WO2016143524A1

WO2016143524A1 - Fiber-reinforced resin material, fiber-reinforced resin molded article and method for producing fiber-reinforced resin molded article

Info

Publication number: WO2016143524A1
Application number: PCT/JP2016/055509
Authority: WO
Inventors: 林　豊; 武俊中山; 福田　寛; 穂奈美野田
Original assignee: 小松精練株式会社
Priority date: 2015-03-09
Filing date: 2016-02-24
Publication date: 2016-09-15
Also published as: JPWO2016143524A1

Abstract

The fiber-reinforced resin material according to the present invention comprises a thermoplastic resin and reinforcing fibers. The fiber-reinforced resin material can be molded through heating, and cannot be remolded through heating after being heated at a specific temperature or at a higher temperature during or after molding.

Description

Fiber-reinforced resin material, fiber-reinforced resin molded body, and method for producing fiber-reinforced resin molded body

The present invention relates to a fiber-reinforced resin material, a fiber-reinforced resin molded body using the material, and a method for producing a fiber-reinforced resin molded body.

As a fiber reinforced resin molding using reinforced fibers and resin, a sheet-like thermosetting prepreg (thermosetting prepreg sheet) using reinforcing fibers such as glass fiber and thermosetting resins such as thermosetting epoxy resin is used. )It has been known.

However, the thermosetting prepreg sheet cannot be remolded, and there is a problem that a low temperature cold storage warehouse is required for storing the uncured (before thermosetting) sheet. Moreover, it took a long time to cure the uncured material of the thermosetting resin, and there was a problem in productivity.

In order to overcome these drawbacks, a fiber reinforced resin molded article using a reinforced fiber and a thermoplastic resin is known. A fiber reinforced resin molded article using a thermoplastic resin can be remolded by heating even after curing.

However, when a fiber reinforced resin molded product obtained using a thermoplastic resin and a reinforced fiber is used in a high temperature environment exceeding 100 ° C., the fiber reinforced resin molded product becomes flexible or deforms. There is. For this reason, the fiber reinforced resin molded article using the thermoplastic resin and the reinforcing fiber is suitable for use at room temperature, although it depends on the glass transition temperature of the thermoplastic resin, and in an environment of about 80 ° C. Suitable when used.

Therefore, a high-strength fiber composite has been proposed in which the surface of a prepreg composed of high-strength fibers and a thermoplastic resin is coated with a thermosetting resin (Patent Documents 1 and 2).

However, in the high-strength fiber composites disclosed in Patent Document 1 and Patent Document 2, the complexity of handling the thermosetting resin and the problem of moldability have not been solved.

JP-A-6-91816 JP 2013-233681 A

INDUSTRIAL APPLICABILITY The present invention provides a fiber reinforced resin material and a fiber reinforced resin material that can be easily molded into a desired shape by heating and that can provide a fiber reinforced resin molded product having a stable form even under a high temperature environment after molding. It aims at providing the resin molding.

The inventors of the present invention have made the present invention as a result of intensive studies in order to solve the above problems.

That is, the present invention has, for example, the following configurations (1) to (14).

(1) The fiber reinforced resin material according to the present invention is a fiber reinforced resin material containing a thermoplastic resin and a reinforced fiber, which can be molded by heating, and has a specific temperature during or after the molding. After heating, it cannot be reshaped by heating.

(2) In the fiber reinforced resin material according to the present invention, the thermoplastic resin may be an epoxy resin.

(3) The fiber reinforced resin material according to the present invention may contain a crosslinking agent having two or more functional groups.

(4) In the fiber reinforced resin material according to the present invention, the cross-linking agent may include at least one of a block type isocyanate compound and a novolac type resin.

(5) In the fiber reinforced resin material according to the present invention, the specific temperature may be 130 ° C. or higher.

(6) The fiber reinforced resin material according to the present invention may not be remolded by heating and pressurizing at a temperature of 150 ° C. and a pressure of 2 MPa after being heated at the specific temperature or higher.

(7) The fiber-reinforced resin molded body according to the present invention is obtained using the fiber-reinforced resin material described in any one of (1) to (6) above.

(8) A fiber-reinforced resin molded body according to the present invention is a fiber-reinforced resin molded body molded by heating the fiber-reinforced resin material according to any one of (1) to (6), It is heated at the specified temperature or higher at the time of molding or after the molding, and after heating at the specified temperature or higher, it cannot be reshaped by heating.

(9) The fiber reinforced resin molded body according to the present invention cannot be remolded by heating and pressurizing at a temperature of 150 ° C. and a pressure of 2 MPa after being heated at the specific temperature or higher.

(10) In the method for producing a fiber reinforced resin molded body according to the present invention, the fiber reinforced resin molded body is molded by applying a solution containing a thermoplastic resin to the reinforced fiber and heating at a predetermined molding temperature. When the fiber reinforced resin molded body is heated at a specific temperature or higher at the time of molding or after molding of the reinforced resin molded body, it cannot be remolded by heating.

(11) In the method for producing a fiber-reinforced resin molded body according to the present invention, the thermoplastic resin may be an epoxy resin.

(12) In the method for producing a fiber-reinforced resin molded body according to the present invention, the solution may contain a crosslinking agent having two or more functional groups.

(13) In the method for producing a fiber-reinforced resin molded body according to the present invention, the cross-linking agent may include at least one of a block-type isocyanate compound and a novolac-type resin.

(14) In the method for producing a fiber-reinforced resin molded body according to the present invention, the specific temperature may be 130 ° C. or higher.

According to the fiber reinforced resin material according to the present invention, since molding by heat is possible, a molded body can be easily manufactured, and a molded body having excellent shape stability by heat can be obtained. A fiber-reinforced resin molded product that can be used even in an environment can be obtained.

Further, according to the fiber reinforced resin molded article according to the present invention, since the form at high temperature is stable, it can be used even in a high temperature environment.

Further, according to the method for producing a fiber-reinforced resin molded body according to the present invention, a fiber-reinforced resin molded body having a stable form at a high temperature can be obtained.

Hereinafter, preferred embodiments of the present invention will be described. However, the present invention is not limited to these embodiments, and many modifications can be made within the spirit and scope of the present invention.

<Fiber-reinforced resin material>
The fiber reinforced resin material according to the present embodiment is a fiber reinforced resin material including a thermoplastic resin and a reinforced fiber, and can be molded by heating (or heating and pressurization), and at the time of the molding or After heating at a specific temperature or higher after the molding, it cannot be remolded by reheating (or heating and pressing).

The thermoplastic resin itself is deformed at a temperature at which it can be heated and molded or at a temperature higher than that temperature. The thermoplastic resin is generally deformed at a temperature higher than the glass transition temperature of the thermoplastic resin. Therefore, in general, a molded body obtained by molding a resin material containing a thermoplastic resin is deformed when heated at a moldable temperature even after molding. It can be used only in an environment where the temperature is lower than the moldable temperature of the thermoplastic resin.

On the other hand, the fiber reinforced resin material according to the present embodiment cannot be re-molded by reheating after heating by heating at a specific temperature or higher during molding or after molding. Therefore, the fiber reinforced resin molded product obtained by molding the fiber reinforced resin material according to the present embodiment is molded using a fiber reinforced resin material containing a thermoplastic resin, although it is a high temperature. It can be used even in an environment of That is, the fiber reinforced resin molded body obtained using the fiber reinforced resin material according to the present embodiment exceeds a specific temperature for making re-molding impossible even after being molded once. Further, it can be used beyond the temperature at the time of molding. The heating time above a specific temperature is, for example, about 15 seconds to 1 hour.

The temperature at which the fiber-reinforced resin material according to the present embodiment is molded (that is, the temperature before heating at a specific temperature or higher) is preferably 70 ° C. to 250 ° C. From the viewpoint of the thermal stability of the obtained fiber reinforced resin molding, the temperature (molding temperature) when molding the fiber reinforced resin material is more preferably 80 ° C. or higher, and more preferably 90 ° C. or higher. Moreover, from the viewpoint of moldability of the obtained fiber reinforced resin molded article, the temperature when molding the fiber reinforced resin material is more preferably 200 ° C. or less, and further preferably 150 ° C. or less. In this case, the heating time (molding time) is 15 seconds to 24 hours, preferably about 1 minute to 1 hour.

In particular, a plurality of fiber reinforced resin materials that have been solidified once, such as a plurality of fiber reinforced resin materials, for example, two or more plate-like fiber reinforced resin materials, two or more chip-like fiber reinforced resin materials, or combinations thereof. When combining and obtaining a molded object, from the viewpoint of integration (strength, appearance quality, etc.) of fiber reinforced resin materials, the temperature at which the fiber reinforced resin material is molded is preferably 130 ° C. or lower.

Also, after a fiber reinforced resin material is molded and heated at a specific temperature or higher, it cannot be remolded by heating at least at a specific temperature. In this case, the specific temperature at which re-molding cannot be performed by heating depends on the use environment of the fiber-reinforced resin molded body obtained by using the fiber-reinforced resin material, but a temperature of 80 ° C. or higher is preferable, and a temperature of 130 ° C. or higher. More preferably it is. Further, from the viewpoint of shape stability due to heat of the obtained fiber-reinforced resin molded body, it is preferable that re-molding cannot be performed by heating and pressurizing at a temperature of 150 ° C. and a pressure of 2 MPa. That is, the fiber reinforced resin material may be any material that cannot be remolded by heating and pressurizing at a temperature of 150 ° C. and a pressure of 2 MPa after being heated at a specific temperature or higher after thermoforming. In this case, the heating and pressurizing time is, for example, about 15 seconds to 1 hour.

In addition, the fiber reinforced resin material in the present embodiment does not include those that can be reshaped by reheating (or heating and pressurizing) at a temperature considerably higher than the specific temperature after being heated at a specific temperature or higher. Absent. From the viewpoint of shape stability of the obtained fiber-reinforced resin molded article, the temperature at which re-molding after heating at a specific temperature or higher is 50 ° C or higher, preferably 100 ° C or higher, more preferably higher than the specific temperature. It is 150 ° C or higher, more preferably 200 ° C or higher. Further, from the viewpoint of reuse of the fiber-reinforced resin molded body, the temperature at which re-molding can be performed is preferably 350 ° C. or less, more preferably 250 ° C. or less, and even more preferably 200 ° C. or less.

If it is not necessary to regenerate, those that cannot be reshaped by reheating are preferred. That is, those which are not softened or deformed by reheating are preferable.

The reinforcing fibers constituting the fiber reinforced resin material according to the present embodiment are preferably carbon fibers. Among the reinforcing fibers, carbon fibers are light and strong, and are preferable from the viewpoint of corrosion resistance.

The shape of the reinforcing fiber is not particularly limited, and may be staple, cotton, thread, string, tape, sheet, woven fabric, knitted fabric, nonwoven fabric, or the like. Further, when the reinforcing fiber is carbon fiber or the like, it may or may not be opened.

The thermoplastic resin constituting the fiber reinforced resin material according to the present embodiment is preferably an epoxy resin. Epoxy resins are preferred from the viewpoints of strength such as fracture toughness, bending strength, impact resistance and compressive strength, and durability including chemical resistance against acid resistance and alkali resistance.

Further, the fiber reinforced resin material according to the present embodiment may contain a crosslinking agent having two or more functional groups. By including such a crosslinking agent, the thermoplastic resin contained in the fiber reinforced resin material loses moldability due to heating when heated at a specific temperature or higher, and is obtained using the fiber reinforced resin material. The shape stability against heat of the obtained fiber-reinforced resin molded body is increased. That is, the obtained fiber reinforced resin molded product is difficult to be remolded by reheating.

Particularly preferred as a cross-linking agent to be included in the fiber reinforced resin material is a block type isocyanate compound or a novolac type resin, and the fiber reinforced resin material may contain at least one of them.

When a block type isocyanate compound or a novolak type resin is used as the crosslinking agent, the thermoplastic resin will be linearly polymerized when a thermoplastic resin, which will be described later, particularly a reactive type thermoplastic resin, is used. At the temperature, the crosslinking agent does not react as a crosslinking agent, and a fiber-reinforced resin material having thermoplasticity can be obtained stably. For example, when a block-type isocyanate compound is used as the crosslinking agent, the isocyanate group is blocked with the blocking agent, and thus does not react as the crosslinking agent. In addition, the crosslinking agent is activated by heating at a specific temperature or higher performed later, for example, the block with the blocking agent is removed, the linear thermoplastic resin is crosslinked so as to bridge each other, or an isocyanate type Bonds with other compounds and low molecular weight thermoplastic resins to become obstacles, impedes fluidity of linear thermoplastic resins at high temperatures, and then fiber reinforced resin materials and fiber reinforced resins obtained using them It is possible to stably prevent the molded body from being reshaped by reheating. Therefore, when a block-type isocyanate compound or novolac resin is used, it is easy to set a specific temperature, and it is easy to manage a state where it has thermoplasticity and can be easily molded, and a state where it cannot be molded. From the viewpoints of productivity and quality stability of the fiber reinforced resin material and the fiber reinforced resin molded article, a block type isocyanate compound or a novolak type resin may be used as a crosslinking agent.

The cross-linking agent having two or more functional groups may be contained in an amount of 1 part by weight or more with respect to 100 parts by weight of the thermoplastic resin, although it varies depending on the number of functional groups of the cross-linking agent and the thermoplastic resin. If the content of the cross-linking agent is less than 1 part by weight, re-molding can be performed even after heating at a specific temperature or higher, and softening or deformation due to heat may be too large, and the object of the present invention may not be achieved. The content of the crosslinking agent is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and still more preferably 15 parts by weight or more with respect to 100 parts by weight of the thermoplastic resin. The upper limit of the content of the crosslinking agent is not particularly limited, but the upper limit is about 100 parts by weight. In addition, even if 100 parts by weight or more of the crosslinking agent is added, there is a risk that the effect of the addition is not so much improved, fragile, or softened easily with respect to the obtained fiber reinforced resin material or fiber reinforced resin molded body. There is. The content of the crosslinking agent is more preferably 60 parts by weight or less, further preferably 50 parts by weight or less, and still more preferably 40 parts by weight or less.

Also, the specific temperature at which re-molding by reheating cannot be performed is preferably 130 ° C. or higher. This specific temperature refers to the temperature at which the fiber reinforced resin material or the fiber reinforced resin molded body is heated during molding or after molding, and the reinforced fiber resin molded body cannot be remolded after heating at that temperature. This is because when a specific temperature is 130 ° C. or higher and a block type isocyanate compound is used as a crosslinking agent, the isocyanate compound having an active NCO is released from the block and acts as a crosslinking agent. These thermoplastic resins are cross-linked in a bridging manner, or combined with isocyanate compounds and low molecular weight thermoplastic resins to become obstacles, which inhibits the flowability of linear thermoplastic resins at high temperatures. I guess that there is.

From the viewpoint of obtaining a thermoplastic resin material that can be easily molded (that is, from the viewpoint of obtaining a fiber-reinforced resin material excellent in thermoplasticity), the specific temperature at which re-molding by reheating is impossible is 150 ° C. or higher. Preferably, it is 190 ° C. or higher, more preferably 200 ° C. or higher. When this specific temperature is low, for example, when obtaining a thermoplastic resin having a linear molecular structure from a reactive thermoplastic resin, the moldability of the fiber-reinforced resin material may be lowered. This is presumed to be because, for example, crosslinking between linear molecules and reaction between crosslinking agents occur simultaneously.

In addition, the upper limit of the specific temperature is 350 ° C., more preferably 300 ° C., even more preferably 270 ° C., and even more preferably from the viewpoint of obtaining a fiber-reinforced resin molded article having a target shape with good productivity. 250 ° C.

In the fiber reinforced resin material according to the present embodiment, the fact that it cannot be reshaped by heating means that it cannot be formed into a specific shape by heating (or heating and pressurizing). In other words, not being able to be reshaped by heating includes not only being unable to be reshaped at all by heating, but also being difficult to regenerate by heating. If it cannot be molded, it will be softened by heating, or force will be applied during heating. It includes deformation that occurs when it is deformed but does not deform unless heated. As described above, the fiber reinforced resin molded product obtained by molding the fiber reinforced resin material may be softened by heating. Preferably, the fiber reinforced resin molded product is softened at the use environment temperature. The thing which does not deform | transform is good.

Further, a preferred example of the fiber reinforced resin material according to the present embodiment will be described in more detail.

The fiber reinforced resin material containing a thermoplastic resin and a reinforced fiber is preferably a fiber reinforced resin material containing a thermoplastic resin and a bundle of reinforced fibers arranged in one direction, and the thermoplastic resin is reactive. It may be a resin.

Since the fiber-reinforced resin material according to the present embodiment includes a thermoplastic resin and a bundle of carbon fibers, the fiber-reinforced resin material has thermoplasticity and can be easily molded by heating (or heating and pressurizing), and has a desired shape. A fiber-reinforced resin molded product can be obtained. The obtained fiber-reinforced resin molded product can be easily re-molded by heat treatment even after being molded once by heat treatment at a temperature lower than a specific temperature, and conversely after heat treatment at a specific temperature or higher. Cannot be reshaped even if the heat treatment is performed again at the specific temperature.

In general, a thermoplastic resin can be deformed any number of times by heating at a moldable temperature, but the fiber-reinforced resin molded body in the present embodiment is not specified after being heated at a specific temperature or higher. Even if heating is performed again at a temperature of 1, this does not deform.

A preferable embodiment of the present embodiment is a case where the reaction type thermoplastic resin is heated to become a thermoplastic resin having a molecular structure bonded in a straight chain. In this state, since the thermoplastic resin is linear, it has a relatively low glass transition temperature, and can be molded any number of times as long as the temperature is equal to or higher than that temperature. Moreover, since the fiber reinforced resin material before heating at a specific temperature or higher does not need to be stored in a strict low temperature environment unlike a thermosetting resin, it can be easily stored.

On the other hand, by heating the fiber reinforced resin material at a specific temperature or higher, a linear thermoplastic resin is further bonded, or preferably, the fiber reinforced resin material includes a crosslinking agent having two or more functional groups. Form stability against heat is improved by heating this fiber reinforced resin material above the temperature at which the cross-linking agent and the linear thermoplastic resin react, or above the temperature at which the cross-linking agents react with each other. To do. That is, it becomes difficult to remold by reheating.

The reason for this is that by heating at a specific temperature or higher, a linear resin becomes a resin having a molecular structure crosslinked by a crosslinking agent, the glass transition temperature of the thermoplastic resin is greatly increased, or thermoplasticity is increased. Even if it is heated again under heating and pressurization conditions that could be molded before processing at that temperature due to the resin becoming thermosetting or other compounds formed by the crosslinking agent, etc., fiber reinforcement It is presumed that the resin material and the fiber reinforced resin molded product obtained using the resin material cannot be remolded.

In addition, about the fiber reinforced resin material which concerns on this Embodiment, it is not necessary to store the thing before heating more than specific temperature like a thermosetting resin at low temperature, and a crosslinking agent is made to react. At the time of heating, the heat treatment can be easily performed without requiring a long time as in the case of curing the thermosetting resin.

The shape of the fiber reinforced resin material of the present embodiment is not particularly limited, and may be a sheet shape, a tape shape, a column shape, a string shape, a linear shape, a granular shape, a chip shape, a plate shape, a block shape, or the like. Moreover, the cross section cut | disconnected by the orthogonal | vertical direction with respect to the fiber-axis direction of a reinforced fiber is circular, elliptical, flat shape, polygonal shape, etc., and is not specifically limited. In addition, the perpendicular direction here should just be a direction substantially perpendicular | vertical to the fiber axis direction of a reinforced fiber, when the fiber axis direction of the reinforced fiber contained in a fiber reinforced resin material has arranged in one direction.

Also, the size of the fiber reinforced resin material is not particularly limited, but in the case of a chip shape in which the fiber axis directions of the reinforced fibers contained in the fiber reinforced resin material are arranged in one direction, the fiber reinforced resin material From the viewpoint of strength such as fracture toughness, bending strength, impact resistance, and compressive strength, the length in the fiber axis direction of the fiber reinforced resin material is preferably 5 mm to 500 mm. The length in the fiber axis direction of the fiber reinforced resin material is more preferably 10 mm or more, and even more preferably 20 mm or more. The length of the fiber reinforced resin material in the fiber axis direction is more preferably 30 mm or more, further preferably 40 mm or more, and further preferably more than 50 mm.

In addition, even when remolded at high temperatures, the chip-like fiber reinforced resin material is superior in moldability in any direction and stability in various strengths compared to the case of using a woven fabric or the like.

Also, the upper limit of the length of the fiber reinforced resin material in the fiber axis direction is not particularly limited. Depending on the size of the obtained fiber reinforced resin molded product, if the length of the fiber reinforced resin material in the fiber axis direction is 500 mm or less, the fiber reinforced resin material may be greatly bent, or the fiber reinforced resin material may be used. Since the anisotropy related to the strength of the resulting fiber reinforced resin molded article can be suppressed, a fiber reinforced resin molded article having stable strength including compressive strength and impact resistance can be obtained. The length in the fiber axis direction of the fiber reinforced resin material depends on the size of the obtained fiber reinforced resin molded article, but is preferably 300 mm or less, and more preferably 100 mm or less.

The length in the fiber axis direction of the fiber reinforced resin material refers to the length in the fiber axis direction of the reinforced fiber that is a component of the fiber reinforced resin material.

Further, the length other than the fiber axis direction is not particularly limited, but from the viewpoint of the productivity of the fiber reinforced resin material and the strength of the obtained fiber reinforced resin molded product, the length other than the fiber axis direction is the length in the fiber axis direction. Shorter than the length is better.

The width of the fiber reinforced resin material is preferably 300 mm or less, preferably 100 mm or less, more preferably 50 mm or less, even more preferably 30 mm or less, even more preferably 10 mm or less, and even more preferably 5 mm or less. . In addition, although there is no restriction | limiting in particular in the lower limit of the width | variety of fiber reinforced resin material, the width | variety of fiber reinforced resin material is good to be 1 mm or more from viewpoints, such as handling property at the time of production and rationalization of cost.

If the width of the fiber reinforced resin material is equal to or less than the above upper limit value, the fiber axis direction of the bundle of reinforcing fibers is likely to be random in the fiber reinforced resin molded body obtained by heating and pressing, and thus the fiber reinforcement obtained From the viewpoint of the strength of the resin molding and its stability, the upper limit of the width of the fiber reinforced resin material is preferably set to the above value.

Also, the relationship between the length and the width of the fiber reinforced resin material in the fiber axis direction is preferably larger in the fiber axis direction than the width. Preferably, when the width of the fiber reinforced resin material is 1, the length in the fiber axis direction is 1.5 or more, preferably 2.0 or more, more preferably 3.0 or more, even more preferably 4.0 or more, Even more preferably, it is 5.0 or more.

In the relationship between the length and width in the fiber axis direction of the fiber reinforced resin material, the fiber reinforced resin material overlaps not only in the surface direction but also in the thickness direction in the fiber reinforced resin molded product if the value is equal to or greater than the above lower limit value. In a three-dimensional random state, the strength is improved, especially in the case of a thick molded body, the compressive strength is improved, and in the case of a thin molded body, the safety of the cut surface in the event of a crack is improved as will be described later. To do. The reason why the compressive strength is improved in this way is considered to be that the movement due to compression is suppressed because the fiber reinforced resin materials are randomly overlapped in three dimensions.

Moreover, about the upper limit in the relationship between the length and width of the fiber reinforced resin material in the fiber axis direction, when the width of the fiber reinforced resin material is 1, the length in the fiber axis direction is preferably 50.0 or less, more preferably 30.0 or less, more preferably 20.0 or less.

In the relationship between the length and width in the fiber axis direction of the fiber reinforced resin material, if the above upper limit is exceeded, the productivity and strength stability of the fiber reinforced resin molded product may be lowered.

The thickness of the fiber reinforced resin material of the present embodiment is not particularly limited, but is 0.10 mm or more, preferably 0.15 mm or more, more preferably 0.20 mm or more, and even more preferably 0.00. It may be 3 mm or more, further 0.5 mm or more, and even more preferably 1.0 mm or more. The upper limit of the thickness of the fiber reinforced resin material is about 100 mm.

If the thickness of the fiber reinforced resin material is not less than the above lower limit value, the handleability of the obtained fiber reinforced resin material is improved. When carbon fiber or basalt fiber is used as the reinforcing fiber, there is anisotropy in strength. Therefore, if the thickness of the fiber reinforced resin material is less than the above lower limit, before manufacturing the fiber reinforced resin molded product The fiber reinforced resin material may break. In addition, when the fiber reinforced resin material is manufactured by heating and pressurizing a fiber reinforced resin material obtained from the viewpoint of the productivity of the fiber reinforced resin material or by using the fiber reinforced resin material, the fiber reinforced resin material is adjusted. The thickness of the fiber-reinforced resin material is preferably equal to or more than the above lower limit value from the viewpoint of strength improvement and strength stability because the material is deformed in the thickness or width direction and the gap is filled.

Further, if the thickness of the fiber reinforced resin material is not more than the above upper limit value, the thermoplastic resin can be sufficiently impregnated into the carbon fiber bundle. Further, the thickness of the fiber reinforced resin material is preferably not more than the above upper limit value from the viewpoint of the productivity of the fiber reinforced resin material and the strength of the fiber reinforced resin molded product obtained using the fiber reinforced resin material. Furthermore, when the thickness of the fiber reinforced resin material is equal to or less than the above upper limit value, when the fiber reinforced resin molded body is manufactured by heating and pressurizing, the fiber reinforced resin molded body is prevented from containing air. , Strength and production are stable.

The thermoplastic resin used by being melted by heat is difficult to impregnate the bundle of reinforcing fibers, so the bundle of reinforcing fibers needs to be made into a thin sheet of 0.13 mm or less. If it is a fiber reinforced resin material, since a reactive thermoplastic resin is used, the thermoplastic resin easily impregnates the bundle of reinforcing fibers, so there is no need to make the bundle of reinforcing fibers thin, and a thick fiber reinforced resin. A material is obtained.

The above description is for a chip shape in which the fiber axis directions of the reinforcing fibers contained in the fiber reinforced resin material are arranged in one direction, but the shape of the fiber reinforced resin material is not limited to these. , Can be any shape.

Further, the fiber volume content (Vf value) in the fiber reinforced resin material of the present embodiment is preferably 20% to 80%. The Vf value of the fiber reinforced resin material is preferably 30% or more, and more preferably 40% or more, from the viewpoint of the strength of the fiber reinforced resin molded article obtained using the fiber reinforced resin material. In addition, from the viewpoint of appearance quality, moldability, and strength of the fiber reinforced resin molded article obtained using the fiber reinforced resin material, the Vf value of the fiber reinforced resin material is more preferably 70% or less, and still more preferably. Is preferably around 60%.

Depending on the shape of the fiber reinforced resin material, when a space is generated inside the fiber reinforced resin material when the fiber reinforced resin material is heated and pressurized to obtain a fiber reinforced resin molded product, The fiber reinforced resin material has a Vf value of 50% or less, more preferably 45% or less. If there is a space between the fiber reinforced resin materials, the strength of the resulting fiber reinforced resin molded product may be reduced or stable. There is a risk that the obtained strength may not be obtained.

<< Thermoplastic resin >>
The thermoplastic resin used for the fiber reinforced resin material according to the present embodiment is epoxy resin, polyamide resin, acrylic resin, polyphenylene sulfide resin, polyvinyl chloride resin, polyethylene, polypropylene, polyacetal resin, polycarbonate, polyurethane, polybutylene terephthalate. , Acrylonitrile butadiene styrene (ABS) resin, modified polyphenylene ether resin, phenoxy resin, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, and aromatic polyester. The thermoplastic resin is preferably a reaction type that cures by adding or heating an additive such as a curing agent, a catalyst, a polymerization initiator, or a polymerization accelerator, or by starting the reaction or promoting the reaction. A resin that has thermoplasticity after curing is preferable. The thermoplastic resin preferably has a linear molecular structure in order to maintain thermoplasticity. Moreover, you may mix | blend and use multiple types of thermoplastic resins.

In addition, the chemical structure of the thermoplastic resin may change after the reaction. For example, the epoxy resin becomes a phenoxy resin after the reaction. Moreover, you may mix | blend a thermosetting resin with a thermoplastic resin in the range which does not deviate from the objective of this invention.

The fiber reinforced resin material obtained by using such a thermoplastic resin can be easily deformed by heating, and cannot be remolded by heating at or above a specific temperature during or after molding. Is.

From the viewpoint of durability including fracture toughness, bending strength, impact resistance, compressive strength, and chemical resistance against acid and alkali resistance, a reactive thermoplastic epoxy is particularly preferable as a reactive thermoplastic resin. Resin. Moreover, when using carbon fiber as the reinforcing fiber, a reactive thermoplastic epoxy resin is preferable from the viewpoint of affinity with the carbon fiber, and the strength of the fiber reinforced resin molded product obtained using the fiber reinforced resin material and Its durability is further improved. In addition, the reactive thermoplastic epoxy resin in this Embodiment includes what becomes a phenoxy resin after reaction. The epoxy resin preferably has a functional group capable of reacting with a cross-linking agent described later, for example, an OH group (—OH).

Since such a reactive thermoplastic resin can be dissolved or dispersed in a liquid or solvent at room temperature before being cured with a curing agent, the resin is impregnated into the bundle of reinforcing fibers. Can do. Further, since the resin is present even inside the bundle of reinforcing fibers, the reinforcing fibers and the thermoplastic resin are sufficiently intertwined (contacted with each other). For this reason, the fiber reinforced resin molded object obtained using the fiber reinforced resin material of this Embodiment has the outstanding intensity | strength, and has the stable intensity | strength which suppressed the dispersion | variation.

In addition, the reaction type thermoplastic resin has a smaller molecular weight of the thermoplastic resin before the reaction than the unreacted thermoplastic resin used after being melted by heating, and improves the fluidity. After the reaction, for example, the number average molecular weight is 10,000. It can be polymerized to 30,000 or more and the state of crosslinking can be adjusted, and the strength can be improved, and flexibility and heat deformation can be adjusted. Moreover, mixing with a crosslinking agent having two or more functional groups is also easy.

The temperature at which the thermoplastic resin can be molded and the glass transition temperature before reacting the thermoplastic resin with the crosslinking agent described below are preferably 70 to 250 ° C. From the viewpoint of the thermal stability of the obtained fiber-reinforced resin molded article, the temperature at which the thermoplastic resin can be molded and the glass transition temperature are more preferably 80 ° C. or higher, and more preferably 90 ° C. or higher. Further, from the viewpoint of moldability of the obtained fiber reinforced resin molded article, the temperature at which the thermoplastic resin can be molded and the glass transition temperature are more preferably 200 ° C. or less, and further preferably 150 ° C. or less.

In particular, a plurality of fiber reinforced resin materials that have been solidified once, such as a plurality of fiber reinforced resin materials, for example, two or more plate-like fiber reinforced resin materials, two or more chip-like fiber reinforced resin materials, or combinations thereof. In the case of obtaining a molded body in combination, the temperature and glass transition temperature at which the thermoplastic resin before heating at a specific temperature or higher can be molded is preferably less than 150 ° C., and 130 ° C. or lower is used between the fiber reinforced resin materials. From the viewpoint of integration (strength, appearance quality, etc.), it is more preferable.

Further, the temperature at which re-molding can be performed by heating the thermoplastic resin after reacting the thermoplastic resin with the crosslinking agent described below or after the crosslinking agents are reacted with each other (after heating at a specific temperature or higher) is higher than 150 ° C. It is preferable. From the viewpoint of the thermal stability of the obtained fiber reinforced resin molded article, the temperature at which the thermoplastic resin can be reshaped by heating is more preferably 190 ° C or higher, and further preferably 240 ° C or higher. In addition, from the viewpoint of moldability of the obtained fiber reinforced resin molded article, the upper limit of the temperature that can be remolded by heating the thermoplastic resin is not particularly limited, and varies depending on the type of resin, the crosslinking agent, etc. It is about 400 ° C.

In general, the glass transition temperature of the thermoplastic resin and the temperature at which the fiber reinforced resin material containing the thermoplastic resin and the reinforced fiber can be molded by heat substantially coincide with each other, and heating above a specific temperature. As a result, the glass transition temperature of the thermoplastic resin increases, and it seems that the moldability at a specific temperature thereafter is lost. However, in the fiber reinforced resin material of the present embodiment, other than the above, specifically, the glass transition temperature of the thermoplastic resin does not coincide with the temperature at which it cannot be molded by heating, and is heated at a specific temperature or higher. Even after that, although the glass transition temperature of the thermoplastic resin hardly increases, there are those that cannot be re-molded even at a temperature that can be molded before the heat treatment above a specific temperature. In such a case, a thermoplastic resin having a small number of cross-linked parts to the linear molecular structure of the thermoplastic resin and / or a low molecular weight thermoplastic resin may react with the crosslinking agent, or a reaction product of the crosslinking agents may be generated. Therefore, it is thought that the fluidity of the thermoplastic resin is hindered, and re-molding by heat cannot be performed.

The glass transition temperature is measured by differential scanning calorimetry (DSC).

Also, the thermoplastic resin after reacting the thermoplastic resin with the crosslinking agent described below includes those that become thermosetting. The thermosetting resin after the reaction between the thermoplastic resin and the crosslinking agent described below includes those that soften by heating and those that deform somewhat by pressure, but have no moldability. Preferably, those which are not softened by heating are more preferable.

<< Crosslinking agent >>
The cross-linking agent used in the fiber-reinforced resin material according to the present embodiment is a cross-linking agent having two or more functional groups (hereinafter also simply referred to as “cross-linking agent”). The crosslinking agent may be arbitrarily selected from those having reactivity with the thermoplastic resin used. When the thermoplastic resin is a reactive resin, it is preferable to use a crosslinking agent having a reaction initiation temperature higher than the reaction initiation temperature of the thermoplastic resin by the curing agent. When the reactive thermoplastic resin solution contains a crosslinking agent as the curing agent, the reactive thermoplastic resin solution is activated at a higher temperature than the crosslinking agent as the curing agent, and the linear thermoplastic resin and the linear It is preferable to use a cross-linking agent that causes a cross-linking reaction with a thermoplastic resin or a reaction between cross-linking agents.

Reaction start temperature of reaction type thermoplastic resin by curing agent, accelerator, etc., and specific temperature, that is, temperature at which fiber reinforced resin material or fiber reinforced resin molded product will not be remolded (for example, linear thermoplastic resin The difference (temperature difference) between the reaction temperature and the crosslinking agent of the present embodiment is a fiber-reinforced resin material excellent in moldability and is stable in shape after heat at a specific temperature or higher. From the viewpoint of obtaining an excellent fiber-reinforced resin molded article, 10 ° C or higher is preferable, 30 ° C or higher is more preferable, and 50 ° C or higher is more preferable. The upper limit of the temperature difference is not particularly limited, but if the temperature difference is too large, it is necessary to make the temperature high when manufacturing a fiber-reinforced resin molded article excellent in thermal stability. ° C or lower is preferable, more preferably 150 ° C or lower, and still more preferably 100 ° C or lower.

As a specific crosslinking agent, when a linear epoxy resin (phenoxy resin) obtained by reacting an epoxy resin is used as a thermoplastic resin, a functional group capable of reacting with the OH group of the epoxy resin. Examples thereof include isocyanate compounds having two or more groups and novolac resins.

Examples of the isocyanate compound having two functional groups include: (1) aliphatic diisocyanates having 6 to 12 carbon atoms [excluding carbon in the NCO group, the same applies to (2) to (4) below], (2 And alicyclic diisocyanates having 6 to 15 carbon atoms, (3) araliphatic diisocyanates having 8 to 12 carbon atoms, (4) aromatic diisocyanates having 6 to 30 carbon atoms, and mixtures of two or more thereof. .

Specific examples of the aliphatic diisocyanate include hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 1,3,6-trimethylhexamethylene diisocyanate and the like.

Specific examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), 1,4-cyclohexane diisocyanate, methylcyclohexane-2,4-diisocyanate (hydrogenated TDI). ), 1,4-bis (2-isocyanatoethyl) cyclohexane and the like.

Specific examples of the araliphatic diisocyanate include p- or m-xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate and the like.

Specific examples of aromatic diisocyanates include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 2,4'- or 4,4'-diphenylmethane diisocyanate. (MDI), naphthalene-1,5-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, and the like. Of these, preferred are aromatic diisocyanates, and particularly preferred is MDI.

As an isocyanate compound having 3 or more functional groups, for example, a urethane-modified product obtained by reacting the above organic diisocyanate (3 mol) with trimethylolpropane (TMP) (1 mol) (for example, HDI or IPDI or TDI and TMP). Modified adducts, etc.), and burette modified products obtained by reacting the organic diisocyanate (3 mol) with water (1 mol) (for example, modified products obtained by reacting HDI or IPDI with water). , Isocyanurate-modified products of the above organic diisocyanates (for example, HDI or IPDI or TDI trimers), dimers of the above-mentioned modified products (for example, urethane-modified products, burette-modified products, or isocyanurate-modified products ( 2 mol) and water or ethylene glycol (1 mol) Etc.), trimers of the above-mentioned modified products (for example, modified products obtained by reacting urethane-modified products, burette-modified products or isocyanurate-modified products (3 mol) with water or ethylene glycol (2 mol)), etc. , And a mixture of two or more thereof. Among these, preferred are an aliphatic polyisocyanate that is a modified product using an aliphatic diisocyanate, an alicyclic polyisocyanate that is a modified product using an alicyclic diisocyanate, and a mixture of two or more of these. More preferably, an isocyanurate-modified aliphatic polyisocyanate, an isocyanurate-modified alicyclic polyisocyanurate, and a mixture of two or more of these.

Preferably, when an isocyanate compound is used, a blocked isocyanate compound in which a functional group is blocked until a temperature equal to or higher than a certain level is applied. As a result, the fiber-reinforced resin molded body can be easily molded, and a fiber-reinforced resin molded body having excellent thermal stability after molding can be easily obtained.

The block type isocyanate compound is a compound that does not react at a temperature lower than a specific temperature, but is capable of obtaining an active NCO by dissociating the blocking agent of the isocyanate compound at a specific temperature or higher. It is said to be masked isocyanate. Examples of the blocking agent include phenols such as phenol and xylenol, oximes such as methyl ethyl ketone oxime, lactams such as caprolactam, and alcohols such as methanol.

The temperature at which dissociation starts is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, more preferably 170 ° C. or higher, and even more preferably 200 ° C. or higher from the viewpoint of moldability. When a reactive thermoplastic resin is used when the temperature at which dissociation starts below 120 ° C., the crosslinking reaction with the crosslinking agent proceeds simultaneously during the reaction of the thermoplastic resin with the curing agent, and before the molding, the plastic epoxy resin There is a possibility that moldability due to heat is lowered.

The temperature at which dissociation begins varies somewhat depending on the type of blocking agent, the presence of a functional group of the thermoplastic resin that becomes a reaction partner with the isocyanate compound, and the presence or absence of a catalyst.

Note that the reaction initiation temperature between the thermoplastic resin (cured with the curing agent) and the crosslinking agent of the present embodiment is that the block agent is dissociated when a block-type isocyanate compound is used. The temperature at which the thermoplastic resin is bonded to the functional group, and the linear molecular structure of the thermoplastic resin is bridged to form a crosslinked molecular structure, or the blocking agent is dissociated and the crosslinking agents are crosslinked. Thus, the temperature at which the fiber-reinforced resin material or the fiber-reinforced resin molded body cannot be re-molded is considered to be the “specific temperature” in the present embodiment.

Also, a novolac resin may be used as a crosslinking agent. The novolak resin has a higher reaction initiation temperature with the functional group of the preceding thermoplastic resin (cured with the curing agent) than the isocyanate compound, and has a preferable reaction initiation temperature easily without blocking the functional group. . As the thermoplastic resin and the novolac resin, those having a reaction start temperature of 200 ° C. or higher are generally available. Moreover, when a novolak resin is used as a crosslinking agent, the flame-retardant property of the obtained fiber-reinforced resin molded article is improved.

<< Reinforcing fiber >>
Examples of the reinforcing fibers used in the fiber-reinforced resin material according to the present embodiment include inorganic fibers, organic fibers, metal fibers, or a combination of these. Specifically, the reinforcing fiber includes carbon fiber, graphite fiber, silicon carbide fiber, alumina fiber, tungsten carbide fiber, boron fiber, glass fiber, basalt fiber, para-aramid fiber, meta-aramid fiber, ultra high molecular weight. Examples include polyethylene fiber, polyarylate fiber, PBO (polyparaphenylene benzoxazole) fiber, polyphenylene sulfide (PPS) fiber, polyimide fiber, fluorine fiber, polyvinyl alcohol (PVA fiber), stainless steel, and iron.

From the viewpoint of light weight and high strength, the reinforcing fibers are preferably carbon fibers and basalt fibers, and particularly preferably carbon fibers.

As the carbon fiber, any of PAN-based and pitch-based carbon fibers can be used. Of these, PAN-based carbon fibers are preferable from the viewpoint of the balance between strength and elastic modulus.

In the present embodiment, any form such as staples, cotton (cotton), bundles of reinforcing fibers arranged in one direction, reinforcing fiber nonwoven fabrics, reinforcing fiber fabrics, reinforcing fiber knitted fabrics are used as the reinforcing fiber. Can do.

In particular, a bundle of reinforcing fibers arranged in one direction and bundled is preferably used. Here, what arranged the reinforcing fiber in one direction is what united the fiber axis direction of the reinforcing fiber. Further, the bundle of reinforcing fibers may be a bundle of two or more reinforcing fibers that are converged, even if they are converged with a sizing agent, and without using a sizing agent. It may be bundled. From the viewpoint of productivity, a product converged with a sizing agent is preferable. In addition, when using a sizing agent, it is good to use a thing with high affinity with a thermoplastic resin. In this case, it becomes easy to impregnate the bundle of reinforcing fibers with the thermoplastic resin, and it becomes easy to obtain a fiber-reinforced resin molded article having excellent strength and stable strength.

The bundle of reinforcing fibers arranged in one direction is preferably a bundle of 1000 or more single fibers of reinforcing fibers, more preferably 10,000 or more, and even more preferably 100,000 or more. The upper limit of the number of reinforcing fiber bundles is not particularly limited, but in the case where the reinforcing fiber bundle is not opened, it is about one million. When the bundle of reinforcing fibers arranged in one direction is opened and used, the number of fibers may be further increased.

Therefore, in the present embodiment, a product obtained by bundling 6000 (6K) single fibers of carbon fiber supplied from a carbon fiber manufacturer, or 12000 (12K), 24000 (24K), 50000 (50K), Product such as 60000 (60K) can be used as it is without opening, or more than one bundle of these can be used as it is without opening. Are better. Of course, a product obtained by bundling a plurality of carbon fibers supplied from a carbon fiber manufacturer may be opened and used.

Further, the carbon fiber may be any of a non-twisted yarn, a twisted yarn, and a flame-retardant yarn.

In the present embodiment, the cross-sectional shape cut in the direction perpendicular to the fiber axis direction of the bundle of carbon fibers is not particularly limited, such as a circle, an ellipse, or a polygon. In addition, the perpendicular direction here should just be a direction substantially perpendicular | vertical to the fiber axis direction of a reinforced fiber (carbon fiber).

In this embodiment, a reactive thermoplastic resin is used, and the resin easily impregnates the inside of the bundle of reinforcing fibers. Therefore, the bundle of reinforcing fibers molded with a large number of single fibers is not necessarily opened. There is no need to do etc. Thereby, the reinforced fiber wound around the drum etc. which are supplied from a fiber maker can be used as it is, and there are few processes and it is excellent in productivity. Moreover, since a thermoplastic resin can be provided at once to a bundle of reinforcing fibers composed of many single fibers, the productivity is excellent.

<Method for producing fiber-reinforced resin material>
Next, a preferred method for producing the fiber reinforced resin material in the present embodiment will be described by taking a chip-like fiber reinforced resin material including a bundle of reinforced fibers arranged in one direction and a thermoplastic resin as an example. Do. In addition, the manufacturing method of the fiber reinforced resin material of this Embodiment is not limited to the following method. In addition, about the matter which overlaps with what was demonstrated previously, description is abbreviate | omitted or simplified partially.

The fiber reinforced resin material of the present embodiment draws out a bundle of reinforcing fibers arranged in one direction, wound around a drum or the like supplied from a fiber maker such as a carbon fiber maker, and then draws a thermoplastic resin solution. Give. In addition, what was pulled out from one drum supplied from a carbon fiber manufacturer or the like may be used as a bundle of reinforcing fibers, or a plurality of drums are attached to a creel, and a bundle of a plurality of reinforcing fibers is further bundled into one bundle. It may be used as a bundle of reinforcing fibers. The bundle of reinforcing fibers may be opened by performing a fiber opening process or may not be opened.

<< Thermoplastic resin solution >>
A preferable thermoplastic resin solution in the present embodiment includes the above-mentioned various reaction-type thermoplastic resins and a curing agent, and further has a higher reaction initiation temperature than the reaction initiation temperature of the thermoplastic resin by the curing agent. The group contains two or more crosslinkers. The thermoplastic resin solution further contains a solvent.

The thermoplastic epoxy resin and the crosslinking agent having 2 or more functional groups are as described above. The thermoplastic resin solution includes not only a solution in which a solute is completely dissolved in a solvent, but also an emulsion and a dispersion.

Solvents include water, dimethylformamide, toluene, xylene, cyclohexane, methyl acetate, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, methanol, ethanol, butanol, isopropyl alcohol, methyl cellosolve, Examples include cellsolve and anon.

By using a resin solution containing a solvent, it becomes easy to adjust the viscosity and fluidity of the resin, and it becomes easy to mix a thermoplastic resin with a curing agent and a crosslinking agent having two or more functional groups.

Curing agents include epoxy resins, aliphatic polyamines, polyaminoamides, ketimines, aliphatic diamines, aromatic diamines, imidazoles, tertiary amines and other amine compounds, phosphate compounds, acid anhydride compounds, mercaptan compounds. Phenol resin, amino resin, dicyandiamide, Lewis acid complex compound and the like.

Further, the thermoplastic resin solution contains additives such as a catalyst, a polymerization initiator, a polymerization accelerator, an antioxidant, an ultraviolet absorber, a pigment, a thickener, an emulsifier, and a dispersant without departing from the object of the present invention. You may add in the range.

The viscosity of the thermoplastic resin solution of the present embodiment is preferably 5 to 1000 mPa · s at room temperature. When the viscosity of the thermoplastic resin solution is 5 mPa · s or more, a sufficient amount of thermoplastic resin can be imparted to the bundle of reinforcing fibers. The viscosity of the thermoplastic resin solution is preferably 10 mPa · s or more, more preferably 50 mPa · s or more. Further, if the viscosity of the thermoplastic resin solution is 1000 mP · s or less, the thermoplastic resin can be penetrated into the bundle of reinforcing fibers. The viscosity of the thermoplastic resin solution is more preferably 800 mPa · s or less, and further preferably 500 mPa · s or less.

The method of applying the thermoplastic resin to the bundle of reinforcing fibers includes a dip method in which the bundle of reinforcing fibers is immersed in the thermoplastic resin solution, a dip nip method in which the bundle is squeezed with a mangle after immersion, a kiss roll, a gravure roll, etc. And a transfer method in which a thermoplastic resin is transferred from the kiss roll or the like to a bundle of reinforcing fibers, or a spray method in which a mist-like thermoplastic resin solution is applied to the bundle of reinforcing fibers. In addition, in the dipping method, transfer method, spray method, etc., the thermoplastic resin is pushed into the reinforcing fiber by bringing the bundle of reinforcing fibers with the thermoplastic resin solution into contact with an orifice, a die, a roll, etc. The amount of the thermoplastic resin applied to the bundle of reinforcing fibers can be adjusted by removing the excess thermoplastic resin.

The amount of the thermoplastic resin solution applied to the reinforcing fiber and the amount of the thermoplastic resin in the thermoplastic resin may be adjusted so that the amount of the thermoplastic resin in the bundle of reinforcing fibers becomes the above-described preferable Vf value.

In this embodiment, since the viscosity of the thermoplastic resin solution is low, even when the thermoplastic resin is applied to one side of the bundle of reinforcing fibers by the transfer method, the thermoplastic resin penetrates to the inside of the bundle of reinforcing carbon fibers. Can be made. Of course, a thermoplastic resin may be applied to both surfaces of the bundle of reinforcing fibers by a transfer method.

After applying a thermoplastic resin to the bundle of reinforcing fibers, drying and / or heat treatment is performed. Drying and heat treatment may be performed simultaneously. In the step of obtaining the fiber reinforced resin material, the reaction based on the thermoplastic resin and the curing agent may be completed, but the reaction is stopped in a certain state (or the reaction rate is reduced). The thermoplastic resin may be completely reacted during the production of the fiber-reinforced resin molded body or during heating at a specific temperature above the temperature at which the crosslinking agent having two or more functional groups starts to react.

The purpose of drying and / or heat treatment after applying the thermoplastic resin to the bundle of reinforcing fibers is to solidify at least the fiber-reinforced resin material and eliminate surface tack. Preferably, a reactive thermoplastic resin reacts with a curing agent, and a tack-free fiber-reinforced resin material containing a thermoplastic resin having a linear molecular structure is obtained.

Since the tack of the surface of the fiber reinforced resin material is eliminated, the handling in the manufacturing process of the fiber reinforced resin material is improved, so that the productivity is improved. In addition, by eliminating tack, a fiber reinforced resin molded product obtained using the fiber reinforced resin material can be easily obtained without anisotropy, and also in the manufacturing process of the fiber reinforced resin molded product. Improved handling and productivity. Moreover, since tackiness is eliminated, even when the fiber reinforced resin material is stored, the fiber reinforced resin material can be prevented from adhering to each other, so that excellent storability can be secured.

As described above, the heating temperature is such that the reaction based on the thermoplastic resin and the curing agent is completely completed, the reaction is stopped in a certain state (or the reaction rate is reduced), and the functional group is It is performed at a temperature at which two or more crosslinking agents are not activated, for example, a temperature and a time at which the reaction between the crosslinking agent and the thermoplastic resin does not start. It should be noted that the cross-linking agent having two or more functional groups may undergo some reaction with the thermoplastic resin without departing from the object of the present invention.

Depending on the thermoplastic resin, the curing agent, the crosslinking agent having two or more functional groups, or a solvent, when an epoxy resin is used as the thermoplastic resin, drying and / or heat treatment may be performed at 40 to 200 ° C. If there is no longer any tack of the thermoplastic resin material, heating may be performed in two steps of drying and heat treatment, or only one of them may be performed. Drying is preferably performed at 40 to 120 ° C. for about 1 minute to 1 hour, and in the case of heat treatment, it is preferably performed at 120 ° C. to 200 ° C. for about 1 minute to 1 hour. More preferably, drying is performed at 60 to 120 ° C. for 10 minutes to 30 minutes, and heat treatment is performed at 121 ° C. to 180 ° C. for 3 minutes to 40 minutes. Such a range of conditions is preferable from the viewpoint of the quality and productivity of the obtained fiber-reinforced resin molded article.

A thermoplastic resin is applied to a bundle of carbon fibers, and after drying and / or heat treatment, the bundle of reinforcing fibers to which the thermoplastic resin is applied is cut to obtain a chip-like fiber reinforced resin material.

The cutting of the bundle of reinforcing fibers provided with the thermoplastic resin is cut in a direction perpendicular to the fiber axis direction of the bundle of reinforcing fibers arranged in one direction. In addition, the perpendicular direction here does not need to be exactly perpendicular to the fiber axis direction of the reinforcing fiber, and may be any one cut in a substantially perpendicular direction. Moreover, what was cut | disconnected in the diagonal direction may be sufficient with respect to the fiber axial direction of the reinforcing fiber bundle arranged in one direction. The length of the cut fiber reinforced resin material is as described above.

In addition, when the shape of the bundle of reinforcing fibers to which the thermoplastic resin is applied is a wide sheet-like or thick columnar shape, etc. A chip-shaped product may be manufactured by cutting in parallel.

In the above description, a chip-like fiber reinforced resin material including a bundle of reinforced fibers arranged in one direction and a thermoplastic resin and a method for manufacturing the same have been described. The shape is not limited, and may be any shape such as a sheet shape, a plate shape, a block shape, a line shape, or a string shape.

<Fiber-reinforced resin molding>
The fiber reinforced resin molded body according to the present embodiment is obtained by molding the above fiber reinforced resin material by heating. Preferably, the fiber reinforced resin material is obtained by heating and pressing. Further, it is obtained by heating a fiber reinforced resin material or a fiber reinforced resin molded body at a specific temperature or higher, and cannot be remolded by reheating.

Since the fiber reinforced resin material constituting the fiber reinforced resin molded body according to the present embodiment includes a thermoplastic resin, it is thermoplastic. Therefore, even after heating and pressurizing once to form a fiber reinforced resin molded article, if it is not heated above a specific temperature, it can be easily selected by heating the fiber reinforced resin molded article, particularly by heating and pressing. It can be reshaped into a shape.

Further, at the same time as or after molding by heating (or heating and pressing) using the above-mentioned fiber reinforced resin material, or after molding by heating (or heating and pressing), a temperature above a specific temperature, that is, substantially In particular, by heating at a temperature at which the thermoplastic resin loses its thermoplasticity and the re-molding of the fiber-reinforced resin molding cannot be performed, it cannot be re-molded by heating again.

This is because the above-mentioned linear thermoplastic resin is crosslinked at a temperature at which the crosslinking agent having a functional group of 2 or more crosslinks with a crosslinking agent having 2 or more functional groups, and the crosslinking agent having a functional group of 2 or more starts reaction. As a result, the linear thermoplastic resin becomes thermosetting, the glass transition temperature rises, the cross-linking agents are bonded to each other, the thermoplasticity is substantially lost, and the fiber-reinforced resin molded article I think that it will be impossible to re-form by heat.

It should be noted that substantially losing thermoplasticity means that the fiber-reinforced resin molded product cannot be re-molded at the temperature at which the fiber reinforced resin molded product is used, and re-moldability at temperatures above the usage environment or some softening in the usage environment. It does not exclude things that change or deform. Preferably, the fiber reinforced resin molded article is not softened or deformed at the temperature of use environment.

The fiber reinforced resin molded product that can no longer be reshaped by reheating is softened or temporarily deformed depending on the magnitude of the temperature or pressure by heating (or heating and pressurizing), Including the ones that may be slightly deformed, but in terms of the intended use and environment of the resulting fiber reinforced resin molded product, it refers to those that cannot be substantially remolded at a level that can achieve the purpose of use, and must be softened or deformed. Good.

For example, when the temperature at which re-molding is not performed by reheating is 100 ° C. or higher, the obtained fiber-reinforced resin molded body is used for applications that are used in a high-temperature environment of about 70 ° C. at high temperatures in summer, such as automobile interior parts. be able to.

In addition, when the temperature at which re-molding is not performed by reheating is 130 ° C. or higher, the obtained fiber-reinforced resin molded body can be used in a portion connected to a driving unit such as a motor. It can be used as a robot arm.

Further, when the temperature at which re-molding is not performed by reheating is 150 ° C. or higher, and further 200 ° C. or higher, the obtained fiber-reinforced resin molded body can be used in a higher temperature environment.

Preferably, after being heated above a specific temperature, it cannot be reshaped by reheating when the temperature is 150 ° C., the pressure is 2 MPa, and the time cannot be reshaped by heating and pressurizing for 15 seconds to 1 hour. .

Hereinafter, with respect to the fiber-reinforced resin molded body of the present embodiment, a chip-like fiber-reinforced resin material including a bundle of reinforcing fibers arranged in one direction, a thermoplastic resin, and a crosslinking agent having two or more functional groups This will be described in more detail in the case of using. In addition, about the matter which overlaps with what was demonstrated previously, description is abbreviate | omitted or simplified partially.

Specifically, the fiber-reinforced resin molded body of the present embodiment is a fiber including a thermoplastic resin and a strip-shaped reinforcing fiber bundle (reinforced fiber bundle) in which a plurality of reinforcing fibers are arranged in one direction. It is made of a reinforced resin material and has a laminated structure in which a bundle of strip-like reinforcing fibers are randomly laminated in three dimensions. By forming a bundle of strip-shaped reinforcing fibers randomly in three dimensions, a molded article having excellent impact resistance and fracture toughness can be obtained.

Here, a bundle of strip-like reinforcing fibers in which a plurality of reinforcing fibers are arranged in one direction is randomly laminated in three dimensions, which is obtained by arranging a plurality of reinforcing fibers in one direction. A plurality of strip-shaped reinforcing fiber bundles, the fiber axis direction of each bundle is randomly arranged with respect to the surface direction of the fiber-reinforced resin molded body, and the bundle of the plurality of reinforcing fibers is a fiber-reinforced resin molded body. This refers to a state in which the layers are stacked so as to overlap each other in the thickness direction. More specifically, a plurality of strip-shaped reinforcing fiber bundles are randomly arranged in the fiber axis direction of each bundle on the upper and lower surfaces of each bundle. In such a state, the bundles are stacked so as to be partially overlapped with each other, and each bundle is slightly inclined at random with respect to the surface direction of the fiber-reinforced resin molded body and folded over each other.

Thus, the fiber reinforced resin material constituting the fiber reinforced resin molded body of the present embodiment is a bundle of a plurality of reinforced fibers arranged in one direction. A bundle of a plurality of reinforcing fibers arranged in one direction is a combination of the fiber axis directions of the plurality of reinforcing fibers constituting the bundle of reinforcing fibers. Therefore, as long as the approximate axial directions of the reinforcing fibers constituting the reinforcing fiber bundle are matched, the reinforcing fiber bundle and the reinforcing fibers constituting the reinforcing fiber bundle may be bent or meandering. In particular, in a fiber reinforced resin molded body formed by heating and pressurizing, the reinforced fiber and the bundle of reinforcing fibers are bent or meandered by the concavo-convex shape of the molded body, the entanglement of the reinforcing fibers and the bundles thereof. There are many. In addition, the concept that a bundle of strip-like reinforcing fibers is randomly stacked in three dimensions is a state in which the reinforcing fibers and the bundle of reinforcing fibers are deformed by bending or meandering due to pressure or the like. Are also included.

In the fiber-reinforced resin molded body, the bundle of strip-shaped reinforcing fibers does not necessarily have to be inclined with respect to the surface direction of the fiber-reinforced resin molded body. May include those not inclined with respect to the surface direction of the fiber-reinforced resin molded body. Further, the fiber reinforced resin material constituting the fiber reinforced resin molded body may contain substances other than the reinforced fiber and the thermoplastic resin, such as a catalyst, an antioxidant, and a pigment.

Thus, the fiber reinforced resin molded body of the present embodiment is obtained using a plurality of fiber reinforced resin materials, and the reinforced fibers arranged in one direction constituting these fiber reinforced resin materials. The fiber axis directions of the bundle are random, and anisotropy is suppressed. That is, as the bundle of reinforcing fibers, the reinforcing fibers are arranged in one direction, but the bundles of a plurality of reinforcing fibers constituting the fiber-reinforced resin molded body have random fiber axis directions. If it sees as the whole molded object, the fiber axis direction of the reinforced fiber is random.

Therefore, the fiber-reinforced resin molded body has no anisotropy and can exhibit uniform strength in all directions.

Furthermore, in the fiber reinforced resin molded product obtained by laminating the carbon fiber fabric, the fiber reinforced resin molded product is easily cracked when a large force is applied, and the fracture surface of the cracked portion is sharp. The cut surface tends to be exposed. For this reason, in the unlikely event that the fiber reinforced resin molded body is cracked due to an accident or the like, there is a risk of causing secondary damage such as causing a cut in the body due to the fracture surface.

In contrast, in the fiber-reinforced resin molded body of the present embodiment, the fiber axis directions of the bundles of reinforcing fibers arranged in one direction constituting the fiber-reinforced resin material are random, and thus a large force is applied. Even in the case of cracking, it is suppressed that the fracture surface becomes sharp and that the sharp fracture surface is exposed. Thereby, since generation | occurrence | production of the above secondary damage is suppressed, the fiber reinforced resin molding which is excellent in safety is obtained.

In particular, if the length of the fiber reinforced resin material and the reinforcing fiber is 10 mm to less than 30 mm, it is easy to crack with a certain force or more, and even if it is cracked, it is difficult to form a sharp fracture surface. Further, if the length of the fiber reinforced resin material and the reinforcing fiber is 30 mm or more, more preferably 40 mm or more, it is difficult to break even when subjected to a stronger impact, and even if it is cracked, a sharp fracture surface is difficult to be formed. Therefore, the characteristic of the fiber reinforced resin molding obtained can be adjusted by the length of the fiber reinforced resin material and the reinforced fiber.

The shape of the fiber-reinforced resin molded body of the present embodiment is not particularly limited, and examples thereof include a sheet shape, a plate shape, and a block shape. In addition, from the shape of interior parts such as car insert panels, the shape of automotive parts such as chassis, the shape of industrial equipment parts such as robot arms, or the shape of parts for household appliances such as TV housings, etc. It may be formed directly into the intended unevenness or curved shape.

Further, the fiber volume content (Vf value) in the fiber reinforced resin material of the present embodiment is preferably 30% to 80%. The Vf value is more preferably 40% or more, still more preferably 50% or more, from the viewpoint of the strength of the fiber-reinforced resin molded product obtained using the fiber-reinforced resin material. Further, from the viewpoint of appearance quality and moldability of the fiber reinforced resin molded article obtained using the fiber reinforced resin material, the Vf value is preferably 70% or less, more preferably around 60%.

As described above, when a space is generated between the fiber reinforced resin material and the fiber reinforced resin material constituting the fiber reinforced resin molded body, the fiber reinforced resin material has a Vf value so that no space is generated. Is preferably 50% or less, more preferably 45% or less. If a space is formed between the fiber reinforced resin material and the fiber reinforced resin material constituting the fiber reinforced resin material, the strength of the obtained fiber reinforced resin molded article may be reduced.

In addition, if the Vf value of the fiber reinforced resin molded product is small, the strength of the fiber reinforced resin molded product may be lowered. Therefore, if a high strength product is required, the fiber reinforced resin molded product described below is used. At the time of heating and pressurization for obtaining, excess thermoplastic resin may be removed to increase the Vf value.

That is, it is preferable that the Vf value of the fiber reinforced resin molding is larger than the Vf value of the fiber reinforced resin material.

Further, the thickness of the fiber-reinforced resin molded body of the present embodiment is not particularly limited and can be arbitrarily set for the intended use of the molded body, for example, 0.1 mm to 1000 mm. is there. Further, the lengths in the vertical direction and the horizontal direction of the fiber-reinforced resin molded body in the present embodiment are not particularly limited, and can be arbitrarily set for the intended use of the molded body.

In the fiber reinforced resin molded body of the present embodiment, since a reactive thermoplastic resin is used, the fiber reinforced resin material constituting the fiber reinforced resin molded body is compared with the thermoplastic resin used by being melted by heating. The thermoplastic resin enters the bundle of reinforcing fibers. Thereby, the fiber reinforced resin molding which has the outstanding intensity | strength and can exhibit the stable intensity | strength can be obtained.

As described above, the fiber-reinforced resin molded body of the present embodiment can be molded even after being cured as compared with a thermosetting resin, and can be stored and stored at a low temperature until molding like a thermosetting epoxy resin. It is easy to use without a problem of period, does not require a long curing time, and is excellent in productivity.

In addition, the fiber-reinforced resin molded body of the present embodiment can be remolded until it is heated at the specific temperature or higher.

In addition, the fiber-reinforced resin molded body of the present embodiment is not re-molded even after being heated again at the specific temperature after being heated above the specific temperature. In addition, as described above, the fiber-reinforced resin molded body of the present embodiment includes those that are somewhat softened or deformed depending on the temperature or pressure even when heated at a specific temperature or higher, but are not remolded. Therefore, it has thermal stability even in an environment of room temperature or higher, and can be used in a wide range of applications.

In addition, the fiber-reinforced resin molded body of the present embodiment is strong and lightweight, and further has been suppressed from deformation against heat, and thus has been conventionally manufactured using a metal such as iron or a thermosetting resin. In addition to objects such as automobile parts such as automobile chassis, building materials such as reinforcing bars, columns, beams, spacers, anchor plates, jack plates, electrical appliances such as TVs, computers, refrigerators, etc. It can be used for various objects and applications such as a member that comes into contact with a drive unit such as a motor of an industrial device such as a robot arm.

Moreover, in the fiber reinforced resin molded product of the present embodiment, by using carbon fiber as the reinforcing fiber and using an epoxy resin as the thermoplastic resin, a molded product excellent in durability, light weight, high strength, and rust prevention property is obtained. Obtainable.

<Method for producing fiber-reinforced resin molded article>
Next, a preferable manufacturing method of the fiber-reinforced resin molded body of the present embodiment (a thermoplastic resin, a reinforcing fiber, and a functional group containing a crosslinking agent having two or more functional groups) will be described. In addition, the manufacturing method of the fiber reinforced resin molding of this Embodiment is not limited to the following method. In addition, a part of the description overlapping with the description previously described is partially omitted or simplified.

The method for manufacturing a fiber-reinforced resin molded body according to the present embodiment includes a step of heating the fiber-reinforced resin material.

When heating, not only heating but also pressing should be performed. For heating and pressurization, heating and pressurization may be performed simultaneously, pressurization may be performed after heating, or heating and pressurization may be performed simultaneously after heating.

Specific examples of the heating and pressurizing method include a mold pressing method, an autoclave method, and a heating / cold pressing method.

More specifically, the fiber axis directions of the bundles of reinforcing fibers arranged in one direction constituting each of the plurality of chip-like fiber reinforced resin materials according to the present embodiment are random. And then heating and pressurizing while removing air from the mold, and then cooling.

In the case of a fiber reinforced resin material in which a thermoplastic resin is added to a woven fabric obtained using the opened reinforcing fibers, a plurality of the fiber reinforced resin materials are laminated by shifting the fiber axis direction or the like. Then, it is placed on the mold, heated and pressurized while venting the air in the mold, and then cooled.

Furthermore, between the fiber reinforced resin materials provided with the thermoplastic resin to the woven fabric obtained by using the opened reinforcing fibers, or the reinforced fibers arranged in one direction constituting the chip-like fiber reinforced resin material on one side. A method of laminating the bundles in such a manner that the fiber axis directions of the bundles are random, heating and pressurizing while removing air in the molds, and then cooling is not particularly limited.

The temperature at which the fiber reinforced resin material is heated is, for example, about 50 to 400 ° C., depending on the type of thermoplastic resin, crosslinking agent and reinforcing fiber used, and the thickness of the fiber reinforced resin molding to be obtained. The pressure when pressing the fiber reinforced resin material is, for example, about 1 to 50 MPa, and the pressing time is, for example, about 15 seconds to 24 hours, preferably 30 seconds to 6 hours, more preferably 1 minute. About 1 hour.

If it is not necessary to mold the desired molded body directly from the fiber reinforced resin material according to the present embodiment and then deform it, the heating temperature of the fiber reinforced resin material cannot be remolded. The temperature or a temperature at which the cross-linking agent reacts (specific temperature), for example, a temperature equal to or higher than a temperature at which the cross-linking agent reacts with the linear thermoplastic resin may be used. Further, the heating time may be any time as long as the fiber-reinforced resin molded product obtained at the temperature cannot be re-molded, and is preferably about 30 seconds to 6 hours, more preferably about 15 seconds to 1 hour.

In addition, if it is possible to re-mold after molding once, the heating temperature at the time of molding is less than the temperature at which the cross-linking agent etc. reacts (specific temperature), and then at a certain temperature or higher at any time What is necessary is just to heat at the temperature. When re-molding, if it is not necessary to re-mold thereafter, the cross-linking agent may be heated at a temperature equal to or higher than the temperature (specific temperature) at which reaction with the linear thermoplastic resin starts.

In addition, even when it is directly molded into a desired shape, it may not be remolded by reheating by heating at a certain temperature or higher after molding.

In addition, when molding a fiber reinforced resin material by heating, the fiber reinforced resin material is sufficiently softened at a low temperature, and is heated to a specific temperature or higher after it is molded into the desired shape with adhesiveness or fluidity. Good. Thereby, the obtained fiber reinforced resin molded product is excellent in shape, appearance quality, strength and the like.

Further, when producing a flat sheet-like fiber reinforced resin molded product, the above method may be used, but a continuous method such as a double belt press method may be used.

Furthermore, when a thick block-shaped fiber reinforced resin molded product or an uneven fiber reinforced resin molded product is produced using this molded product after being molded once into a flat sheet-like fiber reinforced resin molded product, When molding a sheet-like fiber-reinforced resin molded article, it is better not to heat above a specific temperature.

In addition, once a fiber reinforced resin molded body is formed into a sheet shape, plate shape, string shape, line shape, etc., it is reshaped by heating (or heating and pressurizing) to the desired shape at any time. May be. In this case, after forming into the target shape, heating is preferably performed at a specific temperature or higher in order to increase stability against heat.

For example, after molding as a linear fiber reinforced resin molded product, if necessary, combine multiple linear fiber reinforced resin molded products, and then heat at a specific temperature or higher to make a bar with excellent thermal stability And The obtained bar may be used as a reinforcing material for concrete, a brace material, a building material such as a wire, or the like.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. Further, “parts” in the following examples are parts by mass.

(Example 1)
(Fiber reinforced resin material)
In Example 1, as a bundle of reinforcing fibers arranged in one direction, a bundle of 24,000 carbon fibers was used (PAN-based carbon fiber: Torayca (registered trademark) T700SC manufactured by Toray Industries, Inc.).

The following thermoplastic resin solution was applied to one side of the carbon fiber bundle using a kiss roll while pulling out the carbon fiber bundle as it was without performing the fiber opening treatment from the drum around which the carbon fiber bundle was wound. In addition, the cross-sectional shape of the bundle of carbon fibers when pulled out from the drum was a flat shape.

[Thermoplastic resin solution (viscosity: 80 mPa · s)]
-Thermoplastic epoxy resin (Reactive resin: DENATEITE TPEP-AA-MEK-05B: manufactured by Nagase ChemteX Corporation. Solid content: 85% by mass) 100 parts-Curing agent (XNH6850RIN-K: manufactured by Nagase ChemteX Corporation) 6.5 parts ・ Crosslinking agent (HDI compound blocked with oxime (adduct modified). Solid content 55% by weight) 20 parts ・ Methyl ethyl ketone 10 parts

Next, after squeezing the bundle of carbon fibers by bringing the bundle of carbon fibers provided with the thermoplastic resin solution into contact with four rolls (the upper and lower surfaces of the bundle of carbon fibers are alternately contacted twice each) , By drying at 60 ° C. for 10 minutes, followed by heat treatment at 120 ° C. for 10 minutes, a reactive thermoplastic into a bundle of reinforcing fibers arranged in one direction with a length of 50 m, a width of 4 mm, and a thickness of 0.38 mm A tape-like fiber reinforced resin material provided with a resin was obtained. The glass transition temperature of the thermoplastic resin was 100 ° C.

When the cut surface of the fiber reinforced resin material was observed at 100 times using an electron microscope, the resin entered the center of the bundle of carbon fibers.

The viscosity of the thermoplastic resin solution was measured using a B-type viscometer (TVB-15 type viscometer: manufactured by Toki Sangyo Co., Ltd.). Measured at 20, 12 rpm and room temperature (15 ° C.).

The obtained tape-like fiber reinforced resin material (carbon fiber resin material) was subjected to the following (thermal deformation test), (re-molding test), and (storage ease test).

(Deformation test by heat)
The tape-like fiber reinforced resin material obtained was cut into a length of 15 cm and used as Sample 1. Further, Sample 2 obtained by subjecting Sample 1 to heat treatment at 200 ° C. for 10 minutes in a hot air oven was used as Sample 2. In addition, the glass transition temperature of the thermoplastic resin which performed the heat processing for 10 minutes at 200 degreeC was 100 degreeC, and the glass transition temperature was not rising compared with before heat processing.

First, with respect to the cut samples 1 and 2, 5 cm from the end of the long side of each sample is sandwiched between two stainless steel plates so that the 10 cm of the long side of each sample protrudes from the two stainless steel plates. To do.

Next, with respect to Samples 1 and 2, the portions protruding from the two stainless steel plates are placed in a horizontal state in the air, and each sample is placed in each of a 170 ° C. hot air oven and a 240 ° C. hot air oven. Then, after 10 minutes had passed in each hot air oven at 170 ° C. and 240 ° C., it was confirmed whether each sample was scuttled by heat (sagging).

As a result of this test, as for sample 1, those heated at 170 ° C. and 240 ° C. were both softened, and large settling (sagging in a substantially vertical state) was confirmed. On the other hand, for sample 2, the samples heated at 170 ° C. and 240 ° C. were not confirmed to be drooping (sagging).

Therefore, it was confirmed that the shape stability against heat was improved after heating at 200 ° C.

(Re-molding test)
A re-molding test was performed using Sample 1 and Sample 2 prepared as samples in the above (deformation test by heat).

First, each sample was placed on a mold having 5 mm irregularities, preheated at 120 ° C. for 10 minutes, and then heated and heated at 240 ° C. and 4 MPa for 30 minutes in a vacuum state (vacuum degree: −0.1 MPa). Pressure was applied.

After cooling, the sample 1 taken out of the mold was molded into a clean shape along the shape of the mold with a depth of 5 mm, but the sample 2 was in a wavy state, but a clean uneven shape. It was not possible to mold.

Therefore, it was confirmed that the obtained fiber reinforced resin material can be molded by heating at 240 ° C., and after heating at 200 ° C., it cannot be remolded at least at 240 ° C. and 4 MPa.

(Easy storage)
Using the sample 1 prepared as a sample in the above (deformation test by heat), a test relating to storability was performed.

Specifically, after the sample 1 was left in a hot air oven at 60 ° C. for 5 days, the above (deformation test by heat) was performed. That is, with respect to the sample 1, the part protruding from the two stainless steel plates is placed in a horizontal state in the air, and the sample 1 is placed in each of the hot air oven at 170 ° C. and the hot air oven at 240 ° C.

As a result, the sample 1 after being left as it was when left in a hot air oven at 60 ° C. was heated substantially at 170 ° C. and 240 ° C. (sagging to a nearly vertical state), and the thermoplasticity was high. It was confirmed that it was maintained.

Therefore, it was confirmed that Sample 1 can be stored easily without being stored at low temperatures, such as a fiber reinforced resin material before curing using a thermosetting resin or a fiber reinforced resin molded body after molding.

From the above test, the fiber reinforced resin material of Example 1 is a fiber reinforced resin material containing a thermoplastic resin and a reinforced fiber, and can be molded by heating (or heating and pressing), and It was confirmed that re-molding cannot be performed by heating (or heating and pressing) after heating at a specific temperature or higher during molding or after molding. From the above test, in this example, the specific temperature is in the range of more than 120 ° C. and 200 ° C. or less.

(Fiber reinforced resin molding)
Next, the tape-like fiber reinforced resin material is cut so as to have a length of 40 to 50 mm substantially perpendicular to the axial direction of the carbon fiber, and a cross section having a length of 40 to 50 mm, a width of 4 mm, and a thickness of 0.38 mm is flattened. A chip-like fiber-reinforced resin material was obtained in a simple shape. The Vf value of the obtained fiber reinforced resin material was 45%. The length of the carbon fiber in the obtained fiber reinforced resin material is the same as the length of the fiber reinforced resin material because the carbon fiber is a long fiber, and is 40 to 50 mm.

Next, a plurality of the obtained chip-like fiber reinforced resin materials were randomly stacked in a mold, preheated at 120 ° C. for 5 minutes, and then vacuumed using a vacuum press (degree of vacuum: −0 .1 MPa) at 240 ° C. and 4 MPa for 30 minutes.

Thereafter, the thermoplastic resin exuded from the mold was removed to obtain a fiber-reinforced resin molded body formed into a plate shape having a thickness of 1.3 mm. The appearance quality of the obtained fiber reinforced resin molded article was good, and when the cross section of the fiber reinforced resin molded article was observed at 50 times using an electron microscope, there was no space inside. Further, the Vf value of the obtained fiber reinforced resin molded product was 55%.

(Deformation test by heat)
The obtained plate-like fiber reinforced resin molded article was cut into a length of 15 cm and a width of 3 cm and used as a sample. The sample thickness was 1.3 mm.

For the cut sample, 5 cm from the end of the long side of the sample is sandwiched between two stainless plates so that the 10 cm of the long side of the sample protrudes from the two stainless plates.

Next, this sample is placed in a horizontal state in the air so that the part protruding from the two stainless steel plates is placed in each of a hot air oven at 170 ° C. and a hot air oven at 240 ° C. Then, after 10 minutes had passed in each of the hot air ovens at 170 ° C. and 240 ° C., it was confirmed whether the sample was scuttled by heat.

As a result of this test, no stickiness (sagging) was confirmed in any of the samples heated at 170 ° C. and 240 ° C.

Therefore, it was possible to mold by heating at 240 ° C., and after heating at 240 ° C., it was confirmed that the stability of the shape against heat was improved.

(Re-molding test)
In this test, the obtained plate was used as a sample.

First, the sample was placed on a tray-shaped mold having a depth of 5 mm, pre-heated at 240 ° C. for 10 minutes, then heated in a vacuum state (vacuum degree: −0.1 MPa) at 240 ° C. and 4 MPa for 30 minutes. Pressurization was performed.

After cooling, the heated and pressurized sample taken out of the mold was in a state where the plate-like object was slightly depressed, but it was not shaped along the tray shape with a depth of 5 mm, but was remolded. I couldn't.

Therefore, it was confirmed that the fiber reinforced resin material can be molded by heating at 240 ° C., but after being heated at 240 ° C., it cannot be remolded at 240 ° C. and 4 MPa.

From the above test, the fiber reinforced resin molded product of Example 1 is a fiber reinforced resin molded product obtained using a fiber reinforced resin material, and is obtained by heat treatment at a specific temperature or higher. , And could not be reshaped by reheating (or heating and pressing). In this embodiment, the specific temperature is in the range of more than 120 ° C. and 240 ° C. or less.

Therefore, the fiber-reinforced resin molded body of Example 1 can be used even in a high temperature environment of about 240 ° C.

(Example 2)
In Example 2, a bundle of 60000 single carbon fibers was used as a bundle of reinforcing fibers arranged in one direction (PAN-based carbon fiber filament: Pyofil # TRH50 60M manufactured by Mitsubishi Rayon Co., Ltd.).

[Thermoplastic resin solution (viscosity: 15 mPa · s or less (equipment measurement limit value or less))]
-Thermoplastic epoxy resin (reactive resin: DENATEITE XNR6850V: manufactured by Nagase ChemteX Corporation. Solid content: 85% by mass) 100 parts-Curing agent (DENATEITE XNH6850V: manufactured by Nagase ChemteX Corp .: solid content: 30% by mass) 5 parts Crosslinking agent (HDI compound blocked with caprolactam (adduct modified). Solid content 55% by mass) 40 parts Methyl ethyl ketone 200 parts

Next, after squeezing the bundle of carbon fibers by bringing the bundle of carbon fibers provided with the thermoplastic resin solution into contact with four rolls (the upper and lower surfaces of the bundle of carbon fibers are alternately contacted twice each) , By drying at 110 ° C. for 3 minutes, a tape-form in which a reactive thermoplastic resin is applied to a bundle of reinforcing fibers arranged in one direction in a width of 5 to 10 mm and a thickness of 0.5 to 1.5 mm A fiber reinforced resin material was obtained. The glass transition temperature of the thermoplastic resin was 100 ° C.

The viscosity of the thermoplastic resin solution was measured using a B-type viscometer (TVB-15 type viscometer: manufactured by Toki Sangyo Co., Ltd.). It is measured at 20, 60 rpm and room temperature (15 ° C.).

(Deformation test by heat)
The tape-like fiber reinforced resin material (width 8 mm, thickness 1.0 mm) obtained was cut to a length of 15 cm and used as sample 1. Further, Sample 2 obtained by subjecting Sample 1 to heat treatment at 200 ° C. for 10 minutes in a hot air oven was used as Sample 2. The glass transition temperature of the thermoplastic resin subjected to the heat treatment at 200 ° C. for 10 minutes was 110 ° C., which was higher than before the heat treatment.

As a result of this experiment, as for sample 1, those heated at 170 ° C. and 240 ° C. were both softened, and large settling (sagging in a substantially vertical state) was confirmed. On the other hand, for sample 2, the samples heated at 170 ° C. and 240 ° C. were not confirmed to be drooping (sagging).

After cooling, the sample 1 taken out of the mold was molded into a clean shape along the shape of the mold with a depth of 5 mm, but the sample 2 was clean but slightly wavy. It was not uneven and could not be molded.

As a result, the sample 1 after being left as it was when it was heated in a hot air oven at 60 ° C. was heated substantially at 170 ° C. and 240 ° C. (sag almost vertically) and had thermoplasticity. It was confirmed that

Therefore, it was confirmed that it can be easily stored without being stored at low temperature, such as a fiber reinforced resin material before curing using a conventional thermosetting resin or a fiber reinforced resin molded body after molding.

From the above test, the fiber reinforced resin material of Example 2 is a fiber reinforced resin material containing a thermoplastic resin and a reinforced fiber, and can be molded by heating (or heating and pressing), and It was confirmed that re-molding cannot be performed by heating (or heating and pressing) after heating at a specific temperature or higher during molding or after molding. From the above test, in this example, the specific temperature is in the range of more than 120 ° C. and 200 ° C. or less.

(Fiber reinforced resin molding)
Next, the tape-like fiber reinforced resin material is cut so as to have a length of 20 to 30 mm substantially perpendicular to the axial direction of the carbon fiber, and is 20 to 30 mm in length, 5 to 10 mm in width, and 0.5 to 1 in thickness. A 5 mm chip-like fiber-reinforced resin material was obtained. The Vf value of the obtained fiber reinforced resin material was 44 to 53%. The length of the carbon fiber in the obtained fiber reinforced resin material is the same as the length of the fiber reinforced resin material because the carbon fiber is a long fiber, and is 20 to 30 mm.

Next, the obtained chip-like fiber reinforced resin material was randomly laminated in a mold, pre-heated at 120 ° C. for 5 minutes, and then in a vacuum state (vacuum degree: − 0.1 MPa), the pressure was increased from 120 ° C. to 240 ° C. at 2 ° C./min while pressurizing to 4 MPa, and heating and pressurization were performed at 240 ° C. and 4 MPa for 30 minutes.

Thereafter, the thermoplastic resin exuded from the mold was removed to obtain a plate-like fiber-reinforced resin molded body having a thickness of 25.5 mm, a length of 150 mm, and a width of 150 mm. The appearance quality of the obtained fiber reinforced resin molded article was good, and when the cross section of this fiber reinforced resin molded article was observed at 50 times using an electron microscope, no space was confirmed inside. Further, the Vf value of the obtained fiber reinforced resin molded product was 55%.

(Deformation test by heat)
The obtained plate-like fiber reinforced resin molded article was cut into a length of 15 cm and a width of 3 cm and used as a sample. The thickness of the sample was 25.5 mm.

Therefore, it was possible to mold by heating at 240 ° C. After heating at 240 ° C., it was confirmed that the stability of the shape by heat was improved.

(Re-molding test)
In this test, the obtained plate was used as a sample.

After cooling, the sample after heating and pressurization taken out from the mold was slightly depressed but was hardly deformed and could not be reshaped.

From the above test, the fiber reinforced resin molded body of Example 2 is a fiber reinforced resin molded body obtained using a fiber reinforced resin material, and is obtained by heat treatment at a specific temperature or higher. , And could not be reshaped by reheating (or heating and pressing). In this embodiment, the specific temperature is in the range of more than 120 ° C. and 240 ° C. or less.

Further, the fiber reinforced resin molded body of Example 2 is used in an environment of about 240 ° C., for example, in a place where it comes into contact with a drive unit such as a motor of a robot arm that becomes an environment of about 130 ° C. or in a high temperature environment. It can also be used as a spacer or jack plate.

(Example 3)
In Example 3, a plain fabric (Torayca (registered trademark) CO6343B manufactured by Toray Industries, Inc., 3K carbon obtained by bundling and opening 3000 carbon fibers) obtained by using carbon fibers of long fibers as reinforcing fibers of long fibers. Plain fabric obtained using fiber bundles) was used.

First, this plain fabric was immersed in the same thermoplastic resin solution as in Example 2 to give the thermoplastic fabric solution to the plain fabric.

Next, the upper and lower surfaces of the plain woven fabric to which the thermoplastic resin solution is applied are brought into contact with 10 rolls (the upper and lower surfaces of the plain woven fabric are alternately contacted 5 times each), and then rubbed at 60 ° C. for 20 minutes. Dry, and then heated at 110 ° C. for 10 minutes, a sheet-like form in which a reactive thermoplastic resin is applied to a woven fabric obtained by using long carbon fibers having a length of 50 m, a width of 48 cm, and a thickness of 0.39 mm A fiber reinforced resin material was obtained. The thermoplastic resin dried at 60 ° C. and heated at a temperature equal to or higher than the specific temperature heated at 110 ° C. has a glass transition temperature of 100 ° C., and the obtained sheet-like fiber reinforced resin material has a Vf value of 50. %Met.

The following (thermal deformation test), (re-molding test), and (storability test) were performed on the obtained sheet-like fiber reinforced resin material.

(Deformation test by heat)
The obtained sheet-like fiber reinforced resin material was cut into a length of 15 cm and a width of 3 cm and used as Sample 1. The thickness of Sample 1 was 0.39 mm. Further, Sample 2 obtained by subjecting Sample 1 to heat treatment at 200 ° C. for 10 minutes in a hot air oven was used as Sample 2. Using the samples 1 and 2, the following tests were performed. The glass transition temperature of the thermoplastic resin subjected to the heat treatment at 200 ° C. for 10 minutes was 110 ° C., which was higher than before the heat treatment.

First, each sample was placed on a tray-shaped mold having a depth of 5 mm, preheated at 120 ° C. for 10 minutes, and then heated in a vacuum state (vacuum degree: −0.1 MPa) at 150 ° C. and 2 MPa for 15 minutes. And pressurization.

After cooling, the sample 1 taken out of the mold became a clean tray shape along the shape of the mold having a depth of 5 mm, but the sample 2 was slightly depressed, but the depth was 5 mm. It was not possible to reshape the tray.

Therefore, it was confirmed that the obtained fiber reinforced resin material can be molded by heating at 150 ° C., and after heating at 200 ° C., it cannot be remolded at least at 150 ° C. and 2 MPa.

As a result, the sample 1 after being left as it was when left in a hot air oven at 60 ° C. was heated substantially at 170 ° C. and 240 ° C. (sag in a substantially vertical state). It was confirmed to have.

According to the above test, the fiber reinforced resin material of Example 3 is a fiber reinforced resin material containing a thermoplastic resin and a reinforced fiber, and can be molded by heating (or heating and pressing), and It was confirmed that re-molding cannot be performed by heating (or heating and pressing) after heating at a specific temperature or higher during molding or after molding. From the above test, in this example, the specific temperature is in the range of more than 120 ° C. and 200 ° C. or less.

(Fiber reinforced resin molding)
Next, five sheet-like fiber reinforced resin materials are stacked while being shifted in the fiber axis direction, placed on a substantially L-shape of 102 °, preheated at 120 ° C. for 10 minutes, and in a vacuum state (vacuum degree) : -0.1 MPa) at 150 ° C. and 2 MPa for 15 minutes while heating, a substantially L-shaped (L portion angle of 102 °) fiber-reinforced resin molded body was obtained. The thickness of the flat part (part which is not the top of L part) of the obtained fiber reinforced resin molding was 1.25 mm. The Vf value of the fiber reinforced resin molded product was 52%.

(Deformation test by heat)
The obtained substantially L-shaped fiber reinforced resin molded article was cut from a flat portion to a length of 15 cm and a width of 3 cm and used as a sample. The sample thickness was 1.25 mm.

Therefore, it was possible to mold by heating at 150 ° C. After heating at 150 ° C., it was confirmed that the stability of the shape against heat was improved.

(Re-molding test)
In this test, the obtained fiber reinforced resin molded product molded into an L-shape was used as a sample.

First, the sample was placed on a flat mold with the L-shaped apex facing upward, preheated again at 150 ° C. for 10 minutes, and then in a vacuum state (vacuum degree: −0.1 MPa) at 150 ° C. and 2 MPa. Heating and pressurization for 15 minutes were performed.

After cooling, the heated and pressurized sample had a shape in which the L-shaped tip was slightly opened, but could not be reshaped into a flat plate shape.

Therefore, although the fiber reinforced resin material can be molded by heating at 150 ° C., it was confirmed that after heating at 150 ° C., re-molding cannot be performed at 150 ° C. and 2 MPa.

From the above results, the fiber reinforced resin molded body of Example 3 is a fiber reinforced resin molded body obtained using a fiber reinforced resin material, and is obtained by heat treatment at a specific temperature or higher. , And could not be reshaped by reheating (or heating and pressing). In the present embodiment, the specific temperature is in the range of more than 120 ° C. and 150 ° C. or less.

The fiber reinforced resin molded body of Example 3 is used in an environment of about 240 ° C., for example, as an L-shaped plate for reinforcing a steel floor slab that can withstand heat during paving of asphalt. it can.

From the above results, the fiber reinforced resin materials of Example 1, Example 2 and Example 3 can be molded by heating, and an arbitrary molded body can be easily obtained.

In addition, the fiber reinforced resin molded articles of Example 1, Example 2 and Example 3 are excellent in storability, and can be stored without performing special refrigeration and the convenience of industrial use. improves.

Further, if the fiber reinforced resin materials of Examples 1, 2 and 3 are used, it is possible to provide a fiber reinforced resin molded article that can be easily molded by heat and can be used even in a high temperature environment.

Further, the fiber reinforced resin molded bodies of Example 1, Example 2 and Example 3 are heated at a specific temperature or higher as compared with the fiber reinforced resin material having thermoplasticity used to obtain the fiber reinforced resin molded body. This increases the thermal stability of the shape against heat and can be used in a higher temperature environment.

Example 4
Next, the results of an experiment conducted on the specific temperature during or after the molding described above will be described using Example 4.

In Example 4, first, a fiber-reinforced resin material was obtained by changing the amount of the crosslinking agent in the thermoplastic resin solution used in Example 3 to 0 part, 5 parts, and 10 parts. In addition, it was the same as that of Example 3 except having changed the quantity of the crosslinking agent.

Next, the obtained sheet-like fiber reinforced resin material is cut into a length of 10 cm and a width of 4 cm, and the amount of the cross-linking agent is 0 part, 5 parts, and 10 parts as Sample 1, Sample 2, and Sample 3, respectively. Got ready.

Then, after performing heat treatment at 150 ° C. for 10 minutes for each sample, the following molding test was performed, and for each sample, the following molding test was performed without performing heat treatment.

(Molding test)
Four samples are stacked and placed on a flat mold, and in a vacuum state (vacuum degree: -0.1 MPa), (i) 125 ° C., 8 MPa, 10 minutes, (ii) 150 ° C., 8 MPa, 10 minutes (Iii) Heating and pressing were performed at 175 ° C., 8 MPa, 10 minutes, and (iv) 200 ° C., 8 MPa, 10 minutes. That is, the conditions of pressure and time were constant, and heating and pressurization were performed while changing the temperature.

With respect to the fiber reinforced resin material after the molding test, samples 1 to 3 were subjected to the heat treatment at 150 ° C. for 10 minutes and then subjected to the molding test, and samples 1 to 3 were subjected to the molding test without being subjected to heat treatment. In addition to observing the appearance of the obtained sheet-like fiber-reinforced resin molded article, the bending strength was measured. The bending strength was measured at a speed of 5 mm / min and a fulcrum distance of 40 mm. Moreover, the thickness of each fiber reinforced resin molding was 1.0 mm.

As a result, the evaluation results of the appearance quality are shown in Table 1 for Samples 1 to 3 which were subjected to the above-described molding test after heat treatment at 150 ° C. for 10 minutes. For samples 2 and 3, the gloss of the surface became stronger as the heating temperature increased.

On the other hand, although not shown in Table 1, with respect to the appearance quality of Samples 1 to 3 that were subjected to the above molding test without heat treatment, all four samples were integrated, and the surface became smooth. It was mirror-like. That is, it was confirmed that remolding was performed.

Also, the measurement results of bending strength are shown in Table 2. Table 2 shows the measurement of bending strength for Samples 1 to 3 that were subjected to the above-described molding test after heat treatment at 150 ° C. for 10 minutes and Samples 1 to 3 that were subjected to the above-mentioned molding test without performing heat treatment. Results are shown. For Samples 1 to 3 that were not heat-treated, only the case ((i)) in the above-described molding test was heated and pressurized at 125 ° C., 8 MPa, and 10 minutes.

According to the above experimental results, in the case of Example 4, at least the specific temperature is 150 ° C. or lower, and before heating at a specific temperature or higher, the four fiber reinforced resin materials have the appearance and strength. From the viewpoint, it was confirmed that the integral molding was performed. In addition, after heating at a specific temperature or higher, the appearance quality is not sufficient as shown in Table 1, even if the fiber reinforced resin material appears to be integrated (reformed) at first glance. In addition, as shown in Table 2, it did not have sufficient strength and was not integrated (reformed). That is, it was confirmed that after heating at a specific temperature or higher, re-molding cannot be performed by reheating.

(Example 5)
In Example 5, except that the following were used as the thermoplastic resin solution, the same procedure as in Example 3 was applied to a woven fabric obtained by using long-fiber carbon fibers having a length of 50 m, a width of 48 cm, and a thickness of 0.39 mm. A sheet-like fiber reinforced resin material provided with a reactive thermoplastic resin was obtained. In addition, the thermoplastic resin before heating above the specific temperature heated at 110 degreeC after drying at 60 degreeC has a glass transition temperature of 100 degreeC, and Vf value of the obtained sheet-like fiber reinforced resin material is 45. %Met.

[Thermoplastic resin solution (viscosity: 80 mPa · s)]
-Thermoplastic epoxy resin (reactive resin: DENATEITE XNR6850V: manufactured by Nagase ChemteX Corporation. Solid content: 85% by mass) 100 parts-Curing agent (DENATEITE XNH6850V: manufactured by Nagase ChemteX Corp .: solid content: 30% by mass) 5 parts ・ Crosslinking agent (IPDI compound blocked with oxime. Solid content 55% by mass) 30 parts ・ Methyl ethyl ketone 10 parts

(Deformation test by heat)
The obtained sheet-like fiber reinforced resin material was cut into a length of 15 cm and a width of 3 cm and used as Sample 1. The thickness of Sample 1 was 0.39 mm. Further, Sample 2 obtained by subjecting Sample 1 to heat treatment at 200 ° C. for 10 minutes in a hot air oven was used as Sample 2. Using Samples 1 and 2, a heat deformation test was performed in the same manner as in Example 3. The glass transition temperature of the thermoplastic resin subjected to the heat treatment at 200 ° C. for 10 minutes was 120 ° C., which was higher than before the heat treatment.

First, each sample was placed on a tray-shaped mold having a depth of 5 mm, pre-heated at 120 ° C. for 10 minutes, and then heated at 200 ° C. and 4 MPa for 30 minutes in a vacuum state (vacuum degree: −0.1 MPa). And pressurization.

Therefore, it was confirmed that the obtained fiber reinforced resin material can be molded by heating at 200 ° C. and cannot be remolded at 200 ° C. and 4 MPa at least after heating at 200 ° C.

(Easy storage)
Using the sample 1 prepared as a sample in the above (deformation test by heat), a test related to (easy storage) similar to that in Example 3 was performed.

From the above test, the fiber reinforced resin material of Example 5 is a fiber reinforced resin material containing a thermoplastic resin and a reinforced fiber, and can be molded by heating (or heating and pressing), and It was confirmed that re-molding cannot be performed by heating (or heating and pressing) after heating at a specific temperature or higher during molding or after molding. From the above test, in this example, the specific temperature is in the range of more than 120 ° C. and 200 ° C. or less.

(Fiber reinforced resin molding)
Next, five sheet-like fiber reinforced resin materials are stacked while being shifted in the fiber axis direction, placed on a flat plate mold, preheated at 120 ° C. for 10 minutes, and in a vacuum state (vacuum degree: −0 .1 MPa) at 200 ° C. and 4 MPa for 30 minutes while heating to obtain a flat fiber-reinforced resin molded body. The thickness of the obtained fiber reinforced resin molded product was 1.25 mm. The Vf value of the fiber reinforced resin molded product was 47%.

(Deformation test by heat)
The obtained flat fiber-reinforced resin molded product was cut into a length of 15 cm and a width of 3 cm and used as a sample. The sample thickness was 1.25 mm.

The cut sample was subjected to the same test (deformation test by heat) as in Example 3. As a result of this test, no stickiness (sagging) was observed in any of the samples heated at 170 ° C. and 240 ° C.

Therefore, it was possible to mold by heating at 200 ° C., and after heating at 200 ° C., it was confirmed that the stability of the shape against heat was improved.

(Re-molding test)
In this test, the obtained fiber reinforced resin molded product molded into a flat plate shape was used as a sample.

First, the sample is placed on a substantially L-shape of 102 °, preheated again at 200 ° C. for 10 minutes, and then heated at 200 ° C. and 4 MPa for 30 minutes in a vacuum state (vacuum degree: −0.1 MPa). And pressurization.

After cooling, the heated and pressurized sample had a slightly bent shape, but could not be reshaped into a clean L-shape.

Therefore, it was confirmed that the fiber-reinforced resin material can be molded by heating at 200 ° C., but cannot be remolded at 200 ° C. and 4 MPa after being heated at 200 ° C.

From the above results, the fiber reinforced resin molded body of Example 5 is a fiber reinforced resin molded body obtained using a fiber reinforced resin material, and is obtained by heat treatment at a specific temperature or higher. , And could not be reshaped by reheating (or heating and pressing). In this embodiment, the specific temperature is in the range of more than 120 ° C. and 200 ° C. or less.

Further, the fiber-reinforced resin molded body of Example 5 is used in an environment of about 240 ° C., for example, as an L-shaped plate for reinforcing a steel floor slab that can withstand heat during paving of asphalt. it can.

(Example 6)
In Example 6, except that the following were used as the thermoplastic resin solution, the same procedure as in Example 5 was applied to a woven fabric obtained by using long carbon fibers having a length of 50 m, a width of 48 cm, and a thickness of 0.39 mm. A sheet-like fiber reinforced resin material provided with a reactive thermoplastic resin was obtained. In addition, the thermoplastic resin before heating above the specific temperature heated at 110 degreeC after drying at 60 degreeC has a glass transition temperature of 100 degreeC, and Vf value of the obtained sheet-like fiber reinforced resin material is 45. %Met.

[Thermoplastic resin solution (viscosity: 80 mPa · s]
-Thermoplastic epoxy resin (reactive resin: DENATEITE XNR6850V: manufactured by Nagase ChemteX Corporation. Solid content: 85% by mass) 100 parts-Curing agent (DENATEITE XNH6850V: manufactured by Nagase ChemteX Corp .: solid content: 30% by mass) 5 parts ・ Crosslinking agent (hydrogenated MDI type compound blocked with caprolactam. Solid content 55% by mass) 20 parts ・ Methyl ethyl ketone 10 parts

(Deformation test by heat)
The obtained sheet-like fiber reinforced resin material was cut into a length of 15 cm and a width of 3 cm and used as Sample 1. The thickness of Sample 1 was 0.39 mm. Further, Sample 2 obtained by subjecting Sample 1 to heat treatment at 200 ° C. for 10 minutes in a hot air oven was used as Sample 2. Using Samples 1 and 2, the same test as in Example 5 (thermal deformation test) was performed. In addition, the glass transition temperature of the thermoplastic resin which performed the heat processing for 10 minutes at 200 degreeC was 120 degreeC, and the glass transition temperature was rising compared with before heat processing.

First, each sample was placed on a tray-shaped mold having a depth of 5 mm, preheated at 120 ° C. for 10 minutes, and then heated in a vacuum state (vacuum degree: −0.1 MPa) at 150 ° C. and 4 MPa for 30 minutes. And pressurization.

Therefore, it was confirmed that the obtained fiber reinforced resin material can be molded by heating at 150 ° C., and after heating at 200 ° C., it cannot be remolded at least at 150 ° C. and 4 MPa.

(Easy storage)
Using the sample 1 prepared as a sample in the above (deformation test by heat), a test related to (storability) similar to that in Example 5 was performed.

From the above test, the fiber reinforced resin material of Example 6 is a fiber reinforced resin material containing a thermoplastic resin and a reinforced fiber, and can be molded by heating (or heating and pressing), and It was confirmed that re-molding cannot be performed by heating (or heating and pressing) after heating at a specific temperature or higher during molding or after molding. From the above test, in this example, the specific temperature is in the range of more than 120 ° C. and 200 ° C. or less.

(Fiber reinforced resin molding)
Next, five sheet-like fiber reinforced resin materials are stacked while being shifted in the fiber axis direction, placed on a substantially L-shape, preheated at 120 ° C. for 10 minutes, and in a vacuum state (vacuum degree: − 0.1 MPa) at 230 ° C. and 6 MPa for 30 minutes while heating to obtain an approximately L-shaped (L portion angle of 102 °) fiber-reinforced resin molded body. The thickness of the flat part (the part which is not the top of the L part) of the obtained fiber reinforced resin molded product was 1.25 mm. The Vf value of the fiber reinforced resin molded product was 47%.

(Deformation test by heat)
The obtained substantially L-shaped fiber-reinforced resin molded product was cut into a length of 15 cm and a width of 3 cm and used as a sample. The sample thickness was 1.25 mm.

The cut sample was subjected to the same test as in Example 5 (thermal deformation test). As a result of this test, no stickiness (sagging) was observed in any of the samples heated at 170 ° C. and 240 ° C.

Therefore, it was possible to mold by heating at 230 ° C., and after heating at 230 ° C., it was confirmed that the stability of the shape against heat was improved.

(Re-molding test)
In this test, the obtained fiber reinforced resin molded product formed into a substantially L-shape was used as a sample.

First, the sample was placed on a flat mold with the L-shaped apex facing upward, preheated again at 200 ° C. for 10 minutes, and then in a vacuum state (vacuum degree: −0.1 MPa) at 200 ° C. and 4 MPa. Heating and pressurization for 30 minutes were performed.

Therefore, although the fiber reinforced resin material can be molded by heating at 230 ° C., it was confirmed that after heating at 230 ° C., it cannot be remolded at 200 ° C. and 4 MPa.

From the above results, the fiber reinforced resin molded product of Example 6 is a fiber reinforced resin molded product obtained using a fiber reinforced resin material, and is obtained by heat treatment at a specific temperature or higher. , And could not be reshaped by reheating (or heating and pressing). In this embodiment, the specific temperature is in the range of more than 120 ° C. and 230 ° C. or less.

Further, the fiber reinforced resin molded body of Example 6 is used in an environment of about 240 ° C., for example, as an L-shaped plate for reinforcing a steel floor slab that can withstand heat during paving of asphalt. it can.

(Example 7)
In Example 7, a woven fabric obtained by using carbon fibers of long fibers having a length of 50 m, a width of 48 cm and a thickness of 0.39 mm in the same manner as in Example 5 except that the following were used as the thermoplastic resin solution. A sheet-like fiber reinforced resin material provided with a reactive thermoplastic resin was obtained. In addition, the thermoplastic resin before heating above the specific temperature heated at 110 degreeC after drying at 60 degreeC has a glass transition temperature of 100 degreeC, and Vf value of the obtained sheet-like fiber reinforced resin material is 45. %Met.

[Thermoplastic resin solution (viscosity: 80 mPa · s]
-Thermoplastic epoxy resin (reactive resin: DENATEITE XNR6850V: manufactured by Nagase ChemteX Corporation. Solid content: 85% by mass) 100 parts-Curing agent (DENATEITE XNH6850V: manufactured by Nagase ChemteX Corp .: solid content: 30% by mass) 5 parts ・ Crosslinking agent (novolak-type resin, solid content 55% by mass) 20 parts ・ Methyl ethyl ketone 10 parts

(Deformation test by heat)
The obtained sheet-like fiber reinforced resin material was cut into a length of 15 cm and a width of 3 cm and used as Sample 1. The thickness of Sample 1 was 0.39 mm. Further, Sample 2 obtained by subjecting Sample 1 to heat treatment at 200 ° C. for 10 minutes in a hot air oven was used as Sample 2. Using Samples 1 and 2, the same test as in Example 5 (thermal deformation test) was performed. In addition, the glass transition temperature of the thermoplastic resin which performed the heat processing for 10 minutes at 200 degreeC was 100 degreeC, and the glass transition temperature was not rising compared with before heat processing.

From the above test, the fiber reinforced resin material of Example 7 is a fiber reinforced resin material containing a thermoplastic resin and a reinforced fiber, and can be molded by heating (or heating and pressing), and It was confirmed that re-molding cannot be performed by heating (or heating and pressing) after heating at a specific temperature or higher during molding or after molding. From the above test, in this example, the specific temperature is in the range of more than 120 ° C. and 200 ° C. or less.

(Fiber reinforced resin molding)
Next, five sheet-like fiber reinforced resin materials are stacked while being shifted in the fiber axis direction, placed on a flat plate mold, preheated at 120 ° C. for 10 minutes, and in a vacuum state (vacuum degree: −0 .1 MPa) at 270 ° C. and 8 MPa for 30 minutes while heating to obtain a flat fiber-reinforced resin molded body. The thickness of the obtained fiber reinforced resin molded product was 1.25 mm. The Vf value of the fiber reinforced resin molded product was 47%.

Therefore, it was possible to mold by heating at 270 ° C., and after heating at 270 ° C., it was confirmed that the shape stability against heat was improved.

First, the sample is placed on a substantially L-shape of 102 °, preheated again at 150 ° C. for 10 minutes, and then heated in a vacuum state (vacuum degree: −0.1 MPa) at 150 ° C. and 2 MPa for 30 minutes. And pressurization.

Therefore, it was confirmed that the fiber reinforced resin material can be molded by heating at 270 ° C., but cannot be remolded at 150 ° C. and 2 MPa after being heated at 270 ° C.

From the above results, the fiber reinforced resin molded product of Example 7 is a fiber reinforced resin molded product obtained using a fiber reinforced resin material, and is obtained by heat treatment at a specific temperature or higher. , And could not be reshaped by reheating (or heating and pressing). In this embodiment, the specific temperature is in the range of more than 120 ° C. and 270 ° C. or less.

The fiber-reinforced resin molded body of Example 7 is used in an environment of about 240 ° C., for example, as an L-shaped plate for reinforcing a steel floor slab that can withstand heat during paving of asphalt. it can.

From the above results, the fiber reinforced resin materials of Examples 5, 6, and 7 can be molded by heating, and an arbitrary molded body can be easily obtained.

In addition, the fiber reinforced resin molded articles of Example 5, Example 6 and Example 7 are excellent in storability, and can be stored without performing special refrigeration and the convenience of industrial use. improves.

Further, if the fiber reinforced resin materials of Examples 5, 6, and 7 are used, it is possible to provide a fiber reinforced resin molded body that can be easily molded by heat and can be used even in a high temperature environment.

Moreover, the fiber reinforced resin moldings of Example 5, Example 6, and Example 7 are heated at a specific temperature or higher as compared with the fiber reinforced resin material having thermoplasticity used to obtain the fiber reinforced resin molding. This increases the thermal stability of the shape against heat and can be used in a higher temperature environment.

Claims

A fiber reinforced resin material containing a thermoplastic resin and a reinforced fiber, which can be molded by heating, and cannot be remolded by heating after being heated at a specific temperature or higher at the time of molding or after molding. Resin material.
The fiber-reinforced resin material according to claim 1, wherein the thermoplastic resin is an epoxy resin.
The fiber-reinforced resin material according to claim 1 or 2, wherein the fiber-reinforced resin material includes a crosslinking agent having two or more functional groups.
The fiber-reinforced resin material according to claim 3, wherein the crosslinking agent includes at least one of a block-type isocyanate compound and a novolac-type resin.
The fiber-reinforced resin material according to any one of claims 1 to 4, wherein the specific temperature is 130 ° C or higher.
The fiber reinforced resin material according to any one of claims 1 to 5, wherein the fiber reinforced resin material cannot be remolded by heating and pressurizing at a temperature of 150 ° C and a pressure of 2MPa after being heated above the specific temperature. Resin material.
A fiber reinforced resin molded article obtained by using the fiber reinforced resin material according to any one of claims 1 to 6.
A fiber reinforced resin molded article molded by heating the fiber reinforced resin material according to any one of claims 1 to 6, wherein the molded article is heated at the specified temperature or higher during or after the molding. In addition, a fiber-reinforced resin molded body that cannot be re-molded by heating after being heated above the specific temperature.
The fiber-reinforced resin molded body according to claim 8, wherein the fiber-reinforced resin molded body cannot be remolded by heating and pressurizing at a temperature of 150 ° C and a pressure of 2 MPa after being heated at the specific temperature or higher.
A fiber reinforced resin molded body is formed by applying a solution containing a thermoplastic resin to the reinforced fibers and heating at a predetermined molding temperature, and the fibers at a specific temperature or higher during or after the molding of the fiber reinforced resin molded body. A method for producing a fiber-reinforced resin molded body, which cannot be remolded by heating by heating the reinforced resin molded body.
The method for producing a fiber-reinforced resin molded body according to claim 10, wherein the thermoplastic resin is an epoxy resin.
The method for producing a fiber-reinforced resin molded article according to claim 10 or 11, wherein the solution contains a crosslinking agent having two or more functional groups.
The method for producing a fiber-reinforced resin molded article according to claim 12, wherein the cross-linking agent includes at least one of a block-type isocyanate compound and a novolac-type resin.
The method for producing a fiber-reinforced resin molded article according to any one of claims 10 to 13, wherein the specific temperature is a temperature of 130 ° C or higher.