JP2005264366A - Reinforcing fiber fabric roll and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lightweight reinforcing fiber fabric roll exhibiting excellent mechanical characteristics as a reinforcing material and having even excellent handleability. <P>SOLUTION: The reinforcing fiber fabric roll is a roll obtained by laminating a reinforcing fiber fabric to which a resin material sticks to at least one surface of a fabric to a plastic film and winding the resultant laminate. The resin material sticking to the reinforcing fiber fabric is within the range of 2-20 wt.%. The peel angle θ of the plastic film from the reinforcing fiber fabric when unwinding the reinforcing fiber fabric from the roll is within the range of 0-30°. The plastic film has 5-100 μm thickness, ≤1.1 specific gravity and ≤D80 durometer hardness (JIS K7215). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a roll of a reinforcing fiber fabric that exhibits excellent mechanical properties as a reinforcing material and is excellent in handleability, and a method for producing the same.

  More specifically, a reinforcing fiber fabric that exhibits excellent mechanical properties when made into a fiber reinforced resin (FRP) and has excellent handleability even in a dry state prevents loss of effect during storage and transportation, and its effect TECHNICAL FIELD The present invention relates to a reinforcing fiber fabric roll and a method for producing the same.

  Conventionally, as a manufacturing method of fiber reinforced resin (hereinafter referred to as FRP) that requires high quality such as aircraft members, a prepreg obtained by impregnating a matrix resin into a reinforcing fiber substrate in advance is set in a mold. An autoclave molding method is often used in which a bag film is covered and heated and pressurized in an autoclave to cure the resin. This molding method is generally used for aircraft members and the like because it has little void generation in FRP and is of high quality.

  On the other hand, in recent years, cost reduction of aircraft materials has been actively studied. Under such circumstances, a liquid resin is used in a state in which a reinforcing fiber fabric in a dry state (not impregnated with resin) is used in a mold without using an expensive autoclave and the inside of the mold is decompressed (vacuum state) Vacuum injection molding methods (eg Resin Transfer Molding (RTM), Vaccum Assisted RTM (VaRTM), Resin film Infusion (RFI), etc.) are being applied to components such as aircraft and automobiles. .

  However, FRP by vacuum injection molding using dry reinforcing fiber fabrics such as sheets made of reinforcing fibers such as glass fibers and carbon fibers, woven fabrics, and knitted fabrics has a problem of inferior mechanical properties compared to FRP by autoclave molding. there were.

  This is partly due to the fact that the reinforcing fiber fabric is dry, but the main reason is that the matrix resin to be used is greatly restricted in resin viscosity, and only the resin having poor mechanical properties can be used.

  That is, in order to improve the mechanical properties, it is necessary to incorporate in the reinforcing fiber fabric a device that supplements the matrix resin, which must be said to be inferior in the mechanical properties of the resin itself.

  In order to deal with such a problem, a method has been proposed in which sealing is performed by fixing a resin in order to maintain the orientation of the reinforcing fibers, and the reinforcing fiber fabric is formed into a scroll shape through a release sheet (Patent Document 1, etc.). ).

  The purpose of the proposal of Patent Document 1 is to improve mechanical properties by suppressing the disturbance and misalignment of reinforcing fibers. However, the improvement effect of the mechanical properties by the proposal is only for suppressing the disturbance of the reinforcing fiber, and no drastic contrivance has been made to supplement the mechanical properties of the matrix resin itself, so that a sufficient effect can be obtained. Not done.

  In addition, there is a disclosure that the release sheet according to the above proposal is used for preventing adhesion of a resin in a hot press for fixing the resin as the sealing treatment. However, a problem that occurs when a resin material having a function of imparting high mechanical properties is attached to the reinforcing fiber cloth and a drastic device is incorporated into the reinforcing fiber cloth, for example, the resin material becomes a scroll shape. If the reinforcing fibers between the inside and outside of the reinforcing fiber cloth induce pseudo adhesion and try to peel them off forcibly, there will be problems such as injuries and fiber disturbances, and the form of the resin material (unevenness) will be in the reinforcing fiber cloth. There is no contrivance regarding problems of transferring and inducing bending of the reinforcing fiber fabric, various problems caused by shrinkage of the release sheet, and the like.

That is, in the conventional techniques including Patent Document 1, there are examples in which a release paper or the like is inserted. However, problems relating to the characteristics of the release paper itself, for example, expansion and contraction due to moisture absorption of the release paper, wrinkles the reinforcing fiber fabric. Problems such as the weight of the release paper being heavy (specific gravity) causing the scroll itself to become heavier, the problem of roll collapse due to slippage of the release paper and the reinforcing fiber fabric, and the problem of increasing the winding diameter due to the thick release paper However, it has not been solved, and realization of such a technique is desired.
JP 2002-249984 A

  The object of the present invention is to solve the above-mentioned problems of the prior art, exhibit excellent mechanical properties when molded into FRP, have excellent shape stability and handleability, light weight and minimize the winding diameter Another object of the present invention is to provide a roll of reinforcing fiber fabric and a method for producing the same.

  In order to achieve the above object, the present invention takes the following means.

  That is, at least a reinforcing fiber cloth having a resin material attached to one surface of the cloth, and a roll obtained by laminating and winding a plastic film, and the resin material attached to the reinforcing fiber cloth is 2 to 2. The peel angle θ between the plastic film and the reinforcing fiber fabric when the reinforcing fiber fabric is rewound from the roll is in the range of 0 to 30 °, and the plastic film has a thickness of 5 to 20% by weight. A reinforcing fiber fabric roll having a thickness of 100 μm, a specific gravity of 1.1 or less, and a durometer hardness (JIS K7215) of D80 or less.

In addition, the method for producing a reinforcing fiber fabric roll according to the present invention is a method for producing a roll which is wound at least while reinforcing fiber fabrics having a resin material attached to one surface of the fabric and plastic films are alternately laminated. And
(A) a resin adhesion step of adhering the resin material to the reinforcing fiber fabric in the range of 2 to 20% by weight;
(B) A winding process in which the reinforcing fiber cloth to which the resin material is bonded is wound with the plastic film while being laminated so that the peeling angle θ between the reinforcing fiber cloth and the plastic film is in the range of 0 to 30 °.
And the thickness of the plastic film is 5 to 100 μm, and the plastic film satisfies both of the following requirements 1 and 2.

[Requirement 1]: Specific gravity is 1.1 or less.
[Requirement 2]: Durometer hardness (JIS K7215) is D80 or less.

  According to the present invention, it is possible to obtain a reinforcing fiber fabric roll that exhibits excellent mechanical properties when molded into FRP, is excellent in shape stability and handleability, and is lightweight and has a minimum winding diameter. be able to.

  Hereinafter, an example of the best embodiment of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic view showing an embodiment of a reinforcing fiber fabric roll according to the present invention. As shown in FIG. 1, the reinforcing fiber fabric roll 3 is a roll wound up while alternately laminating the reinforcing fiber cloth 1 and the plastic film 2.

  FIG. 2 is a schematic perspective view showing one embodiment of the reinforcing fiber fabric of the present invention. As shown in FIG. 2, the reinforcing fiber fabric 1 includes an auxiliary fiber yarn in a direction perpendicular to the reinforcing fiber yarn 5 and the auxiliary fiber yarn (warp direction auxiliary yarn) 7 aligned in one direction. A unidirectional fabric (non-crimp fabric) in which strips (weft-direction auxiliary yarns) 6 are arranged at equal pitches and intersects with the warp-direction auxiliary yarns 7.

  The resin material 4 adheres to one surface of such a cloth in a dot shape, and keeps the cloth. The presence of the resin material 4 makes it possible to supplement the characteristics of the matrix resin itself when FRP is used and to exhibit high mechanical characteristics.

  In the reinforcing fiber cloth of the present invention, a resin material is adhered to the reinforcing fiber cloth in an amount of 2 to 20% by weight in order to make up for insufficient mechanical properties of the matrix resin itself particularly in vacuum injection molding. That is, such a resin material compensates for the lack of matrix properties. The reinforcing fiber fabric to which such a resin material is attached is different from a normal woven fabric, and if it is simply wound as it is, the reinforcing wire fabric 1 tends to cause pseudo-adhesion, and in that case, when the reinforcing fiber fabric 1 is pulled out. Then, the reinforcing fiber yarn 5 is disturbed and fluff is generated.

  One of the features of the present invention is that it is a roll wound up while laminating the reinforcing fiber fabric 1 and the plastic film 2 in order to solve this problem. With the plastic film 2, the resin material 4 in the lower layer of the scroll and the reinforcing fiber yarn 5 in the upper layer stick to each other to prevent the reinforcing fiber yarn 5 from being distorted or injured when pulled out. It can be done.

  From such a viewpoint, the peel angle θ between the plastic film 2 and the reinforcing fiber fabric 1 needs to be in the range of 0 to 30 °. When the peeling angle exceeds 30 °, the resin material 4 is taken on the plastic film 2 when the peeling angle is peeled off. As a result, the fluff and the fiber are disturbed, so that the intended effect of the present invention cannot be achieved.

  The peel angle between the plastic film and the reinforcing fiber fabric is determined from the following measurement method.

  FIG. 4 is a conceptual diagram showing a flow of a method for measuring the peel angle θ between the plastic film 2 and the reinforcing fiber fabric 1. The reinforcing fiber fabric 1 of the outermost layer is pulled out from the reinforcing fiber fabric roll 3 by 30 cm, and the end portion of the reinforcing fiber fabric 1 is cut to adjust the length. The reinforcing fiber fabric roll 3 is placed on a stand, and the position where the scroll is peeled when the end portion of the reinforcing fiber fabric 1 is cut is arranged in the direction of 3 o'clock as shown in FIG. Rotate the scroll 3 at a speed of 30 seconds / circumference, and stop the rotation at the 9 o'clock position (FIG. 4B). The contact point between the unfolded reinforcing fiber cloth 1 and the reinforcing fiber cloth roll 3 is defined as d, and the tangential direction of the reinforcing fiber cloth 1 at the contact point d is defined as a tangent line f. With respect to the angle between the tangent line f and the vertical direction e of the floor surface, the maximum angle from the start of rotation to the stop is defined as the peeling angle θ.

  A method for obtaining the peel angle θ will be described with reference to FIGS. From the contact point d between the reinforcing fiber fabric roll 3 and the reinforcing fiber fabric 1, the vertical direction e of the floor surface is set to 0 °, and the angle with the tangent line f of the reinforcing fiber fabric at the contact point d is obtained. Such an angle is defined as a peeling angle θ.

  More specifically, the peeling angle θ in FIG. 4B is 0 °. That is, such a fabric is within the range of the peeling angle of the present invention. As described above, when the peel angle θ is in the range of 0 to 30 °, it is possible to suppress the disturbance of the reinforcing fiber yarn and the generation of the fluff when the reinforcing fiber fabric roll 3 is pulled out. It is possible to obtain a reinforcing fiber fabric roll which is expressed and has excellent handleability.

  Further, the peel angle θ in FIG. 4C is 70 °. That is, such a fabric is outside the range of the peel angle of the present invention. When the peel angle θ exceeds 30 ° as described above, when the reinforcing fiber fabric roll 3 is pulled out, the reinforcing fiber yarns are disturbed or crushed, and excellent mechanical properties cannot be expressed. Moreover, it is inferior to handleability.

  In addition to the above, one of the features of the present invention is that the reinforcing fiber roll can be reduced in diameter and weight as much as possible. From such a viewpoint, it is important that the plastic film has a thickness of 5 to 100 μm. More preferably, it is 10-50 micrometers, More preferably, it is the range of 15-35 micrometers. When it is less than 5 μm, it is easily broken when wound up, and the handleability is poor. On the other hand, when the thickness exceeds 100 μm, not only the winding diameter of the reinforcing fiber fabric roll becomes large (bulky) but also the weight becomes heavy, which is not preferable. If the winding diameter is large or the weight is heavy, not only the handling property when pulling out the scroll is deteriorated, but also the transportation cost becomes high when transporting. In addition, when using the reinforcing fiber fabric, the plastic film is often discarded. However, if the thickness of the plastic film is too thick, it is not preferable because the discarded amount itself is increased, which is not preferable. The range is important. .

In addition to the above, one of the features of the present invention is that the reinforcing fiber fabric roll can be made as light as possible. Furthermore, since the resin material adheres to one surface of the above-mentioned reinforcing fiber cloth, there is a point that the form (unevenness) can be transferred to prevent bending of the reinforcing fiber. From this viewpoint, the material used for the plastic film needs to satisfy both of the following requirements 1 and 2.
[Requirement 1]: Specific gravity is 1.1 or less.
[Requirement 2]: Durometer hardness (JIS K7215) is D80 or less.

  The requirement 1 contributes to weight reduction of the reinforcing fiber fabric roll. If a film with a specific gravity exceeding 1.1 is used, the plastic film is laminated alternately with the reinforcing fiber fabric, so that not only the scroll becomes heavy, but also the core of the scroll must be able to withstand the load. There is a problem coming.

  The requirement 2 contributes to prevention of transfer of the resin material to the reinforcing fiber fabric. Such a viewpoint cannot be conceived from the conventional reinforcing fiber cloth, and the effect is exhibited only by the reinforcing fiber cloth of the present invention having the resin material attached for the purpose of supplementing the mechanical properties of the matrix resin itself. Is.

  If the durometer hardness exceeds D80, the plastic film becomes too hard and does not become a cushioning material, but causes bending of the reinforcing fibers via the resin material. In addition, although it does not specifically limit to a minimum, in order to form a film, it is common that it is D5 or more.

  The reinforcing fiber fabric roll of the present invention can solve the problems of the present invention by satisfying the above requirements.

From the viewpoint of preventing bending of the reinforcing fiber, it is preferable that the material used for the plastic film further satisfies the following requirement 3.
[Requirement 3]: Rockwell hardness (JIS K7202) is R70 or less.

  The requirement 3 is an index for expressing the same effect as the requirement 2, and if it exceeds R70, the reinforcement fiber may be bent. In addition, although a minimum is not specifically limited, In order to form a film, it is common that it is R10 or more.

  The plastic film used in the present invention preferably has a moisture absorption rate of 1% or less. If the moisture absorption rate exceeds 1%, the plastic film tends to expand and contract, causing not only the problem of wrinkles in the reinforcing fiber cloth and an increase in the weight of the scroll, but also the possibility of attaching moisture to the reinforcing fiber cloth. More preferably, it is 0.5% or less, More preferably, it is 0.1%. In addition, the moisture absorption here is a value measured according to JIS K7209 (23 ° C., 24 hr).

  The plastic film used in the present invention has a shrinkage ratio in the longitudinal direction of 7% or less and / or a shrinkage ratio R3 = (shrinkage ratio in the longitudinal direction) / (shrinkage ratio in the width direction) in the range of 2 to 10. Is preferred. From another viewpoint, the shrinkage in the width direction is preferably 3% or less. More preferably, the shrinkage rate in the longitudinal direction is 5% or less, R3 is in the range of 3 to 8, and the shrinkage rate in the width direction is 1% or less.

  When the contraction rate in the longitudinal direction exceeds 7%, the reinforcing fiber cloth is likely to be bent (bokeh) due to the tightening of the reinforcing fiber cloth. Moreover, when the shrinkage rate in the width direction exceeds 3%, the width of the reinforcing fiber fabric tends to be small, and the basis weight may vary. The reason why a shrinkage rate smaller than the shrinkage rate in the longitudinal direction is preferable is that the reinforcing fiber fabric is more easily dimensionally changed in the width direction. Further, when R3 is less than 2, it is difficult to produce a thin plastic film, and when it exceeds 10, anisotropy is too strong and the fabric may be bent. In addition, this shrinkage rate refers to the shrinkage ratio when a 300 mm square plastic film is heated at 100 ° C. for 1 hour. The longitudinal direction of the film refers to the winding direction of the plastic when forming the roll, and the shrinkage in the longitudinal direction is the shrinkage in the longitudinal direction measured after leaving the film in an oven heated to 100 ° C. for 2 hours. is there. Further, the film width direction refers to a direction perpendicular to the film longitudinal direction, and the width direction shrinkage ratio is a shrinkage ratio in the width direction measured after leaving the film in an oven heated to 100 ° C. for 2 hours.

  Both the shrinkage ratio in the longitudinal direction is 7% or less and the shrinkage ratio R3 = (shrinkage ratio in the longitudinal direction) / (shrinkage ratio in the width direction) is in the range of 2 to 10 both. The above-mentioned problems can be solved even if only one of them is satisfied.

  The plastic film used in the present invention preferably has a longitudinal elongation of 180% or more. More preferably, it is 200% or more. When the elongation is less than 180%, the plastic film is excessively stretched in the longitudinal direction when forming the scroll, and not only is the situation in which the inner layer side of the scroll is excessively tightened, the plastic film may be torn, It can be a manufacturing problem. The upper limit of the elongation is not particularly limited, but is generally 1000% or less when handled as a film.

  The plastic film used in the present invention preferably has an elongation ratio R1 = (elongation ratio A in the longitudinal direction) / (elongation ratio B in the width direction) in the range of 0.1 to 0.7. More preferably, it is the range of 0.3-0.5. When R1 is less than 0.1, it means that the anisotropy of the plastic film is too large, and a handling problem is likely to occur. On the other hand, if R1 exceeds 0.7, the widthwise elongation becomes small, so that the plastic film is likely to be wrinkled when a scroll is formed.

  The elongation in the longitudinal direction is 180% or more, and the elongation ratio R1 = (elongation in the longitudinal direction A) / (elongation in the width direction B) is in the range of 0.1 to 0.7. It is most preferable that both are satisfied, but even if only one of them is satisfied, the above problem can be solved.

  The plastic film used in the present invention preferably has a tensile strength in the longitudinal direction of 1.5 MPa or more. More preferably, it is 2 MPa or more. When the tensile strength is less than 1.5 MPa, the plastic film is easily broken when forming a scroll, which may cause a problem in production. There is no particular upper limit on the tensile strength, but it is generally 15 MPa or less.

  The plastic film used in the present invention has a tensile strength ratio R2 = (longitudinal tensile strength C) / (lateral tensile strength D) in the range of 0.8 to 1.6. preferable. More preferably, it is the range of 1-1.4. When R2 is less than 0.8, it means that anisotropy is too large, and a problem in handling is likely to occur. On the other hand, when R2 exceeds 1.6, the strength in the width direction becomes small, which may cause a problem in the production of a scroll.

  In addition, the tensile strength in the longitudinal direction is 1.5 MPa or more, and the tensile strength ratio R2 = (tensile strength C in the longitudinal direction) / (tensile strength D in the width direction) is 0.8 to 1. A range of 6 is most preferable if both are satisfied. Even if only one of them is satisfied, the above problem can be solved.

  Furthermore, the plastic film used in the present invention preferably has a surface roughness in the range of 1 to 30 μm. More preferably, it is 3-15 micrometers, More preferably, it is the range of 5-10 micrometers. By having the surface roughness in such a range, even when laminated in the reinforcing fiber cloth scroll, slippage in the inner layer can be suppressed, and particularly when a long reinforcing fiber cloth is used as a scroll, The effect is expressed.

  From such a viewpoint, it is preferable that the length of the reinforcing fiber cloth of the reinforcing fiber cloth roll of the present invention in the longitudinal direction exceeds 50 m because the effects of the present invention can be exhibited to the maximum. More preferably, it is 100 m or more, More preferably, it is 150 m or more. In addition, it is common that the winding amount of the fabric which does not use the prepreg and the resin material generally used is 50 m or less.

  The form of the reinforcing fiber fabric of the present invention is not particularly limited, and may be any form such as a woven fabric, a knitted fabric, or a non-woven fabric, and the reinforcing fiber yarns may be arranged in one direction, two directions, or multiple directions. . Among them, a unidirectional strong fiber fabric is preferable. In particular, the effect of the present invention can be exhibited to the maximum when the reinforcing fiber capable of expressing high mechanical properties is a unidirectional woven fabric, a unidirectional sheet or a unidirectional nonwoven fabric arranged in only one direction. . Among unidirectional fabrics, a unidirectional non-crimp fabric without crimps as shown in FIG. 2 is preferable because high strength can be expected.

  Here, the unidirectional fabric is a warp yarn or weft yarn in which reinforcing fiber yarns are arranged in a line so as to be parallel to each other, and auxiliary yarns are reinforcing fiber yarns (warp yarns) in the orthogonal direction. , Or weft yarn) to indicate a woven structure. The woven structure may be any woven structure such as plain weave, twill weave, and satin weave. The auxiliary yarn refers to one having a fineness of 1/5 of the reinforcing fiber yarn. Furthermore, the unidirectional woven fabric according to the present invention uses auxiliary yarns in the warp direction and the weft direction, and constitutes a woven structure by crossing the warp auxiliary yarns and the weft auxiliary yarns. Or a unidirectional non-crimp fabric in which the weft yarn is not bent.

  The bi-directional woven fabric refers to a yarn in which reinforcing fiber yarns are used for both the warp and the weft in place of the auxiliary yarn used in the unidirectional woven fabric. In this case as well, auxiliary yarns may be used together, and the woven structure is formed by the intersection of the warp auxiliary yarns and the weft auxiliary yarns so that the reinforcing fiber yarns (warp yarns or weft yarns) are not substantially bent. A bi-directional non-crimp fabric may be used.

  For example, in the case of three directions, the multidirectional woven fabric refers to a woven structure in which reinforcing fiber yarns are arranged in the 90 ° direction in addition to ± 45 °. Moreover, in the case of 4 directions, it points out that the reinforced fiber thread has further arranged in the 0 degree direction on the 3 way woven fabric.

  A unidirectional sheet is not formed by restraint by a woven structure, but is laminated without being mixed together and fixed with a binder, a support (for example, mesh, nonwoven fabric, etc.), a knot yarn, etc. It refers to a fabric formed.

  A unidirectional nonwoven fabric refers to a fabric formed by entanglement of reinforcing fiber yarns without forming the fabric by restraint by a woven structure.

  As the reinforcing fiber used in the present invention, glass fiber, carbon fiber, organic fiber (for example, aramid fiber, polyparaphenylene benzobisoxazole fiber, phenol fiber, polyethylene fiber, polyvinyl alcohol fiber), metal fiber, or ceramic fiber, Among these, carbon fibers are light in weight, are excellent in specific strength and specific modulus, chemical resistance, and heat resistance, and are preferable as reinforcing fibers.

In particular, when carbon fiber is used as the reinforcing fiber and the fabric is in a woven form, the carbon fiber yarn composed of the carbon fiber is 12,000 filaments or more, and the basis weight of the carbon fiber in the reinforcing fiber fabric is 300 g. / M ² or less is preferable. Reinforcing fiber fabrics that satisfy these requirements are less prone to misalignment because the number of crossing points of the carbon fiber yarns is reduced, and once the winding is formed, it is likely to bend. However, if the roll is laminated with a plastic film as in the present invention, the plastic film plays a role as a cushioning material, can suppress bending, and maximize the effects of the present invention. It can be done.

  The auxiliary fiber yarns (warp direction auxiliary yarns) 7 and the like shown in FIG. 2 are preferably high in tensile elongation at break and substantially free of heat shrinkage, the lineup of yarn fineness, water absorption resistance, Carbon fiber or glass fiber excellent in cost balance is preferably used.

  The resin material 4 is preferably attached only to the surface of the fabric. Since a large amount of resin adheres only on the surface, the resin material functions efficiently as an interlayer reinforcing material in the molded product, and can exhibit higher mechanical properties (particularly impact resistance). Further, the effect of the present invention can be exhibited to the maximum extent only in such a form.

  The resin material 4 used in the present invention may be a thermoplastic resin, a thermosetting resin, or a mixture thereof. When high mechanical properties (especially impact resistance) are expressed as FRP obtained using such a reinforcing fiber fabric, it is preferable to use a thermoplastic resin having excellent toughness as a main component.

  Thermoplastic resins include polyamide, polycarbonate, polyacetal, polyphenyline oxide, polyphenyline sulfide, polyarylate, polyester, polyamideimide, polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, polyether Examples include ketones, polyketones, polyether nitriles, phenoxy and the like.

  Examples of the thermosetting resin include an epoxy resin, an unsaturated polyester resin, a vinyl ester resin, and a phenol resin.

  The glass transition temperature Tg of such a resin material is preferably in the range of 20 to 150 ° C. in order to facilitate adhesion to the fabric. More preferably, it is 40-140 degreeC, More preferably, it is the range of 60-130 degreeC. When the Tg is less than 20 ° C., not only the high temperature characteristics when FRP is used are likely to be deteriorated, but also it may be difficult to impart the resin material as a solid material, which causes manufacturing problems. In addition, when the resin material is adhered to the fabric, the resin material must be heated to a temperature higher than the glass transition temperature of the resin material so that the resin is softened or melted. If the Tg exceeds 150 ° C., the resin material is bonded without being heated to a high temperature. In addition, there is a concern about damage to the surface treatment agent (sizing agent, coupling agent, etc.) treated on the reinforcing fiber. From this point of view, it is preferable to apply a resin composition in which Tg is adjusted with a thermoplastic resin as a main component and a thermosetting resin as a subcomponent as the resin material of the present invention.

  The resin material is preferably 2 to 20% by weight. The range of 11 to 15% by weight is more preferable. In order to develop high mechanical properties, it is preferable that the amount of adhesion is as large as possible. However, if the amount exceeds 20% by weight, the resin material covers the entire surface of the reinforcing fiber fabric. And VaRTM) have a problem that it becomes difficult for the matrix resin to be impregnated in the thickness direction of the fabric, making application difficult.

  On the other hand, if the resin material is less than 2% by weight, not only the fabric cannot be sealed but also the high mechanical properties cannot be expressed, and the effects of the present invention cannot be obtained.

  The adhesion form of the resin material is preferably linear or dot-like. More preferably, it is point-like. When the resin material is in the form of dots, the resin material can be distributed over the entire surface of the reinforcing fiber fabric with a small amount of resin material. On the other hand, if the resin material is fibrous, it is difficult to cover the entire surface of the fabric even with a large amount of resin material. Such a form is preferably properly used depending on the purpose of use.

  Here, in order to make the resin material dot-like, the resin is preferably made into particles having a diameter of 400 μm or less. Such a particulate resin material can be applied onto a reinforcing fiber fabric, and the particulate resin can be softened or melted by heating to be adhered to the fabric. In this way, since the resin material is unlikely to cover the entire surface of the cloth when adhered in a dot shape, the matrix resin is greatly impregnated in the fabric thickness direction particularly when FRP is formed by vacuum injection molding. Less likely to be disturbed.

  Such a resin material is preferably attached to at least one surface of the reinforcing fiber fabric with a thickness in the range of 2 to 100 μm, and further, a layer having a gap between the resin material and the resin material is formed. Is preferred. More preferably, it is the range of 5-90 micrometers. When the thickness 2 of the resin material is less than 2 μm, it becomes difficult to exhibit high mechanical properties (particularly impact resistance) as FRP obtained using such a reinforcing fiber fabric.

  On the other hand, when the thickness of the resin material exceeds 100 μm, when forming the reinforcing fiber fabric roll, the form (unevenness) of the resin material is transferred to the reinforcing fiber fabric to induce bending of the reinforcing fiber, resulting in a decrease in mechanical properties. In addition, the effect of the plastic film as a cushioning material becomes thin, making it difficult to apply. In addition, by forming a layer having a gap, the matrix resin can easily flow in the fabric thickness direction, particularly when FRP is formed by vacuum injection molding, so that excellent impregnation can be achieved.

  The reinforcing fiber cloth from the reinforcing fiber cloth roll of the present invention is preferably formed into FRP by vacuum injection molding as described above, specifically, by a molding method such as RTM, VaRTM, RFI and the like. That is, the reinforcing fiber cloth from the reinforcing fiber cloth roll of the present invention exhibits the maximum effect when it is subjected to vacuum injection molding.

  Next, the manufacturing method of the reinforcing fiber fabric roll 3 of FIG. 2 will be described. The method for producing a reinforcing fiber fabric roll according to the present invention is a method for producing a roll which is wound while alternately laminating a reinforcing fiber fabric having a resin material attached to one surface of the fabric and a plastic film. It is manufactured through the following steps (A) to (B).

The plastic film used here is a plastic film that satisfies the above-described requirements. The requirement that the plastic film must satisfy is that the thickness of the plastic film is 5 to 100 μm, and the material used for the plastic film satisfies both of the following requirements 1 and 2.
[Requirement 1]: Specific gravity is 1.1 or less.
[Requirement 2]: Durometer hardness (JIS K7215) is D80 or less.

Hereinafter, the manufacturing method of a reinforcing fiber fabric scroll will be described in more detail. FIG. 3 is a schematic view showing one embodiment of a method for producing a reinforcing fiber fabric roll of the present invention.
(A) Resin adhesion process 8
The resin material 4 is adhered to the reinforcing fiber fabric 8 prepared in advance in the range of 2 to 20% by weight. More specifically, the reinforcing fiber fabric is preheated with the hot roller 10 in advance, and the resin material 4 is in the range of 2 to 20% by weight on one surface of the fabric 8 using the resin material spraying devices 9a, 9b and 9c. Sprinkle to

  The resin material 4 spread on one surface is heated by the far infrared heater 11 and fused to the fabric 8. Although heating temperature is dependent also on the resin material to be used, generally the range of 80-300 degreeC is preferable. More preferably, it is the range of 100 degreeC-200 degreeC.

If necessary, the resin material 4 fused to the surface of the fabric piece may be cooled before winding.
(B) Winding step 12
The reinforcing fiber cloth to which the resin material 4 is adhered is wound up while being laminated so that the peel angle θ with the plastic film 2 is in the range of 0 to 30 °, whereby the reinforcing fiber cloth roll 3 is obtained.

  Here, in order to wind up while laminating so that the peel angle θ is in the range of 0 to 30 °, the winding tension of the reinforcing fiber fabric is wound in the range of 30 to 1000 N / m, and the plastic film is wound. It can be implemented by winding the take-up tension in the range of 1 to 500 N / m. More preferably, the winding tension of the reinforcing fiber fabric is wound in the range of 50 to 400 N / m, and the winding tension of the plastic film is set in the range of 5 to 100 N / m.

  When the winding tension of the reinforcing fiber fabric is less than 30 N / m, there arises a problem that the obtained scroll is easily collapsed. On the other hand, if the winding tension of the reinforcing fiber fabric exceeds 1000 N / m, a problem that wrinkles are likely to occur in the reinforcing fiber fabric. Further, when the winding tension of the plastic film is less than 1 N / m, there arises a problem that the plastic film cannot be pulled out stably. On the other hand, when the winding tension of the plastic film exceeds 500 N / m, there is a problem that the film extends too much and the reinforcing fiber fabric is wound more than necessary or the film is torn.

  Here, from the viewpoint of suppressing the collapse of the obtained scroll, the plastic film is preferably laminated and wound while being stretched in the range of 1 to 5%. A slight tightening force applied after the plastic film is wound up has an effect of stabilizing the winding shape.

  The reinforcing fiber cloth in the reinforcing fiber cloth roll 3 thus obtained is used as a reinforcing material for FRP.

In the present invention, each physical property value used in the description is obtained as follows.
(1) Peel angle:
The reinforcing fiber fabric 1 of the outermost layer is pulled out from the reinforcing fiber fabric roll 3 by 30 cm, and the end portion of the reinforcing fiber fabric 1 is cut to adjust the length. The reinforcing fiber fabric roll 3 is placed on a stand, and the position where the scroll is peeled when the end portion of the reinforcing fiber fabric 1 is cut is arranged in the direction of 3 o'clock as shown in FIG. Rotate the scroll 3 at a speed of 30 seconds / circumference, and stop the rotation at the 9 o'clock position (FIG. 4B). The contact point between the unfolded reinforcing fiber cloth 1 and the reinforcing fiber cloth roll 3 is defined as d, and the tangential direction of the reinforcing fiber cloth 1 at the contact point d is defined as a tangent line f. With respect to the angle between the tangent line f and the vertical direction e of the floor surface, the maximum angle from the start of rotation to the stop is defined as the peeling angle θ.

A method for obtaining the peel angle θ will be described with reference to FIGS. From the contact point d between the reinforcing fiber fabric roll 3 and the reinforcing fiber fabric 1, the vertical direction e of the floor surface is set to 0 °, and the angle with the tangent line f of the reinforcing fiber fabric at the contact point d is obtained. Such an angle is defined as a peeling angle θ.
(2) Durometer hardness of plastic film:
The value measured in accordance with JIS K7215.
(3) Rockwell hardness of plastic film:
The value measured in accordance with JIS K7202.
(4) Shrinkage ratio in the longitudinal direction of the plastic film:
The shrinkage rate in the longitudinal direction of the film after the plastic film is left in an oven heated to 100 ° C. for 2 hours.
(5) Shrinkage ratio in the width direction of the plastic film:
The shrinkage rate in the width direction of the film after the plastic film is left in an oven heated to 100 ° C. for 2 hours.
(6) Longitudinal elongation of the plastic film:
The value measured according to JIS Z1702.
(7) Elongation rate in the width direction of the plastic film:
The value measured according to JIS Z1702.
(8) Tensile strength in the longitudinal direction of the plastic film:
The value measured according to JIS Z1702.
(9) Tensile strength in the width direction of the plastic film:
The value measured according to JIS Z1702.
(10) Adhesion thickness of adhering resin material:
The cross section of the reinforcing fiber fabric is observed with an electron microscope, and the thickness of the resin material adhered to the fabric surface is the thickness determined from the observed magnification.
(11) Surface roughness of plastic film:
The value measured according to JIS B0601.

The raw materials used in Examples and Comparative Examples were as follows.
1. Plastic film Polyethylene film: 25 μm thick, vertical tensile strength of 2 MPa or more, transverse tensile strength of 1.7 MPa or more, vertical tensile elongation of 200% or more, transverse tensile elongation of 480% or more, density of 0 .92 g / cm ³ , moisture absorption of less than 0.05%, shrinkage in the longitudinal direction of 4%, shrinkage in the width direction of 0.8%, R3 = 5, surface roughness of 10 μm or less.
2. Release paper Silicone release paper: manufactured by Lintec Co., Ltd. Koutashi WBE90R-DT (thickness 120 μm, moisture absorption 3.6%, longitudinal shrinkage 0.2%, width shrinkage 0.2%, R3 = 1).
3. Reinforcing fiber yarn PAN-based carbon fiber: 24,000 filaments, fineness 1,030 tex, tensile strength 5,900 MPa, tensile elastic modulus 295 GPa, breaking elongation 2.0%).
4). Warp auxiliary yarn Glass fiber: ECE225 1/0 1.0Z made by Nitto Glass Fiber, fineness 22.5 tex, elongation 3% or more, binder type “DP”.
5). Weft auxiliary yarn Polyamide 66 fiber: 7 filaments, fineness 1.7 tex
6). Resin material Polyether sulfone resin (Sumitomo Chemical Co., Ltd. Sumika Excel (registered trademark) 5003P) 60 wt% (main component) and the following epoxy resin composition 40 wt% (subcomponent) in a twin screw extruder What was melt-kneaded and freeze-ground. Average particle system D50 (measured with LMS-24 manufactured by Seishin Corporation) 115 μm, glass transition point 92 ° C.
Epoxy resin composition-21 parts by weight of Epicoat (registered trademark) 806 manufactured by Japan Epoxy Resin Co., Ltd., 12.5 parts by weight of NC-3000 manufactured by Nippon Kayaku Co., Ltd., and TEPIC manufactured by Nissan Chemical Industries, Ltd. -4 parts by weight of P stirred at 100 ° C until uniform.

Example 1
The 184 reinforcing fiber yarns were aligned in parallel with each other and arranged in one direction at a density of 1.8 yarns / cm to form a 1 m wide sheet-like reinforcing fiber yarn group. In addition, warp direction auxiliary yarns are aligned in parallel to each other, arranged in the same direction as the reinforcing fiber yarn group at a density of 1.8 yarns / cm, and alternately arranged in one direction with the reinforcing fiber yarns. Then, a warp auxiliary yarn group was formed. Both were used to form a sheet-like warp direction yarn group.

  Next, the weft direction auxiliary yarns are aligned parallel to each other and arranged in a direction perpendicular to the warp direction yarn group at a density of 3 / cm, and the warp direction auxiliary yarns and weft direction are arranged. The auxiliary yarn and yarn were crossed into a plain weave structure using a loom to form a unidirectional non-crimp fabric.

26 g / m ² (14% by weight) was applied to the surface of the unidirectional non-crimp fabric while uniformly dispersing the resinous resin material using a Tribo II gun manufactured by Nordson Co., Ltd. A far-infrared heater was passed under the condition of min, and the resin material was adhered to the surface of the fabric piece (resin adhesion step).

  Next, the fabric is cooled to fix the resin material, and a plastic film supply device is provided immediately before the fabric is wound by the winding device, and a plastic film using a material having a durometer hardness of D50 and a Rockwell hardness of R10 or less. And a fabric were overlapped, and a length of 100 m was simultaneously wound up (winding step). The winding tension of the reinforcing fiber fabric at the start of winding was 300 N / m, and the winding tension of the plastic film was 30 N / m. Such a reinforcing fiber fabric roll was left in a room at 40 ° C. for one week.

  The obtained reinforcing fiber fabric scroll was not easily touched by the plastic film with the lower layer resin material and the upper reinforcing fiber fabric, so that the reinforcing fiber was not disturbed or crushed and could be pulled out easily. . Moreover, the surface of the reinforcing fiber fabric scroll covered with the plastic film was smooth, and no unevenness due to wrinkles was observed. Further, even when viewed microscopically, the plastic film is a cushion of the surface unevenness of the fabric, and the reinforcing fiber yarns are also straight in the thickness direction of the fabric. The peel angle θ was 0 °.

Comparative Example 1
A reinforcing fiber fabric roll was obtained in the same manner as in Example 1 except that no plastic film was used. Thereafter, in the same manner as in Example 1, the reinforcing fiber fabric roll was left in a room at 40 ° C. for one week.

  It was difficult for the obtained reinforcing fiber fabric scroll to be peeled off when the lower layer resin material of the scroll and the upper reinforcing fiber fabric were in direct contact with each other when they were pulled out. If you try to peel it off forcibly, the upper-layer reinforcing fibers are distorted and a large amount of scalp is generated, making it impossible to obtain product value.

Comparative Example 2
A reinforced fiber fabric roll was obtained in the same manner as in Example 1 except that release paper was used instead of the plastic film. Thereafter, in the same manner as in Example 1, the reinforcing fiber fabric roll was left in a room at 40 ° C. for one week.

  In the obtained reinforcing fiber cloth roll, although the peel angle θ is 0 ° and can be easily pulled out, the release paper is not only uneven due to moisture absorption, but the unevenness is transferred to the reinforcing fiber cloth, The reinforcing fiber fabric was bent. Further, even when viewed microscopically, the release paper was not a cushion for the surface irregularity of the fabric, and the reinforced fiber yarns were unevenly transferred in the thickness direction of the fabric. Furthermore, when the scroll was transported, the winding shape collapsed easily as compared with the scroll of Example 1, and accordingly, meandering of the reinforcing fiber fabric was observed. In addition to this, the winding diameter is larger and heavier than the scroll of Example 1, and there was a problem in carrying.

  The present invention can be suitably used for a structural member of a transportation device such as an aircraft, a ship, and an automobile, a building member, and the like, but is not limited thereto.

It is the schematic which shows one embodiment of the reinforcing fiber fabric roll of this invention. It is a schematic perspective view which shows one aspect | mode as a reinforcing fiber fabric used for this invention. It is the schematic which shows one embodiment of the manufacturing method of the reinforcing fiber fabric scroll of this invention. It is a conceptual diagram which shows the flow of the measuring method of peeling angle (theta) in this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 8: Reinforcing fiber cloth 2: Plastic film 3: Reinforcing fiber cloth scroll 4: Resin material 5: Reinforcing fiber yarn 6, 7: Auxiliary fiber yarn 8: Adhesion process 9a: Engraving roll 9b: Doctor blade 9c: Vibration Net 10: Hot roller 11: Far-infrared heater 12: Winding step 13: Winding device θ: Peeling angle a: Length of the winding thickness b: Half length of the outer circumference of the winding c: Direction of rotation d: contact e: reference line perpendicular to the floor surface f: tangent of the reinforcing fiber fabric

Claims (16)

  A roll obtained by laminating and winding at least a reinforcing fiber cloth having a resin material adhered to one surface of the cloth and a plastic film, and the resin material adhering to the reinforcing fiber cloth is 2 to 20 weights %, And the peel angle θ between the plastic film and the reinforcing fiber fabric when the reinforcing fiber fabric is rewound from the roll is in the range of 0 to 30 °, and the plastic film has a thickness of 5 to 100 μm, A reinforcing fiber fabric roll having a specific gravity of 1.1 or less and a durometer hardness (JIS K7215) of D80 or less.   The reinforcing fiber fabric roll according to claim 1, wherein the material of the plastic film is Rockwell hardness (JIS K7202) R70 or less.   The reinforcing fiber fabric roll according to claim 1 or 2, wherein the plastic film has a moisture absorption rate (JIS K7209) of 1% or less.   The plastic film has a shrinkage ratio of 7% or less in the longitudinal direction and / or a shrinkage ratio R3 (shrinkage ratio in the longitudinal direction / shrinkage ratio in the width direction) = 2 to 10. The reinforcing fiber fabric roll according to any one of 1 to 3.   The plastic film has a longitudinal elongation of 180% or more and / or an elongation ratio R1 (longitudinal elongation A / elongation B in the width direction) = 0.1 to 0.7. The reinforcing fiber roll according to any one of claims 1 to 4.   The plastic film has a tensile strength in the longitudinal direction of 1.5 MPa or more, and / or a tensile strength ratio R2 (tensile strength C in the longitudinal direction / tensile strength D in the width direction) = 0.8 to 1.6. The reinforcing fiber fabric roll according to any one of claims 1 to 5, which is in a range.   The reinforcing fiber fabric roll according to any one of claims 1 to 6, wherein the plastic film has a surface roughness in the range of 1 to 30 µm.   The reinforcing fiber fabric roll according to any one of claims 1 to 7, wherein the reinforcing fiber fabric is wound with a fabric length exceeding 50 m. The reinforcing fiber fabric is a carbon fiber woven fabric, the carbon fiber yarn used is 12,000 filaments or more, and the basis weight of the carbon fiber in the reinforcing fiber fabric is 300 g / m ² or less. The reinforcing fiber fabric roll according to any one of claims 1 to 8.   The reinforcing fiber fabric roll according to any one of claims 1 to 9, wherein the reinforcing fiber fabric is a unidirectional sheet or a unidirectional woven fabric.   The reinforcing fiber fabric roll according to any one of claims 1 to 10, wherein the resin material is attached only to the surface of the fabric.   The reinforcing fiber fabric roll according to any one of claims 1 to 11, wherein the resin material has a glass transition temperature Tg of 20 to 150 ° C.   The resin material is attached to at least one surface of the reinforcing fiber fabric with a thickness in the range of 2 to 100 μm and forms a layer having a gap. The reinforcing fiber fabric roll described.   The reinforcing fiber fabric roll according to any one of claims 1 to 13, wherein the resin material is attached in a linear or dotted form.   The reinforcing fiber fabric roll according to any one of claims 1 to 14, wherein the reinforcing fiber fabric is used for vacuum injection molding. At least a method for producing a roll of a laminate of a reinforcing fiber fabric having a resin material attached to one surface of the fabric and a plastic film,
(A) a resin attachment step of attaching the resin material to the reinforcing fiber fabric in the range of 2 to 20% by weight;
(B) A winding process in which the reinforcing fiber cloth to which the resin material is adhered is wound with the plastic film while being laminated so that the peeling angle θ between the reinforcing fiber cloth and the plastic film is in the range of 0 to 30 °.
And a plastic film having a thickness of 5 to 100 μm, a specific gravity of 1.1 or less, and a durometer hardness (JIS K7215) of D80 or less is used as the plastic film. A method for producing a fiber fabric scroll.

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