be used in general industrial applications such as sports goods, automobiles, pressure vessels, aircraft, tendons and the like.

It is a schematic diagram which shows the apparatus used for the high-speed releasability evaluation which consists of a creel, a guide, a dancer roll, a godd roll, and a winder used by the Example and the comparative example.

  The present invention is a tow prepreg comprising a reinforcing fiber bundle impregnated with a matrix resin composition containing particulate components, wherein the average maximum stress value in the tack test results is in the range of 5,000 to 55,000 Pa. It exists in the prepreg.

  In order to obtain a tow prepreg having good unwindability from a paper tube, process passability at the time of FW molding, and shape retention, the average maximum stress value of the tack test result is in the range of 5,000 Pa to 55,000 Pa. There is a need. These will be described below.

<Tow prepreg>
A tow prepreg is a narrow intermediate substrate obtained by impregnating a resin composition with a reinforcing fiber bundle in which several thousands to several tens of thousands of filaments are arranged in one direction. The tow prepreg of the present invention is obtained by impregnating a matrix resin composition of the present invention described later into a reinforcing fiber bundle. The fiber diameter and the number of filaments constituting the reinforcing fiber bundle are not particularly limited, but the fiber diameter is preferably 3 to 100 μm, and the number is preferably 1,000 to 70,000.

  The term "fiber diameter" in the present invention means the equivalent area circle equivalent diameter of the cross section of each fiber.

  If the fiber diameter is less than 3 μm, for example, the filament may move in a lateral direction (that is, a direction perpendicular to the fiber direction) on the surface of a roll, a bobbin, etc. When it does, it may be cut or fuzz may occur, and when it exceeds 100 μm, the filament becomes hard and the flexibility tends to decrease.

  As the reinforcing fiber bundle in the present invention, reinforcing fibers used for ordinary fiber reinforced composite materials such as glass fibers, carbon fibers, aramid fibers, graphite fibers, boron fibers and the like can be used. Among them, carbon fibers with a strand strength of 3500 MPa or more according to JIS R 7601; graphitic fibers; more preferably carbon fibers with a strand strength of 4500 MPa or more; graphite fibers; still more preferably carbon fibers with a strand strength of 5000 MPa or more . In particular, when used as a pressure vessel or tendon, the strand strength of the carbon fiber bundle to be used is preferably as high as possible.

  When the reinforcing fiber bundle is a carbon fiber bundle, the fiber diameter of the filament is preferably 3 to 12 μm, and the number thereof is preferably 1,000 to 70,000.

  If the fiber diameter is less than 3 μm, for example, the filament may be cut or fuzzed when it causes lateral movement on the surface of a roll, a bobbin or the like in various processing processes. The upper limit is usually about 12 μm because of the difficulty in producing carbon fibers.

<Dissolvability of tow prepreg>
Although the method for producing the tow prepreg will be described later, unlike the sheet-like prepreg, the tow prepreg is not usually covered with the film or release paper, and the paper fiber etc. as it is with the glass fiber bundle or carbon fiber bundle. It is taken up on a bobbin. Then, the tow prepreg wound around a paper tube is unwound and used.

  Therefore, if the tack (tackiness) of the tow prepreg is strong, there is a problem that the resistance during unwinding is strong and the unwinding at high speed can not be performed, or the single yarn of the reinforcing fiber bundle is taken and the unwinding can not be performed properly. .

<Shape retention of tow prepreg>
Usually, the tow prepreg is wound around the paper tube while being reciprocated in the axial direction of the paper tube. For this reason, when unwinding the tow prepreg, it is necessary to use a guide for fixing the position of the tow prepreg, since the position of the tow prepreg to be unwound moves in the axial direction of the paper tube. Although the shape of the guide to be used varies, in general, a freely rotating roll or comb having circumferential grooves on the surface is used. The unwound tow prepreg is fixed in position by passing through the grooves on the surface of the roll and the teeth of the comb. When coming into contact with a roll or a comb, the tow prepreg may be folded, but if the tack of the tow prepreg is too strong, it will not be opened as it is folded. When the tow prepreg is too soft, for example, the shape of the matrix resin composition in contact with a roll or a comb may change due to the viscosity of the matrix resin composition contained in the tow prepreg being too low. If the shape of the tow prepreg changes significantly, the quality and physical properties of the molded product may be adversely affected, which is a problem.

<Process passability of tow prepreg>
For example, when using a tow prepreg in FW forming, it is generally wound around a guide or several rolls to a mandrel. If the tack of the tow prepreg is too strong, the tow prepreg may be strongly abraded by the surface of the roll during the process, and the reinforcing fiber bundle may be damaged. When the reinforcing fiber bundle is damaged, the quality and physical properties of the molded product may be adversely affected.

  As a result of intensive studies, the present inventors consisted of reinforcing fiber bundles impregnated with a matrix resin composition containing particulate components, and the average maximum stress value obtained as a result of the tack test conducted in the procedure described below It has been found that the tow prepreg, which is in the range of 5,000 Pa to 55,000 Pa, is excellent in the unwindability from a paper tube, the process passability, and the form retention.

<Tack test>
The tack of toe prepreg can be measured by the following tack test.

Device: Tack Tester TA-500 (manufactured by UBM)
Contact area of plunger with sample: 3.1 cm ²
Plunger pressing time: 10 seconds Plunger pressing pressure : 90,000 Pa
Plunger rise speed: 1 mm / sec Measurement temperature: 23 ° C
Measurement humidity: 50% RH
procedure:
1) Place the tow prepreg on the sample table and fix it. At this time, the surface of the tow prepreg in contact with the plunger is the surface (that is, the surface on the side of the paper tube) which was not visible when the tow prepreg was wound on the paper tube.
2) Apply a pressure of 90,000 Pa to the plunger and press the tow prepreg for 10 seconds.
3) Raise the plunger at 1 mm / sec.
4) The maximum value of the stress value during raising the plunger is taken as the maximum stress value, and measurement is made a total of three times, and the average value of the obtained maximum stress values is taken as the average maximum stress value.

If the average maximum stress value of the tow prepreg obtained in the tack test is larger than 55,000 Pa, the strong tack of the tow prepreg can not unravel at high speed, or it can be reopened when the tow prepreg is folded. The problem of no If the average maximum stress value is less than 5,000 Pa, the tow prepreg may not stick to the mandrel during FW forming, or may slip when wound onto the mandrel. The average maximum stress value of the tow prepreg according to the present invention is more preferably 50,000 Pa or less.

<Viscosity of matrix resin composition>
As a major factor affecting the strength of the tack of tow prepreg, there is the viscosity of the matrix resin composition contained in the tow prepreg. The viscosity of the matrix resin composition at 30 ° C. is preferably 5 Pa · s to 300 Pa · s in order to obtain a tow prepreg excellent in unwindability from process, processability, and shape retention. The pressure is more preferably 10 Pa · s to 200 Pa · s, and particularly preferably 10 Pa · s to 100 Pa · s.

  When the viscosity at 30 ° C. of the matrix resin composition is larger than 300 Pa · s, the tack of the tow prepreg becomes strong, and the average maximum stress value of the above-mentioned tack test results becomes larger than 55,000 Pa, or It may be difficult to impregnate the reinforcing resin bundle with the matrix resin composition. If the viscosity of the matrix resin composition at 30 ° C. is less than 5 Pa · s, the average maximum stress value is smaller than 5,000 Pa, or the shape of the tow prepreg is too soft when passing through the guide. It may change.

<Content of matrix resin composition>
Another major factor affecting the strength of toe prepreg tack is the content of the matrix resin composition.

  The content of the matrix resin composition contained in the tow prepreg is preferably 20% by mass or more and 40% by mass or less. If the amount is 20% by mass or less, the matrix resin composition can not be sufficiently spread easily in the reinforcing fiber bundle, and many voids may be generated in the molded product. When the content of the matrix resin composition is 40% by mass or more, the average maximum stress value of the tack test result is larger than 55,000 Pa, or the fiber content volume ratio of the reinforcing fiber composite material is lowered, and the mechanical properties are effective. Can not be expressed. The content of the matrix resin composition is set to 20% by mass or more and 30% by mass or less in order to further improve the unwindability, processability, form retention, and mechanical property performance more effectively. Is more preferred.

  In order to obtain a tow prepreg having an average maximum stress value of 5,000 Pa to 55,000 Pa which is excellent in unwindability from a paper tube, processability, and form retention, the following matrix resin It is preferred to use the composition.

<Matrix resin composition 1>
Containing at least the following components (A) to (C), the content of the component (B) is 5 to 20 parts by mass with respect to 100 parts by mass of the component (A), and the content of the component (C) is specified The matrix resin composition which is 1-30 mass parts with respect to 100 mass parts of organic compound components, and whose primary particle diameter of component (C) is 1-30 micrometers.

Component (A): Epoxy resin Component (B): Boron trichloride amine complex Component (C): particulate thermoplastic resin That is, the matrix resin composition 1 is component (C) as the aforementioned "particulate component". : Contains particulate thermoplastic resin. The “specific organic compound component” is as described above, and in addition to the components (A) to (C) in the matrix resin composition 1, the state of polyether sulfone dissolved in the component (E) or epoxy resin described later When the thermoplastic resin is contained, the component (A), the component (B), the other component (E), and the thermoplastic resin dissolved in the epoxy resin all correspond to the "specific organic compound component", Content of the component (C) with respect to a total of 100 mass parts shall be 1-30 mass parts.

<Matrix resin composition 2>
The composition contains at least the following component (A), component (C) and component (D), and the total content of the component (C) and component (D) is 3 to 30 based on 100 parts by mass of the specific organic compound component The matrix resin composition which is a mass part and whose primary particle diameter of a component (C) is 1-30 micrometers.

Component (A): Epoxy resin Component (C): particulate thermoplastic resin Component (D): particulate epoxy resin curing agent, or particulate epoxy resin curing agent and particulate epoxy resin curing assistant The matrix resin composition 2 contains the component (C) as a particulate component described above: particulate thermoplastic resin, and the component (D): particulate epoxy resin curing agent, or particulate epoxy resin curing agent And a particulate epoxy resin curing aid. The “specific organic compound component” is as described above, and in the matrix resin composition 2, in addition to the component (A), the component (C), and the component (D), it is dissolved in the component (E) or epoxy resin described later In the case of including a thermoplastic resin such as polyether sulfone, the component (A) and the other component (E), and the thermoplastic resin dissolved in the epoxy resin all correspond to the "specific organic compound component", The total content of the component (C) and the component (D) is 3 to 30 parts by mass with respect to 100 parts by mass in total.

<Component (A)>
Component (A) is an epoxy resin.

  Usually, the term epoxy resin is used as the name of one category of thermosetting resin and the name of the category of chemical substance having a compound having an epoxy group in the molecule, but in the present invention, it is used in the latter meaning.

  As the component (A), it is preferable to use a difunctional epoxy resin having an aromatic ring in the molecule as a main component or the total amount of 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 are adjusted to an appropriate range. be able to.

  In addition, the "bifunctional epoxy resin" here means the compound which has two epoxy groups in a molecule | numerator.

  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 epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, resorcinol diglycidyl ether epoxy resin, hydroquinone diglycidyl ether epoxy Resin, terephthalic acid diglycidyl ester type epoxy resin, bis phenoxy ethanol orange glycidyl ether type epoxy resin, bisphenol fluoro orange glycidyl ether type epoxy resin, bis cresol fluoro orange glycidyl ether type epoxy resin, etc. may be mentioned, but are limited thereto Instead of the epoxy resin, two or more epoxy resins may be used in combination.

  Above all, as a bifunctional epoxy resin having an aromatic ring in the molecule, the viscosity of the matrix resin composition can be adjusted to a suitable range, and the mechanical properties of the cured product can be adjusted to a proper range. From the point of view, bisphenol A type epoxy resin is preferable, and in particular, 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 preferable.

<Component (B)>
Component (B) is a boron trihalide amine complex.

  As the boron trihalide amine complex, a complex comprising a boron halide such as boron trichloride or boron trifluoride and an organic amine is preferable. That is, as the component (B), a boron trichloride amine complex and a boron trifluoride amine complex are preferable.

  Specifically, for example, a boron trifluoride aniline complex, a boron trifluoride p-chloroaniline complex, a boron trifluoride ethylamine complex, a boron trifluoride isopropylamine complex, a boron trifluoride benzylamine complex, a boron trifluoride A dimethylamine complex, a boron trifluoride diethylamine complex, a boron trifluoride dibutylamine complex, a boron trifluoride piperidine complex, a boron trifluoride dibenzylamine complex, a compound in which a fluorine atom is replaced by a chlorine atom, and Examples include boron trichloride dimethyloctylamine complex and the like.

  Among these complexes, a boron trichloride dimethyloctylamine complex which is particularly excellent in the solubility in epoxy resin, the pot life of the composition to be contained, and industrially easy to obtain can be preferably used.

  The fiber-reinforced composite material produced by using these complexes as a curing agent has a strength suitable for developing excellent tensile strength in the strength of adhesion between the matrix resin composition and the surface of the reinforcing fiber. You can get it.

  When an epoxy resin having an aromatic ring in the molecule is used as the component (A), it is preferable to use a boron trichloride amine complex as the component (B) because it can be cured in a short time at a lower temperature.

  The preferable blending amount of the component (B) is usually 5 parts by mass or more, preferably 8 parts by mass or more, and usually 20 parts by mass with respect to 100 parts by mass of the component (A) contained in the matrix resin composition of the present invention. It is not more than mass part, preferably not more than 18 mass parts, more preferably not more than 17 mass parts. When the blending amount of the component (B) is extremely large or extremely small, the heat resistance of the cured resin may be lowered.

<Component (C)>
Component (C) is a particulate thermoplastic resin.

  Examples of the thermoplastic resin include polyamide, polyethylene, polyvinyl formal, polyether sulfone, polyphenyl sulfone, polysulfone, polyether imide, polyphenylene ether, polyphenylene sulfide, polycarbonate, polyether ether ketone, polyether ether sulfone and the like.

  Further, as the primary particle diameter of the component (C), it is preferable that the Sautamine diameter (Sauter's mean diameter (Sauter average particle diameter), SMD) measured by a laser diffraction / scattering particle size analyzer is 1 μm to 30 μm, More preferably, it is 2 μm to 15 μm. By including the component (C) in the reinforcing fiber bundle, an effect of preventing single fibers from being densely packed can be obtained. As a result, the volume of voids in the reinforcing fiber bundle can be increased, and more matrix resin composition can be contained in the reinforcing fiber bundle, and if sufficiently impregnated with the matrix resin composition, the matrix present in the surface of the tow prepreg The resin composition can be reduced. By reducing the matrix resin composition present on the surface of the tow prepreg, the tack of the tow prepreg can be reduced.

  Furthermore, the form of the tow prepreg formed by impregnating the reinforcing fiber bundle with the matrix resin composition having a relatively low viscosity changes easily when an external force is applied, and the width of the tow prepreg is increased by the surface tension of the matrix resin composition. It is thin and the cross section is rounded. The presence of the component (C) in the reinforcing fiber bundle can suppress the change in the shape of the above-described tow prepreg.

  If the primary particle diameter of the component (C) is smaller than 1 μm, there is a possibility that the effect of preventing the close packing of single fibers in the reinforcing fiber bundle may not be obtained, and if larger than 30 μm, the reinforcing fiber When the bundle is impregnated with the matrix resin composition, the component (C) is extremely separated by filtration, and the effect of preventing the single fibers in the reinforcing fiber bundle from being densely packed can not be obtained. The component (C) separated by filtration in the process or FW process using tow prepreg may adhere to and accumulate on the roll or the guide, which may cause a process problem.

  In order to obtain a tow prepreg having an average maximum stress value of 5,000 Pa to 55,000 Pa as a tack test result, in the matrix resin composition 1 described above, component (C) with respect to 100 parts by mass of the specific organic compound component The content of is preferably 1 to 30 parts by mass, and more preferably 2 to 10 parts by mass of component (C). If the amount of component (C) is too small, it may be difficult to sufficiently increase the volume of voids between fibers in the reinforcing fiber bundle, and if too large, the voids in the reinforcing fiber bundle The volume of the mold may become too large, and many voids may occur in a molded article produced using the tow prepreg.

  In the matrix resin composition 2 described above, the total content of the component (C) and the component (D) described later is preferably 3 to 30 parts by mass with respect to 100 parts by mass of the specific organic compound component. It is more preferable to set it as -20 mass parts. Furthermore, it is especially preferable to make content of a component (C) into 5-10 mass parts.

  When the component (C) and the component (D) are used in combination, considering the curability of the matrix resin composition by the component (D) and the action of providing an appropriate gap between the fibers in the reinforcing fiber bundle as described above, The total content is preferably 3 parts by mass or more, and the upper limit is preferably 30 parts by mass for the same reasons as in the case of matrix resin composition 1 described above.

<Component (D)>
Component (D) is a particulate epoxy resin curing agent, or a particulate epoxy resin curing agent and a particulate epoxy resin curing aid (combination use).

  The particulate epoxy resin curing agent in the component (D) is at least one selected from the group consisting of an epoxy resin imidazole adduct compound, an epoxy resin amine adduct compound, a modified aliphatic amine compound, dicyandiamide and an aromatic polyamine Is preferred. The particulate epoxy resin curing aid is preferably at least one selected from the group consisting of an epoxy resin imidazole adduct compound, an epoxy resin amine adduct compound, a modified aliphatic amine compound, and a urea compound. However, a compound different from the particulate epoxy resin curing agent used in combination is selected as the epoxy resin curing aid.

  The average particle diameter of the component (D) is preferably 1 μm to 30 μm, and more preferably 2 μm to 15 μm, of the sautamin diameter measured by a laser diffraction / scattering type particle size analyzer. The component (D) not only cures the component (A) epoxy resin but also exerts the same effect as the component (C) described above, that is, an effect of providing an appropriate gap between fibers in the reinforcing fiber bundle.

  In order to obtain a tow prepreg having an average maximum stress value of 5,000 Pa to 55,000 Pa as a tack test result, and to sufficiently cure the component (A) epoxy resin, in the matrix resin composition 2 described above, the specific organic compound The total content of the components (C) and (D) is preferably 3 to 30 parts by mass, and more preferably 4 to 20 parts by mass with respect to 100 parts by mass of the components. Furthermore, it is especially preferable to make content of a component (C) into 5-10 mass parts.

  When the amount is less than 3 parts by mass, the volume of the voids in the reinforcing fiber bundle may not be sufficiently increased, or the component (A) epoxy resin may not be sufficiently cured. If the amount is more than 30 parts by mass, the volume of the voids in the reinforcing fiber bundle becomes too large, and many voids are generated in a molded article produced using the tow prepreg, or the mechanical properties of the cured product due to excessive curing agent. May decrease.

<Component (E)>
In the matrix resin composition of the present invention, any of matrix resin compositions 1 and 2 may further contain component (E): rubber particles.

  Component (E) is blended to improve the toughness of the matrix resin composition after curing. Component (E) includes at least one rubber particle selected from the group consisting of crosslinked rubber particles and core-shell rubber particles obtained by graft polymerizing a polymer different from the polymer constituting the crosslinked rubber particles on the surface of the crosslinked rubber particles. Preferably used.

  With respect to the crosslinked rubber particles, the type of rubber is not limited, and for example, butadiene rubber, acrylic rubber, silicone rubber, butyl rubber, NBR, SBR, IR, EPR and the like are used. As an example of a crosslinked rubber particle, product name: YR-500 series (made by Tohto Kasei Co., Ltd.) etc. is mentioned.

  As a core component which comprises core-shell type rubber particles, the thing similar to the said crosslinked rubber particle is mentioned. Among them, a crosslinked rubbery polymer composed of styrene and butadiene is preferable because of its high toughness improvement effect.

  The shell component constituting the core-shell rubber particles is preferably graft-polymerized to the above-mentioned core component and preferably chemically bonded to the polymer constituting the core component. The term "chemical bond" as used herein means a bond between atoms that combines atoms or ions to form a molecule or a crystal. In particular, the chemical bond here means a covalent bond formed by the electron pair being shared by two atoms.

  As a component constituting such a shell component, it is possible to use, for example, a polymer obtained by polymerizing at least one selected from the group consisting of an acrylic acid ester type monomer, a methacrylic acid ester type monomer, and an aromatic vinyl monomer. it can. When a crosslinked rubbery polymer composed of styrene and butadiene is used as the core component, a mixture of methyl methacrylate which is a methacrylic acid ester and styrene which is an aromatic vinyl compound can be suitably used as the shell component. .

  In addition, it is preferable that a functional group that reacts with the component (A), that is, an epoxy resin, be introduced into the shell component in order to stabilize the dispersed state of the core-shell type rubber particles. As such a functional group, for example, a hydroxyl group, a carboxyl group and an epoxy group can be mentioned, and among these, an epoxy group is preferable. As a method of introducing an epoxy group, there is a method of graft polymerization on the core component by using, for example, 2,3-epoxypropyl methacrylate in combination with the above-mentioned shell component.

  As a specific commercial product, product name using acrylic rubber: W-5500 or product name: J-5800 (manufactured by Mitsubishi Rayon Co., Ltd.), product name using silicone / acrylic composite rubber: SRK-200E ( Product name consisting of Mitsubishi Rayon Co., Ltd., product of butadiene, alkyl methacrylate and styrene copolymer: product of Paraloid EXL-2655 (manufactured by Kuwaha Chemical Industry Co., Ltd.), copolymer of acrylic acid ester and methacrylic acid ester Name: Staphyloid AC-3355 or product name: TR-2122 (made by Takeda Pharmaceutical Co., Ltd.), product name consisting of butyl acrylate / methyl methacrylate copolymer: PARALOID EXL-2611 or product name: EXL-3387 (Made by Rohm & Haas) etc. can be mentioned.

  The component (E) may be dispersed in the component (A) using a stirrer, a roll mill or the like at the time of preparation of the matrix resin composition, but a masterbatch type in which the component (E) is dispersed in advance in an epoxy resin The use of the rubber particle-dispersed epoxy resin is preferable because not only the preparation time of the matrix resin composition can be shortened but also the dispersion state of the rubber particles in the matrix resin composition can be improved. Furthermore, it is particularly preferable that the rubber particles and the matrix resin component are chemically or physically bonded.

  Such masterbatch-type crosslinked rubber particle-dispersed epoxy resin includes acrylic rubber-containing product name: BPF 307 or product name: BPA 328 (manufactured by Nippon Shokubai Co., Ltd.); core component of copolymer of styrene and butadiene Product Name: MX-113 or Product Name: MX-416; Product Name Containing Butadiene Rubber: Product Name Containing Core Shell Rubber Particles Containing Methyl Methacrylate and a Shell Component Having a Functional Group Reactive with an Epoxy Resin Product Name: MX -156; Product name containing silicone rubber: MX-960 (manufactured by Kaneka Co., Ltd.) and the like.

  In order to improve the toughness of the matrix resin composition after curing, particularly for improving the breaking pressure when used in a pressure vessel described later, the component (E) should be rubber particles containing butadiene rubber. preferable. That is, butadiene rubber particles and core-shell rubber particles having butadiene rubber particles as a core component are preferable, and core-shell rubber particles having butadiene rubber particles as a core component are particularly preferable.

  The particle diameter of the component (E) in the cured product of the matrix resin composition is preferably 50 nm or more and 400 nm or less, and more preferably 50 nm or more and 300 nm or less. The particle size of the component (E) in the cured product can be measured by the following method.

<When the particle size of the component (E) can be confirmed by a scanning electron microscope (SEM)>
The particle diameter of the component (E) or component (E) confirmed by observing an arbitrary range of 100 μm ² of the fracture surface of the test body when the fracture toughness value of the cured resin is measured according to ASTM D5045 E) The diameter of the recessed part which dropped off is measured at any ten places, and the average value thereof is taken as the particle size in the cured product of component (E).

<If the particle size of the component (E) is difficult to confirm by SEM>
The cured resin plate is immersed in dichloromethane to elute the component (E). An arbitrary 100 μm ² range of the cured resin plate in which the component (E) is eluted is observed with a scanning probe microscope, and the diameter of the concave part where the identified component (E) is eluted is measured at any ten locations and the average thereof Let the value be the particle size in the cured product of component (E).

  In order to bring the particle size in the cured product into the above range, it is preferable to use a component (E) in which the volume average particle size of the primary particles is 50 nm or more and 400 nm or less, more preferably 50 nm or more and 300 nm or less. A matrix resin composition is prepared using a masterbatch type rubber particle-dispersed epoxy resin dispersed in component (A) using a roll mill or the like, or in which component (E) is previously dispersed in component (A). By doing this, the particle size of the component (E) in the cured product of the epoxy resin composition can be controlled within the above range. The volume average particle size of the primary particles of the rubber particles can be measured by a laser diffraction / scattering type particle size analyzer or the like.

  The preferable blending amount of the component (E) is usually 10 parts by mass or more, preferably 16 parts by mass or more, more preferably 20 parts by mass with respect to 100 parts by mass of the component (A) contained in the matrix resin composition of the present invention. The amount is usually 110 parts by mass or less, preferably 100 parts by mass or less, and more preferably 80 parts by mass or less.

  When the component (E) is extremely large, dispersion in the component (A) becomes difficult, the matrix resin composition has a high viscosity, and handling and impregnation into reinforcing fiber bundles become difficult, and tack of the produced tow prepreg May become stronger. On the other hand, when the amount of the component (E) is extremely small, the improvement in toughness of the matrix resin composition after curing is insufficient, and the effect of the component (E) may not be obtained.

<Additives>
Furthermore, the matrix resin composition of the present invention may be silica powder, Aerosil, microballoon, inorganic particles such as antimony trioxide, alumina, titanium oxide etc., flame retardants such as phosphorus compounds, carbon particles such as carbon black, activated carbon, etc. (A) A thermoplastic resin dissolved in an epoxy resin, and additives such as an antifoaming agent and a wetting agent may be blended according to the purpose to such an extent that the effect of the present invention is not impaired.

  Component (A), that is, a thermoplastic resin dissolved in an epoxy resin, for example, polyamide, polyethylene, polyvinyl formal, polyether sulfone, polyphenyl sulfone, polysulfone, polysulfone, polyether imide, polyphenylene ether, polyphenylene sulfide, polycarbonate, polyether Ether ketone, polyether ether sulfone etc. are mentioned.

  The tow prepreg of the present invention can be produced by any known production method. Among them, it is preferable to prepare according to the following procedure.

<Preferred tow prepreg production method>
(1) The matrix resin composition is supplied to at least one surface of the reinforcing fiber bundle (tow) which has been heated and spread in advance.
(2) The impregnated matrix resin composition is uniformly impregnated into the reinforcing fiber bundle.
(3) The temperature of the tow prepreg is cooled to about room temperature.
(4) The tow prepreg is wound on a paper tube or the like.

  It is desirable that the reinforcing fiber bundle to be subjected to the step (1) be widened and have a flat shape, because the contact area with the matrix resin composition becomes wide. Examples of the method of widening include a method of rubbing with a cylindrical bar, a method of applying vibration, and a method of crushing. Furthermore, when widening the reinforcing fiber bundle, it is preferable to heat the reinforcing fiber bundle to about the softening point of the applied sizing agent in order to soften and facilitate the spreading of the sizing agent usually applied to the reinforcing fiber bundle. Furthermore, this preheating of the tow also has the effect of raising the temperature of the reinforcing fiber bundle in advance so that the temperature of the resin composition does not decrease when the matrix resin composition penetrates into the reinforcing fiber bundle. If the temperature of the reinforcing fiber bundle is heated to a temperature before the contact with the reinforcing fiber bundle of the matrix resin composition by heating, the temperature of the reinforcing fiber bundle after the contact between the reinforcing fiber bundle and the matrix resin composition is before the contact Never lower than the resin temperature of As a heating method, any of noncontact heating methods such as contact heating with a heating body, infrared heating, atmosphere heating and the like can be used.

  In the present invention, the widening of the reinforcing fiber bundle may be performed inline or off-line. For example, commercially available spread tape-like reinforcing fiber bundles are regarded as off-line expanded reinforcing fiber bundles.

  As a method of supplying the matrix resin composition, a resin bath method, a rotating roll method, a transfer method on paper, and a nozzle drop described in JP-A-09-176346, JP-A-2005-335296 and JP-A-2006-063173. The resin contact and toe transfer methods described in Japanese Patent Application Laid-Open Nos. 08-073630, 09-031219, and 8-73630 can be mentioned.

  Among them, the rotating roll method, the resin contact, and the tow transfer method are preferable as the method for supplying the matrix resin composition because of the control of the supply amount of the matrix resin composition and the ease of implementation. In addition, the width of the reinforcing fiber bundle is not usually stabilized, and there are variations in how it is spread. Therefore, as described in JP-A-8-73630, it is effective to narrow and stabilize the tow width immediately before or at the time of resin contact after the reinforcing fiber bundle is widened. As a specific example, there is a method of providing a groove having a predetermined width at or just before the resin discharge port and running the reinforcing fiber bundle in the groove to narrow the width of the reinforcing fiber bundle.

  The heating upon impregnation of the matrix resin composition into the reinforcing fiber bundle can be performed by a known method. Above all, a method of rubbing with a heating body such as a heating roll or a heating plate, passing through a heating furnace when the reinforcing fiber bundle supplied with the matrix resin composition runs idle, or heating by noncontact heating means such as infrared heating It is preferable to Heating by non-contact heating means so that the temperature of the reinforcing fiber bundle and the matrix resin composition does not fall between the supply of the matrix resin composition to the reinforcing fiber bundle and the heating body, and between the heating body and the heating body. It is even more preferable that

  Furthermore, in the impregnation step, an external force is applied to the reinforcing fiber bundle to move the filaments constituting the reinforcing fiber bundle in the lateral direction (that is, the direction orthogonal to the fiber direction) to change the relative position between the filaments to It is preferable to add the step of increasing the chance of contact. It is possible to increase the uniform impregnation effect more than the impregnation effect by mere pressure or capillary action.

  Specifically, the reinforcing fiber bundle is folded, the reinforcing fiber bundle is widened, the reinforcing fiber bundle is crimped, or the reinforcing fiber bundle is twisted or the like. In these means, the folding means and the twisting means tend to narrow the width of the reinforcing fiber bundle as well as the narrowing means. And if the means which has the effect | action which narrows the width | variety of a reinforced fiber bundle and the means which extends the width | variety of a reinforced fiber bundle are used together, the effect of uniform impregnation will become high. In addition, what is necessary is just to carry out at the time of resin impregnation, and if a state without a twist after impregnation is required, it may retwist after impregnation. In the case of false twisting, it is not necessary to carry out untwisting, and it is desirable when untwisted reinforcing fiber bundles are required. If rubbing is added simultaneously with or immediately after twisting, the width of the reinforcing fiber bundle tends to widen, and the uniformity of the impregnation becomes higher due to the movement of the resin in the thickness direction.

  In uniform impregnation by lateral movement of the filament, it is useful for making the reinforcing fiber bundle contact with a rotating body rotating at a peripheral speed less than the traveling speed of the reinforcing fiber bundle and rubbing it, for fluff deposition, roll cleaning, etc. If it is abraded, the reinforcing fiber bundle does not get entangled on the surface of the rotating body, and the rotating body is rubbed with the reinforcing fiber bundle, and since it is rotating, the surface in contact with the reinforcing fiber bundle is always cleaned It is also useful for improving the manufacturing environment. However, it is preferable that the circumferential speed of the rotating body be 50% or more and 99% or less of the traveling speed of the reinforcing fiber bundle. If the circumferential speed of the rotating body is less than 1/2 of the traveling speed of the reinforcing fiber bundle, the reinforcing fiber bundle may be fluffed by being strongly abraded, and it may be wound in a later process or wound on a paper tube. Problems can arise when unwinding the tow prepreg.

  If the matrix resin composition is not uniformly impregnated in the reinforcing fiber bundle, the mechanical properties of the produced reinforcing fiber composite material may be deteriorated, and the effects of the present invention may not be sufficiently obtained.

  The reinforcing fiber bundle uniformly impregnated with the matrix resin composition is cooled to about room temperature by using a known cooling means such as rubbing on a cooling body or non-contact cooling means before the winding process to a paper tube. It is preferable to keep the If it is rolled up without sufficient cooling, the matrix resin composition has a low viscosity, so that when it is rolled up, slippage occurs and the winding form is disturbed, or if it is wound up once, heat escapes from the central part Because the temperature is high and the temperature is high for a relatively long time, the pot life of the matrix resin composition may be shortened.

  The tow prepreg of the present invention thus obtained has the advantages (features) that it is excellent in unwinding from a paper tube, processability and drapeability, and is therefore suitable for filament winding molding, pultrusion and the like.

  Hereinafter, the present invention will be further described by way of examples and comparative examples.

<Example and Comparative Example>
The raw material of the resin composition used in each Example, the preparation method, and the measuring method of each physical property are shown below. The composition of each matrix resin composition and the measurement results of physical properties are summarized in Tables 1 and 2. In addition, the numerical value of each component in Table 1 and 2 represents the mass part number of each component mix | blended with a matrix resin composition. The scope of the present invention is not limited to the examples.

<Raw material>
[Component (A)]
jER1001
"Product name" jER1001
"Component" bisphenol A type epoxy resin (bifunctional epoxy resin)
(Epoxy equivalent weight: 475 g / eq)
"Supplier" Mitsubishi Chemical Corporation CY-184
Product Name: Araldite CY-184
"Component" Hexahydrophthalic acid diglycidyl ester (epoxy equivalent: 158 g / eq)
"Supply source" Huntsman Japan Ltd. [Master batch rubber particle dispersed epoxy resin in which component (E) is dispersed in component (A)]
MX-257
"Product Name" Kanae 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 diameter: 200 nm): 37% by mass
"Supplier" Kaneka Corporation MX-154
"Product Name" Kanae Ace MX-154
"Component" Bisphenol A type epoxy resin (bifunctional epoxy resin. Epoxy equivalent: 189 g / eq): 60% by mass, and butadiene core-shell type rubber particles (volume average particle size: 100 nm): 40% by mass
"Supplier" Kaneka Corporation [Component (B)]
DY9577
Product Name DY 9577
"Component" Boron trichloride amine complex "Supplier" Huntsman Japan KK [Component (C)]
2001 UD
Product Name ORGASOL 2001 UD NAT1
"Component" polyamide 12 (Sautamin diameter: 5.3 μm)
"Supplier" Arkema Inc.
1002 UD
Product Name ORGASOL 1002D NAT1
"Component" Polyamide 12 (Sautamin diameter: 18 μm)
"Supplier" Arkema Inc.
Vestosint 2159
Product Name Vestsint 2159
"Component" Polyamide 12 (Sautamin diameter: 10 μm)
"Supplier" Evonik Industries AG
[Component (D)]
DICY15
"Product Name" jER Cure DICY15
"Component" dicyandiamide (Sautamin diameter: 2 μm)
"Supplier" Mitsubishi Chemical Corporation PN-23
Product Name Amicure PN-23
"Component" amine adduct type curing agent (Sautamin diameter: 6μm)
"Supplier" Ajinomoto Fine Techno Co., Ltd. 2014FG
"Product Name" Ankamin 2014FG
"Component" modified aliphatic amine (Sautamin diameter: 2μm)
"Supplier" Air Products Japan Co., Ltd. A matrix resin composition having the composition described in Tables 1 and 2 was prepared as follows. In addition, the numerical value of each component in a table represents a mass part.

<Resin preparation of Example 1>
A portion of MX-257 was dispersed 2001UD using a roll mill. After weighing MX-257 dispersed with 2001 UD and the remaining MX-257, CY-184, DY 9577 into a flask, the contents are visually observed while heating the contents at 40 to 65 ° C. using a water bath The mixture was stirred until uniform, to obtain a matrix resin composition of Example 1.

<Resin preparation of Example 2>
A portion of MX-257 was dispersed with 1002D using a roll mill. After weighing MX-257 dispersed with 1002 D and the remaining MX-257, CY-184, DY 9577 into a flask, the contents are visually observed while heating the contents at 40 to 65 ° C. using a water bath The mixture was stirred until uniform, to obtain a matrix resin composition of Example 2.

<Resin preparation of Example 3>
Disperse 2001 UD in MX-257 using a roll mill. After weighing MX-257 and DY9577 dispersed with 2001 UD into a flask, the contents were stirred at 40 to 65 ° C. using a water bath, and stirred until the contents were visually uniform, Example 3 The matrix resin composition of

Resin Preparation of Examples 4 to 7
Vestosint 2159 was dispersed on a part of MX-257 using a roll mill. After weighing MX-257 dispersed Vestosint 2159 and the remaining MX-257, CY-184, DY 9577 into a flask, the contents are visually observed while heating the contents at 40 to 65 ° C. using a water bath The mixture was stirred until uniform and matrix resin compositions of Examples 4 to 7 were obtained.

Resin Preparation of Examples 8 to 11
Vestosint 2159 was dispersed on a part of MX-257 using a roll mill. The remaining MX-257 and jER 1001 were weighed into a flask and stirred until the contents were visually uniform while heating the contents at 80-110 ° C. using a water bath. The mixture of the remaining MX-257 and jER1001 prepared was removed from the flask and allowed to cool to about room temperature. Weigh the contents of MX-257 dispersed with Vestosint 2159, the mixture of the remaining MX-257 and jER1001, DY 9577 into a flask and then use the water bath to heat the contents at 40 to 65 ° C while visually observing the contents The mixture was stirred until uniform and matrix resin compositions of Examples 8 to 11 were obtained.

<Resin preparation of Example 12>
In part of MX-257, DICY15, PN-23, 2014FG, and 2001UD were dispersed using a roll mill. Weigh MX-257 dispersed with DICY15, PN-23, 2014FG, and 2001 UD and the remaining MX-257 into a flask, and then heat the contents at 40-55 ° C using a water bath. The matrix resin composition of Example 12 was obtained by stirring until the substance was visually uniform.

<Resin preparation of Example 13>
PN-23 and 2001 UD were dispersed in part of MX-257 using a roll mill. After weighing PN-23, and MX-257 dispersed with 2001 UD, and the remaining MX-257, and CY-184 into a flask, use a water bath while warming the contents at 40-55 ° C. The mixture was stirred until the contents were visually uniform, to obtain a matrix resin composition of Example 13.

<Preparation of Resin of Comparative Example 1>
After weighing all the raw materials into a flask, while heating the contents at 40 to 65 ° C. using a water bath, the contents are stirred until the contents become visually uniform, and a matrix resin composition of Comparative Example 1 is obtained. The

Resin Preparation of Comparative Examples 2 to 4
Vestosint 2159 was dispersed on a part of MX-257 using a roll mill. After weighing MX-257 dispersed Vestosint 2159 and the remaining MX-257, CY-184, DY 9577 into a flask, the contents are visually observed while heating the contents at 40 to 65 ° C. using a water bath The mixture was stirred until uniform and matrix resin compositions of Comparative Examples 2 to 4 were obtained.

<Method of measuring viscosity of matrix resin composition>
The viscosity at the time of temperature rising was measured on the following measurement conditions about the matrix resin composition obtained by the above-mentioned each Example and comparative example, and the viscosity at 30 degreeC was calculated | required.

Measurement conditions Device: AR-G2 (manufactured by TA Instruments)
Working plate: 35 mm パ ラ レ ル Parallel plate Plate gap: 0.5 mm
Measurement frequency: 10 rad / sec
Heating rate: 2 ° C / min
Stress: 3000 dynes / cm ²
<Production of tow prepreg>
Matrix resin composition obtained in each of the above-described Examples and Comparative Examples, and high-strength carbon fiber manufactured by Grafil Product name: 37-800 (tensile strength: 5520 MPa, tensile modulus of elasticity: 255 GPa, number of filaments: 30,000) To produce a tow prepreg.

  First, the said carbon fiber was heated to 50-100 degreeC, and it was made to widen to 11-15 mm in width.

  The matrix resin composition heated to 40 to 65 ° C. is quantitatively supplied to the widened carbon fiber bundle (hereinafter simply referred to as “carbon fiber bundle”) using a matrix resin composition supply device, and further, The carbon fiber bundle was uniformly impregnated using a resin impregnation device constituted of a heating roll. As one of the impregnation means, a method was adopted in which the filaments were moved in the lateral direction (direction orthogonal to the fiber direction of the filaments) so that the matrix resin composition uniformly impregnated the reinforcing fiber bundles. After cooling this to room temperature, it was wound on a paper tube.

<Measurement of average maximum stress value>
A tack test was performed on each of the tow prepregs obtained in the above-mentioned <Production of tow prepregs> in the following procedure to determine an average maximum stress value.

[Tack test]
Device: Tack Tester TA-500 (manufactured by UBM)
Contact area of plunger with sample: 3.1 cm 2
Plunger pressing time: 10 seconds Plunger pressing pressure : 90,000 Pa
Plunger rise speed: 1 mm / sec Measurement temperature: 23 ° C
Measurement humidity: 50% RH
procedure:
1) The tow prepreg was placed on the sample table and fixed. At this time, the surface of the tow prepreg in contact with the plunger was the surface (that is, the surface on the side of the paper tube) which was not visible when the tow prepreg was wound on the paper tube.
2) A pressure of 90,000 Pa was applied to the plunger, and the tow prepreg was pressed for 10 seconds.
3) The plunger was raised at 1 mm / sec.
4) The maximum stress value during raising the plunger was taken as the maximum stress value, and measurement was made a total of three times, and the average value of the obtained maximum stress values was taken as the average maximum stress value.

<High-speed dissolution evaluation of tow prepreg>
High speed dissolution of tow prepreg by unwinding the tow prepreg wound on a paper tube by 200 m at a speed of 50 m / min using the device consisting of creel, guide, dancer roll, godd roll and winder shown in FIG. 1 I made an evaluation. Moreover, the tension of unwinding was 1000 g. In the case where ringing did not occur during this period and the guide, rolls and the like in the process could be unwound without causing winding, it was judged as pass.

<Evaluation of form retention of tow prepreg>
When the tow prepreg passes through the guide in a process such as FW molding, it is folded and reopened to determine whether the tow width before passing through the guide becomes equal, that is, the form retention of the tow prepreg is Evaluated by the method.
procedure:
1) The tow prepreg wound around a paper tube was unrolled by about 20 cm.
2) The approximately central portion of the cut tow prepreg of about 20 cm in length is folded about 5 cm. At this time, the crease line was along the reinforcing fibers, and when the tow prepreg was folded, the paper tube side was inside.
3) A tow prepreg of about 20 cm in length was placed on a desk, and a 5 cm long, 1 cm wide, 2 mm thick resin plate was placed on the folded portion of the tow prepreg, and a 200 g weight was placed on the resin plate.
4) After standing for 15 seconds in this state, a 200 g weight and a resin plate were removed.
5) The both ends of a tow prepreg having a length of about 20 cm were held by hand, and both ends were pulled so that the tow prepreg was stretched. In this case, the case where the folded portion was opened was passed, and the case where it was not opened was rejected.

<Evaluation of tow prepreg of Example 1>
The tow prepreg of Example 1 was produced as described above. Component (C) is significantly filtered out in the preparation process and does not adhere to or deposit on the roll or guide, and further, process troubles due to adhesion or deposition of the component (C) filtered off on the roll or guide also occur I did not. The tow prepreg of Example 1 produced was an appropriate tack, and was good in terms of the unwindability from a paper tube, the processability in the FW forming process, and the form retention. In addition, it also passed in the tow prepreg high-speed unraveling evaluation and the form retention evaluation of the tow prepreg.

<Tow prepreg evaluation of Examples 2 to 11>
The tow prepregs of Examples 2 to 11 were produced as described above. Component (C) is significantly filtered out in the preparation process and does not adhere to or deposit on the roll or guide, and further, process troubles due to adhesion or deposition of the component (C) filtered off on the roll or guide also occur I did not. The prepared tow prepregs of Examples 2 to 11 were suitable tacks, and were good in view of the unwindability from a paper tube, the processability in the FW forming process, and the form retention.

<Tow prepreg evaluation of Examples 12 and 13>
The tow prepregs of Examples 2 to 10 were produced as described above. The component (C) and the component (D) are separated by filtration in the preparation process, and do not adhere to or deposit on the roll or guide. Furthermore, the component (C) separated by filtration is adhered to the roll or guide, resulting from deposition. There were no process problems. The tow prepregs of Examples 12 and 13 produced were suitable tacks, and were good in view of the unwindability from a paper tube, the processability in the FW forming process, and the form retention.

<Tow prepreg evaluation of Comparative Example 1>
The tow prepreg of Comparative Example 1 was produced as described above. No process trouble occurred in the manufacturing process. The prepared tow prepreg of Comparative Example 1 was very strong in tack, and when it was unwound at high speed from a paper tube, the resistance was strong and could not be solved smoothly, or ringer was generated. In addition, since the tack is very strong, the guide, the roll, and the like are wound in the FW forming process, and the tow prepreg folded by the guide can not be widened again. Moreover, it was also disqualified in the tow prepreg high-speed unraveling evaluation and the form-retaining evaluation of tow prepreg.

<Tow prepreg evaluation of Comparative Examples 2 to 4>
The tow prepregs of Comparative Examples 2 to 4 were produced as described above. Component (C) is separated by filtration in the preparation process, deposited in large amounts on rolls and guides, and further adhered to rolls and guides by component (C) separated by filtration, the end yarns of reinforcing fibers are taken for deposition And winding on the guide occurred. The prepared tow prepregs of Comparative Examples 2 to 4 were very weak in tackiness and were good in terms of the unwindability from the paper tube and the process passability in the FW forming process, and the form retention, but in the case of FW forming The tow prepreg did not adhere to the liner, causing problems.

1 Tow pre-preg 2 guide 3 dancer roll 4 goded roll wound on paper tube

Claims (10)

  A tow prepreg comprising a reinforcing fiber bundle impregnated with a matrix resin composition containing particulate components, wherein the average maximum stress value in the tack test results is in the range of 5,000 to 55,000 Pa.   The tow prepreg according to claim 1, wherein the viscosity of the matrix resin composition at 30 ° C is 5 to 300 Pa · s.   The tow prepreg according to claim 1 or 2, wherein the reinforcing fiber bundle is a carbon fiber bundle.   The resin content rate is 20-40 mass%, The tow prepreg as described in any one of Claims 1-3. The matrix resin composition contains the following components (A) to (C), and the content of the component (B) is 5 to 20 parts by mass with respect to 100 parts by mass of the component (A); The content of C) is 1-30 mass parts with respect to 100 mass parts of specific organic compound components, and the primary particle diameter of component (C) is 1-30 micrometers, Any one of Claims 1-4 The tow prepreg as described in.
Component (A): Epoxy resin Component (B): Boron trichloride amine complex Component (C): Particulate thermoplastic resin The matrix resin composition contains the following component (A), component (C) and component (D), and the total content of the component (C) and component (D) is relative to 100 parts by mass of the specific organic compound component The tow prepreg according to any one of claims 1 to 4, which is 3 to 30 parts by mass, and the primary particle diameter of the component (C) is 1 to 30 μm.
Component (A): Epoxy resin Component (C): particulate thermoplastic resin Component (D): particulate epoxy resin curing agent, or particulate epoxy resin curing agent and particulate epoxy resin curing auxiliary   The particulate epoxy resin curing agent in the component (D) is at least one selected from the group consisting of epoxy resin imidazole adduct compounds, epoxy resin amine adduct compounds, modified aliphatic amine compounds, dicyandiamide and aromatic polyamines The tow prepreg according to claim 6.   The particulate epoxy resin curing aid in the component (D) is at least one selected from the group consisting of an epoxy resin imidazole adduct compound, an epoxy resin amine adduct compound, a modified aliphatic amine compound and a urea compound (however, The tow prepreg according to claim 6 or 7, which is a compound different from the particulate epoxy resin curing agent used in combination as a part of the component (D). The matrix resin composition further comprises the following component (E), and the content of the component (E) is 10 to 110 parts by mass with respect to 100 parts by mass of the component (A). The tow prepreg according to any one of the preceding claims.
Component (E): rubber particles   The tow prepreg according to claim 9, wherein the component (E) is a rubber particle containing butadiene rubber.