WO2024048076A1

WO2024048076A1 - Apparatus for producing fiber-reinforced composite sheet and method for producing fiber-reinforced composite sheet

Info

Publication number: WO2024048076A1
Application number: PCT/JP2023/025162
Authority: WO
Inventors: 一迅人見; 幸司永田
Original assignee: Dic株式会社
Priority date: 2022-08-31
Filing date: 2023-07-06
Publication date: 2024-03-07

Abstract

This apparatus for producing a fiber-reinforced composite sheet comprises: a first feed roll for feeding a first carrier film; a first application unit for applying a first resin composition onto the first carrier film; a reinforcement fiber supply unit for supplying cut pieces of reinforcement fibers onto the first resin composition; a second feed roll for feeding a second carrier film; a second application unit for applying a second resin composition onto the second carrier film; a conveyance unit for conveying the first carrier film and the second carrier film; and a pressure application unit for applying pressure on the first carrier film and the second carrier film that have interposed therebetween a laminate containing the second resin composition and the first resin composition to which the cut pieces have been supplied. The pressure application unit has a crown roll that extends in the axial direction orthogonal to the conveyance direction.

Description

Manufacturing device for fiber-reinforced composite sheet and method for manufacturing fiber-reinforced composite sheet

The present disclosure relates to a manufacturing device for a fiber-reinforced composite sheet and a method for manufacturing a fiber-reinforced composite sheet.

Sheet molding compounds (SMC, also referred to as fiber-reinforced composite sheets), in which reinforcing fiber materials such as glass fibers are impregnated with resin compositions (e.g., resin compounds), are used, for example, in housing components, automobile parts, and electrical parts. It is widely used. During SMC manufacturing, when gas is entrained in the resin composition, the gas can become bubbles within the SMC. If the bubbles remain in the SMC, there is a concern that the mold may be damaged during press molding of the SMC. Therefore, it is necessary to remove air bubbles from inside the SMC (degassing or defoaming).

For example, in Patent Document 1 listed below, an SMC material having a resin compound and reinforcing fiber material that is continuously conveyed is pressurized from both sides of the SMC material from upstream to downstream in the conveying direction. A method of obtaining a sheet molding compound by impregnating a resin compound with a resin compound is disclosed.

Japanese Patent Application Publication No. 2014-205287

Even when the method described in Patent Document 1 is carried out, the SMC may not be sufficiently degassed. For this reason, a method that allows more accurate degassing is desired.

An object of one aspect of the present disclosure is to provide a fiber-reinforced composite sheet manufacturing apparatus and a fiber-reinforced composite sheet manufacturing method that can perform deaeration with high accuracy.

A manufacturing apparatus for a fiber reinforced composite sheet according to one aspect of the present disclosure includes a first delivery roll that sends out a first carrier film, and a first application section that applies a first resin composition onto the first carrier film that is being transported. a reinforcing fiber supply unit that supplies cut pieces of reinforcing fiber onto the first resin composition; a second delivery roll that delivers the second carrier film; and a reinforcing fiber supply unit that supplies cut pieces of reinforcing fiber onto the first resin composition; A second application section for coating, a conveyance section for conveying the first carrier film and the second carrier film, and a first carrier sandwiching the laminate containing the first resin composition and the second resin composition to which the cut pieces have been supplied. It includes a pressure section that presses the film and the second carrier film, and the pressure section has a crown roll extending in an axial direction perpendicular to the conveyance direction of the first carrier film and the second carrier film.

In this fiber-reinforced composite sheet manufacturing apparatus, the pressure unit that presses the first carrier film and the second carrier film sandwiching the laminate has an axis perpendicular to the conveying direction of the first carrier film and the second carrier film. It has a crown roll extending in the direction. As a result, when the laminate is pressurized by the crown roll, the gas present between the first carrier film and the second carrier film is pushed out toward both ends of the laminate in the axial direction to the crown roll. . Thereby, the laminate is degassed with high accuracy via the both ends.

The taper angle of the crown roll is 0.1° or more and 1.3° or less, and the dimension of the crown roll along the axial direction may be 2000 mm or less. The difference between the center diameter of the crown roll and the end diameter of the crown roll in the axial direction may be 0.5 mm or more and 8 mm or less. In these cases, extrusion of gas by the crown roll is performed well.

The pressurizing section may have a smooth receiving roll corresponding to the crown roll. In this case, the gas is well extruded by the crown roll.

The pressure section may include a smooth roll that presses the laminate, and the smooth roll may be located at the most downstream position of the pressure section in the conveyance direction. In this case, a flat fiber-reinforced composite sheet can be produced satisfactorily.

The pressure unit has a first uneven roll and a second uneven roll that are adjacent to each other in the conveying direction and are located on substantially the same plane, and the surface of the first uneven roll is intermittently arranged along the axial direction. A plurality of first convex portions are provided on the surface of the second uneven roll, and a plurality of second convex portions are provided intermittently along the axial direction. The convex portion and the plurality of second convex portions may be provided alternately. In this case, since the pressure applied to the laminate by the first textured roll and the second textured roll is dispersed, the laminate can be sufficiently heated while suppressing the occurrence of the textured pattern caused by the first textured roll and the second textured roll. Can be pressurized to

A method for manufacturing a fiber-reinforced composite sheet according to another aspect of the present disclosure includes a step of applying a first resin composition onto a first carrier film being conveyed, and cutting reinforcing fibers onto the first resin composition. a step of supplying the pieces; a step of applying a second resin composition onto the second carrier film being conveyed; and a step of bringing the first carrier film and the second carrier film close to each other and applying the first resin composition to which the cut pieces have been supplied. A step of forming a laminate containing the composition and a second resin composition, and a step of pressurizing the laminate by a pressure section, the press section conveying the first carrier film and the second carrier film. It has a crown roll extending in an axial direction perpendicular to the direction.

In this manufacturing method, the pressure section has a crown roll extending in the axial direction perpendicular to the conveyance direction of the first carrier film and the second carrier film. As a result, when the laminate is pressurized by the crown roll in the step of pressurizing the laminate in the pressurizing section, the gas present between the first carrier film and the second carrier film is released in the axial direction. The laminate is extruded into a crown roll towards both ends. Thereby, the laminate is degassed with high accuracy via the both ends.

According to the present disclosure, it is possible to provide a fiber-reinforced composite sheet manufacturing apparatus and a fiber-reinforced composite sheet manufacturing method that can perform deaeration with high accuracy.

FIG. 1 is a schematic diagram showing the main configuration of a fiber-reinforced composite sheet manufacturing apparatus according to an embodiment. FIG. 2 is a schematic diagram of the crown roll. FIG. 3 is a schematic diagram of the case where each of the two adjacent rolls in FIG. 1 is a textured roll. FIG. 4 is a schematic diagram showing the configuration of a degassing device included in a manufacturing apparatus for a fiber-reinforced composite sheet according to a modification.

Hereinafter, preferred embodiments of the present disclosure will be described in detail, with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant explanations will be omitted. Furthermore, the dimensional ratios in the drawings are not limited to the ratios shown.

[Manufacturing equipment for fiber reinforced composite sheet]
FIG. 1 is a schematic diagram showing the main configuration of a fiber-reinforced composite sheet manufacturing apparatus according to the present embodiment. FIG. 1 is an example of the fiber-reinforced composite sheet manufacturing apparatus of the present disclosure, and therefore, the present disclosure is not limited to the form illustrated in FIG. 1. Hereinafter, in order to explain this embodiment more clearly, it will be explained based on FIG. 1. A manufacturing apparatus 1 shown in FIG. 1 is an apparatus for manufacturing fiber-reinforced composite sheets (details will be described later, hereinafter also referred to as "SMC"), which is also called a sheet molding compound (manufacturing for fiber-reinforced composite sheets). equipment). The manufacturing apparatus 1 includes a first delivery roll 2, a first application section 3, a reinforcing fiber supply section 4, a second delivery roll 5, a second application section 6, a conveyance section 7, and a pressure section 8. , and a take-up roll 9. Hereinafter, in the manufacturing apparatus 1, the flow direction of the SMC or a member for manufacturing the SMC (hereinafter referred to as an SMC manufacturing member) from the first delivery roll 2 to the take-up roll 9 will be referred to as the transport direction MD.

The first delivery roll 2 is a roll around which the first carrier film F1 is wound, and is located at the most upstream position of the manufacturing apparatus 1. The first carrier film F1 is one of the members for SMC manufacturing, and is pulled out by the conveyance section 7. The first carrier film F1 is used as one of the supporting members for transporting the SMC. The first carrier film F1 may have a single layer structure or a laminated structure. When the first carrier film F1 has a laminate structure, the first carrier film F1 may be a laminate film. The first carrier film F1 is, for example, a polyethylene film, a polypropylene film, a laminate film of polyethylene and polypropylene, a polyethylene terephthalate film, a nylon film, or the like.

The first coating section 3 is a section that coats the first resin composition 3a on the first carrier film F1 that is being transported, and is located downstream of the first delivery roll 2. A coating film (not shown) made of the first resin composition 3a is formed on the first carrier film F1 that has passed through the first application section 3. The amount of the first resin composition 3a applied by the first application section 3 is, for example, 0.3 kg/m ² or more and 2.0 kg/m ² or less, but is not limited thereto. The first resin composition 3a is one of the main materials constituting the SMC. Details of the first resin composition 3a will be described later.

The reinforcing fiber supply unit 4 is a part that supplies cut pieces CC of the reinforcing fibers RF onto the coating film made of the first resin composition 3a. Therefore, the portion of the reinforcing fiber supply section 4 that supplies the cut pieces CC is located downstream of the first application section 3. The reinforcing fiber supply unit 4 includes a pull-out roll 11 that pulls out a bundle (for example, roving) of reinforcing fibers RF, and a cutting device 12 that cuts the reinforcing fibers RF. Note that the cut piece CC is one of the main materials constituting the SMC, and is used to improve the strength of the SMC. Details of the reinforcing fiber RF will be described later.

The cutting device 12 produces a plurality of cut pieces CC by cutting the reinforcing fiber RF into predetermined dimensions. In this embodiment, the reinforcing fiber supply section 4 is located above the first delivery roll 2 and the first application section 3. Thereby, the cut pieces CC are scattered onto the coating film made of the first resin composition 3a using gravity. In this case, since the cut pieces CC can fall uniformly onto the first resin composition 3a without orientation, it may be difficult for the SMC to become brittle in a particular direction. For example, the reinforcing fibers RF are pulled out by the pull-out roll 11 or the like and cut by the cutting device 12 so that the content of cut pieces CC in the SMC is 30% by mass or more and 70% by mass or less.

The second delivery roll 5 is a roll around which the second carrier film F2 is wound. The second carrier film F2 is another one of the SMC manufacturing members and functions as another one of the supporting members for transporting the SMC. The second carrier film F2 may have the same structure as the first carrier film F1, for example.

The second application section 6 is a section that applies the second resin composition 6a onto the second carrier film F2 that is being transported, and is located downstream of the second delivery roll 5. A coating film (not shown) made of the second resin composition 6a is formed on the second carrier film F2 that has passed through the second application section 6. The amount of the second resin composition 6a applied by the second application section 6 is, for example, 0.3 kg/m ² or more and 2.0 kg/m ² or less, but is not limited thereto. The second resin composition 6a is the same composition as the first resin composition 3a, and is one of the main materials constituting the SMC.

The conveying unit 7 is a device for conveying the first carrier film F1 and the like to the winding roll 9. The conveyance unit 7 is, for example, a conveyor belt such as a belt conveyor that conveys at least the first carrier film F1, but is not limited thereto. In this embodiment, the conveyance unit 7 conveys not only the first carrier film F1 but also the second carrier film F2 to the winding roll 9.

The pressure unit 8 includes a first carrier film F1 and a second carrier film that sandwich the first resin composition 3a supplied with the cut pieces CC and the second resin composition 6a facing the first resin composition 3a. This is a part that pressurizes F2, and is located downstream of the first application section 3 and the second application section 6. In this embodiment, the pressurizing section 8 has a plurality of rolls included in the manufacturing apparatus 1. These multiple rolls include, for example, other rolls in addition to the crown roll, as described below. Other rolls may include, for example, a smooth roll with a smooth surface and no change in diameter in the axial direction, an uneven roll with an uneven surface, and the like. Moreover, the pressurizing part 8 may have a receiving roll that becomes a pair of the above-mentioned roll. At least a portion of the pressurizing section 8 overlaps the conveying section 7 in the vertical direction. As shown in FIG. 1, the pressure section 8 includes a pair of receiving rolls 21, a crown roll 22, rolls 23 to 26, a smooth roll 27, and smooth receiving rolls 30a to 30f.

The pair of receiving rolls 21 are members that receive the first carrier film F1 coated with the first resin composition 3a and the second carrier film F2 coated with the second resin composition 6a. The pair of receiving rolls 21 includes a first smooth roll 21a in contact with the second carrier film F2 and a second smooth roll 21b in contact with the first carrier film F1. A laminate S containing the first resin composition 3a, the second resin composition 6a, and reinforcing fibers RF is formed between the first carrier film F1 and the second carrier film F2 that have passed through the pair of receiving rolls 21. be done. Note that the laminate S is a sheet-like member that will later become an SMC.

The crown roll 22 is a member for removing gas present between the first carrier film F1 and the second carrier film F2, and is located downstream of the pair of receiving rolls 21. The gas includes, for example, air bubbles existing inside the laminate S, air bubbles existing between the laminate S and the first carrier film F1, air bubbles existing between the laminate S and the second carrier film F2, etc. It is. These bubbles are, for example, gases involved during application of the first resin composition 3a, gases involved during application of the second resin composition 6a, first resin composition 3a and/or second resin composition 6a. It is formed from gas generated by a chemical reaction, gas adhering to the cut piece CC, gas drawn in when the first carrier film F1 and the second carrier film F2 are overlapped, and the like.

FIG. 2 is a schematic diagram of the crown roll. As shown in FIG. 2, the crown roll 22 is a member extending in the axial direction AD orthogonal to the conveyance direction MD. The outer diameter of the crown roll 22 is different from the pair of receiving rolls 21, the smooth roll 27, and the smooth receiving rolls 30a to 30f, and is nonuniform in the axial direction AD. In this embodiment, the outer diameter of the crown roll 22 becomes smaller as it approaches both ends from the center of the crown roll 22 in the axial direction AD. Therefore, in the axial direction AD, the outer diameter OD1 (center diameter) at the center of the crown roll 22 is the largest, and the outer diameter OD2 (end diameter) at the end 22a of the crown roll 22 is the smallest. The outer diameter OD1 is, for example, 100 mm or more and 200 mm or less. Note that there may be a region in the center of the crown roll 22 in the axial direction AD where the outer diameter does not change (that is, also referred to as a region where no taper is provided or a region where the outer diameter is uniform). In other words, a smooth roll region may be provided in the center of the crown roll 22. In this case, the dimension of the region along the axial direction AD is, for example, less than half the dimension of the crown roll 22 along the axial direction AD.

In this embodiment, the taper angle of the crown roll 22 is 0.1° or more and 1.3° or less. This taper angle corresponds to a multiple of the slope angle θ of the crown roll 22 shown in FIG. The taper angle may be 0.1° or more and 1.0° or less, or 0.2° or more and 0.8° or less. Further, the dimension of the crown roll 22 along the axial direction AD is, for example, 1000 mm or more and 2000 mm or less. The dimension may be 1100 mm or more, 1200 mm or more, 1300 mm or more, 1800 mm or less, 1600 mm or less, or 1500 mm or less. Alternatively, the difference between the outer diameter OD1 and the outer diameter OD2 is, for example, 0.5 mm or more and 8 mm or less. In these cases (i.e., when the crown roll 22 has the above taper angle and the above dimensions, or when the difference between the outer diameter OD1 and the outer diameter OD2 is within the above range), the laminate S passes through the crown roll 22. At this time, the gas existing between the first carrier film F1 and the second carrier film F2 is successfully removed from both ends of the laminate S in the axial direction AD.

The material of the crown roll 22 is not particularly limited, but from the viewpoint of preventing damage to the laminate S, silicone, elastomer, nitrile rubber, urethane rubber, etc. are used. Further, the hardness of the crown roll 22 measured in accordance with JIS K 6253-1997 is, for example, 40 or more and 55 or less.

In order to make the crown roll 22 perform its gas removal function well, a smooth receiving roll 30a is provided below the crown roll 22. The smooth receiving roll 30a is a receiving member corresponding to the crown roll 22, and is spaced apart from the crown roll 22. The dimension of the smooth receiving roll 30a along the axial direction AD is approximately the same as that of the crown roll 22. The material of the smooth receiving roll 30a is not particularly limited, and examples include metal, alloys such as stainless steel, rubber, and plastic. The outer diameter of the smooth receiving roll 30a is not particularly limited, but is, for example, 50% or more and 90% or less of the outer diameter OD1 of the crown roll 22. In the following, it is assumed that the smooth receiving rolls 30a to 30f have the same dimensions, but the present invention is not limited to this.

The gap between the crown roll 22 and the smooth receiving roll 30a is a region through which the laminate S sandwiched between the first carrier film F1 and the second carrier film F2 passes. corresponds to Therefore, when passing through the gap between the crown roll 22 and the smooth receiving roll 30a, at least a portion of the laminate S is pressurized by the crown roll 22 and the smooth receiving roll 30a. Here, the gap is the minimum gap between the crown roll 22 and the smooth receiving roll 30a. In this embodiment, the smooth receiving roll 30a is provided within the conveyance section 7. For this purpose, a transfer belt (not shown) is provided between the crown roll 22 and the smooth receiving roll 30a. Therefore, the minimum gap in this embodiment corresponds to the total thickness of the SMC, the first carrier film F1, the second carrier film F2, and the transfer belt.

Each of the rolls 23 to 26 is a member that presses the laminate S in order to promote impregnation of the first resin composition 3a and the second resin composition 6a into the reinforcing fibers RF in the laminate S, and It is located downstream of the roll 22. Each of the rolls 23 to 26 is arranged in order along the conveyance direction MD. The rolls 23 to 26 are located substantially on the same plane. Here, "substantially" the same plane means that the deviation in the height direction at the portions of the roll surfaces of the rolls 23 to 26 that contact the first carrier film F1 and the second carrier film F2 is the maximum diameter of the rolls 23 to 26. This means that it is within ±10%. The material of the rolls 23 to 26 is not particularly limited, and includes, for example, metal, alloy such as stainless steel, rubber, plastic, and the like.

FIG. 3 is a schematic diagram of the case where each of the two

adjacent rolls

23 and 24 in FIG. 1 is an uneven roll. As shown in FIG. 3, the roll 23 (first uneven roll) and the roll 24 (second uneven roll) that are adjacent to each other in the transport direction MD are located on substantially the same plane, and are similar to the crown roll 22. It extends along the axial direction AD. The dimensions of the

rolls

23 and 24 along the axial direction AD are, for example, comparable to the crown roll 22.

The surface 23a of the roll 23 is provided with a plurality of protrusions 23b (first protrusions) arranged intermittently along the axial direction AD. Similarly, the surface 24a of the roll 24 is provided with a plurality of convex portions 24b (second convex portions) arranged intermittently along the axial direction AD. Each of the

protrusions

23b and 24b is a portion that protrudes along the radial direction of the

rolls

23 and 24. Although each of the

convex portions

23b and 24b has an annular shape when viewed from the axial direction AD, the shape is not limited to this. The tips of the

protrusions

23b and 24b may or may not be rounded. The

convex portions

23b and 24b may have a tapered shape.

In the axial direction AD, the plurality of convex portions 23b and the plurality of convex portions 24b are provided alternately. Therefore, in the axial direction AD, one protrusion 24b among the plurality of protrusions 24b may be arranged between two adjacent protrusions 23b among the plurality of protrusions 23b. That is, the plurality of

convex portions

23b and 24b are arranged in a comb shape. Thereby, the convex portion 23b can come into contact with a part of the stacked body S, and the convex portion 24b can come into contact with another part of the stacked body S. Note that the roll 25 may have the same shape as the roll 23, and the roll 26 may have the same shape as the roll 24. In this case, in the axial direction AD, the plurality of convex portions provided on the roll 25 are provided alternately with the multiple convex portions 24b of the roll 24, and are provided alternately with the multiple convex portions of the roll 26.

The maximum diameter of the

rolls

23 and 24 is, for example, 100 mm or more and 200 mm or less. The dimensions of the

convex portions

23b and 24b along the axial direction AD are, for example, 2 mm or more and 10 mm or less. In the axial direction AD, the gap between two adjacent convex portions 23b and the gap between two adjacent convex portions 24b are, for example, 5 mm or more and 20 mm or less. From the viewpoint of applying uniform pressure to the laminate S, the dimensions of the

convex portions

23b and 24b along the axial direction AD and the gap may be approximately the same. The amount of protrusion of the

convex portions

23b and 24b is, for example, 5 mm or more and 15 mm or less.

In order to allow the rolls 23 to 26 to perform well in impregnating the reinforcing fibers RF, smooth receiving rolls 30b to 30e are provided below the rolls 23 to 26, respectively. The smooth receiving rolls 30b to 30e are receiving members corresponding to the rolls 23 to 26, respectively, and are spaced apart from the rolls 23 to 26. The gap between the roll 23 and the smooth receiving roll 30b is approximately the same as the minimum gap between the crown roll 22 and the smooth receiving roll 30a. In this embodiment, each of the smooth receiving rolls 30b to 30e is also provided within the conveying section 7.

The smoothing roll 27 is a member that applies pressure evenly to the laminate S in order to flatten the surface of the laminate S, and is located downstream of the rolls 23 to 26. The smooth roll 27 is located at the most downstream position in the pressure section 8 . The dimension of the smooth roll 27 along the axial direction AD is, for example, comparable to that of the crown roll 22. The material of the smooth roll 27 is not particularly limited, and includes, for example, metal, alloy such as stainless steel, rubber, and plastic. The outer diameter of the smooth roll 27 is not particularly limited, but is, for example, 50% or more and 90% or less of the outer diameter OD1 of the crown roll 22.

A smooth receiving roll 30f is provided below the smoothing roll 27 so that the smoothing roll 27 can effectively flatten the laminate S. The smooth receiving roll 30f is a receiving member corresponding to the smooth roll 27, and is spaced apart from the smooth roll 27. The gap between the smooth roll 27 and the smooth receiving roll 30f is approximately the same as the minimum gap between the crown roll 22 and the smooth receiving roll 30a. In this embodiment, a smooth receiving roll 30f is also provided within the conveyance section 7.

The winding roll 9 is a member that winds up the first carrier film F1 and the second carrier film F2 sandwiching the laminate S, and is located at the most downstream side of the manufacturing apparatus 1. The winding roll 9 winds up the laminate S that has passed through all the rolls included in the pressure section 8 . The winding roll 9 on which the laminate S has been wound is conveyed to a constant temperature machine or the like, if necessary. Thereby, the chemical reaction (for example, B-stage formation) of the first resin composition 3a and the second resin composition 6a included in the laminate S can be promoted. In this embodiment, the laminate S wound up by the take-up roll 9 may be referred to as SMC, and the laminate S after the chemical reaction has been completed may be referred to as SMC.

The thickness of the laminate S thus obtained, that is, the thickness of the SMC manufactured by the manufacturing apparatus 1, is adjusted as appropriate depending on the application and the like. The thickness of SMC generally ranges from 1 to 4 mm.

[SMC manufacturing method]
Below, an example of a method for manufacturing SMC using the above-mentioned fiber reinforced composite sheet manufacturing apparatus will be described.

First, the first resin composition 3a is applied onto the first carrier film F1 that is being transported (first step). By carrying out the first step, a coating film made of the first resin composition 3a is formed on the first carrier film F1. Next, the cut pieces CC of the reinforcing fibers RF are supplied onto the first resin composition 3a (second step). In the second step, the cut pieces CC obtained by the cutting device 12 are scattered. Then, the cut pieces CC scattered from above the first resin composition 3a land irregularly on the first resin composition 3a. As a result, cut pieces CC are uniformly provided on the first resin composition 3a without orientation.

Furthermore, the second resin composition 6a is applied onto the second carrier film F2 that is being transported (third step). By carrying out the third step, a coating film made of the second resin composition 6a is formed on the second carrier film F2. The third step is performed, for example, in synchronization with the first step and the second step. Therefore, the third step may not be performed after the first step, or may not be performed after the second step.

After implementing the first to third steps, the first carrier film F1 and the second carrier film F2 are brought close to each other, and the first resin composition 3a and the second resin composition 6a to which the cut pieces CC have been supplied are made. A laminate S is formed (fourth step). In the fourth step, a laminate S is formed by conveying the first carrier film F1 and the second carrier film F2 to the receiving roll 21. Next, the laminate S is pressurized by the pressurizing section 8 (fifth step). In the fifth step, the laminate S is pressurized by the receiving roll 21, the crown roll 22, the rolls 23 to 26, the smooth roll 27, and the smooth receiving rolls 30a to 30f. As a result, the gas present between the first carrier film F1 and the second carrier film F2 is removed, the reinforcing fibers RF are impregnated with the resin composition, and the laminate S is flattened. Subsequently, the laminate S sandwiched between the first carrier film F1 and the second carrier film F2 is wound up. The above steps are performed in the manufacturing apparatus 1.

The laminate S wound up by the winding roll 9 may be heated (ripened) using, for example, a constant temperature machine. In this case, a B-staged sheet-like molding material (SMC) having excellent film releasability and the like is obtained.

[First resin composition 3a and second resin composition 6a]
The first resin composition 3a and the second resin composition 6a (hereinafter simply referred to as "resin composition") are not particularly limited as long as they are commonly used for manufacturing SMC. Thermosetting resin compositions are generally widely used in the production of SMC. Therefore, the resin composition may include a thermosetting resin composition. Specific examples of the thermosetting resin composition include vinyl ester resin compositions, epoxy resin compositions, unsaturated polyester resin compositions, and the like.

<Vinyl ester resin composition>
The vinyl ester resin composition is a thermosetting resin composition containing a vinyl ester resin. Examples of the vinyl ester resin include those using an epoxy resin and (meth)acrylic acid as reaction raw materials. As used herein, "(meth)acrylic acid" refers to either or both of acrylic acid and methacrylic acid, and "(meth)acrylate" refers to either or both of acrylate and methacrylate. It is.

Specific examples of epoxy resins include diglycidyloxybenzene, diglycidyloxynaphthalene, aliphatic epoxy resin, biphenol type epoxy resin, bisphenol type epoxy resin, novolac type epoxy resin, alicyclic epoxy resin, glycidylamine type epoxy resin, Heterocyclic epoxy resins, glycidyl ester epoxy resins, triphenolmethane epoxy resins, phenol or naphthol aralkyl epoxy resins, phenylene or naphthylene ether epoxy resins, oxodoridone modified epoxy resins, brominated epoxy resins of these, etc. Can be mentioned. The epoxy resin may be an epoxy resin obtained by elongating the specific example described above using an elongating agent. One type of epoxy resin may be used alone, or two or more types may be used in combination.

Examples of aliphatic epoxy resins include various aliphatic polyol compounds and one or more of these alkylene oxide adducts that are polyglycidyl etherified with epihalohydrin. Aliphatic polyol compounds include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 2-methylpropanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3- Isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl 1,5-pentanediol , neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, 2,2,4-trimethyl-1,3-pentanediol, and other aliphatic diol compounds; 2,2-bis( Alicyclic diol compounds such as 4-hydroxyphenyl)propane; tri- or more functional aliphatic polyol compounds such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, etc. It will be done.

Examples of biphenol-type epoxy resins include biphenol compounds such as biphenol and tetramethylbiphenol, and one or more of these alkylene oxide adducts, which are polyglycidyl etherified with epihalohydrin.

Examples of bisphenol-type epoxy resins include bisphenol compounds such as bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene, and biscresol fluorene, and polyglycidyl etherification of one or more of these alkylene oxide adducts with epihalohydrin. Can be mentioned.

Examples of novolac-type epoxy resins include those obtained by polyglycidyl etherifying a novolak resin made of one or more of various phenolic compounds such as phenol, dihydroxybenzene, cresol, xylenol, naphthol, dihydroxynaphthalene, bisphenol, and biphenol with epihalohydrin. Can be mentioned.

Examples of the alicyclic epoxy resin include 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, and the like.

Examples of the glycidylamine type epoxy resin include N,N-diglycidylaniline, triglycidylaminophenol, tetraglycidylxylene diamine, 4,4'-methylenebis[N,N-diglycidylaniline], and the like.

Examples of the heterocyclic epoxy resin include 1,3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate, and the like.

Examples of the glycidyl ester type epoxy resin include phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, diglycidyl-p-oxybenzoic acid, and dimer acid glycidyl ester.

Examples of elongating agents for epoxy resins include the aforementioned various biphenol compounds, the aforementioned various bisphenol compounds, dibasic acid compounds, acid group-containing polyester resins, and the like.

From the viewpoints of impregnability into reinforcing fibers RF, strength of molded products, etc., the resin composition is a bisphenol-type epoxy resin or an epoxy resin obtained by elongating this with an elongating agent (hereinafter abbreviated as "epoxy resin (1)"). But that's fine. In this case, the epoxy equivalent of the epoxy resin is preferably in the range of 170 to 360 g/eq, more preferably in the range of 200 to 300 g/eq.

The reaction between the epoxy resin and (meth)acrylic acid can be carried out by heating at a temperature of about 60 to 140°C in the presence of any esterification catalyst. If necessary, a reaction solvent may be used or a polymerization inhibitor may be added. In addition, the reaction ratio of the epoxy resin and (meth)acrylic acid is determined by adjusting the molar ratio of the functional groups [carboxy group/ [guepoxy group] is preferably in the range of 0.6 to 1.1.

Vinyl ester resin has hydroxyl groups produced by the reaction between an epoxy resin and an extender and the reaction between an epoxy resin and (meth)acrylic acid. The hydroxyl group can be used as a reactive group, for example, by adding a compound capable of reacting with the hydroxyl group, such as a polyisocyanate compound, to the vinyl ester resin composition. When the epoxy resin (1) is used, the hydroxyl value of the vinyl ester resin (hereinafter abbreviated as "vinyl ester resin (1)") obtained by reacting the epoxy resin (1) with (meth)acrylic acid is: For example, 100 to 300 mg/KOH. In addition, the hydroxyl value of the resin is a value measured by the method described in Examples described later.

The resin composition may contain multiple types of vinyl ester resins. From the viewpoints of impregnation into reinforcing fibers, strength of molded products, etc., vinyl ester resin is prepared by combining vinyl ester resin (1) (bisphenol type epoxy resin or epoxy resin obtained by elongating this with an elongating agent with (meth)acrylic acid). (reacted vinyl ester resin). In this case, the ratio of the vinyl ester resin (1) to the total mass of the vinyl ester resin may be 70% by mass or more, or 80% by mass or more. The higher the ratio, the more preferable. From the viewpoint of resin impregnation into reinforcing fibers RF, the viscosity (measured value at 25° C.) of the vinyl ester resin composition is, for example, in the range of 0.2 to 8 Pa·s. In addition, the viscosity of the resin composition is a value measured by the method described in Examples described later.

The vinyl ester resin composition may contain a polymerizable unsaturated group-containing compound other than the vinyl ester resin. Moreover, one type of the polymerizable unsaturated group-containing compound may be used alone, or two or more types may be used in combination.

Examples of the polymerizable unsaturated group-containing compound include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2- Ethylhexyl (meth)acrylate, octyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isotridecyl (meth)acrylate, n-stearyl (meth)acrylate, ethylene glycol (meth)acrylate alkyl ether, propylene glycol ( Aliphatic mono(meth)acrylate compounds such as meth)acrylate alkyl ether; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl mono(meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl methacrylate Alicyclic mono(meth)acrylate compounds such as; heterocyclic mono(meth)acrylate compounds such as glycidyl(meth)acrylate and tetrahydrofurfuryl acrylate; benzyl(meth)acrylate, phenyl(meth)acrylate, phenylbenzyl(meth)acrylate; ) acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzylbenzyl (meth)acrylate , phenylphenoxyethyl (meth)acrylate, and other aromatic ring-containing mono(meth)acrylate compounds; the molecular structures of the various mono(meth)acrylate monomers include (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxypropylene chains, ) A (poly)oxyalkylene-modified mono(meth)acrylate compound into which a polyoxyalkylene chain such as an oxytetramethylene chain is introduced; a lactone into which a (poly)lactone structure is introduced into the molecular structure of the various mono(meth)acrylate compounds mentioned above. Modified mono(meth)acrylate compounds; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc. Aliphatic di(meth)acrylate compounds; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, tricyclo Alicyclic di(meth)acrylate compounds such as decanedimethanol di(meth)acrylate; aromatic ring-containing di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; Polyoxyalkylene-modified di(meth)acrylates in which (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylene chains, etc. are introduced into the molecular structure of meth)acrylate compounds. Compounds: Lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the various di(meth)acrylate compounds; trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, etc. Aliphatic tri(meth)acrylate compound; The aliphatic tri(meth)acrylate compound has (poly)oxy groups such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains in the molecular structure of the aliphatic tri(meth)acrylate compounds. A (poly)oxyalkylene-modified tri(meth)acrylate compound with an alkylene chain introduced; a lactone-modified tri(meth)acrylate compound with a (poly)lactone structure introduced into the molecular structure of the aliphatic tri(meth)acrylate compound; Tetrafunctional or higher functional aliphatic poly(meth)acrylate compounds such as erythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate; molecules of the aliphatic poly(meth)acrylate compounds Tetrafunctional or higher (poly)oxyalkylene-modified poly(meth)acrylates with (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains introduced into the structure. Compounds include tetrafunctional or higher-functional lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic poly(meth)acrylate compound.

From the viewpoint of the strength, heat resistance, etc. of the molded product, the polymerizable unsaturated group-containing compound may be an aromatic ring-containing (meth)acrylate compound. In this case, from the viewpoint of impregnation into the reinforcing fibers, the polymerizable unsaturated group-containing compound may be an aromatic ring-containing mono(meth)acrylate compound.

When the resin composition contains a vinyl ester resin and a polymerizable unsaturated group-containing compound, the mass ratio of the vinyl ester resin to the polymerizable unsaturated group-containing compound (vinyl ester resin)/(polymerizable unsaturated group-containing compound ) ranges from 30/70 to 85/15. In this case, the impregnating properties of the reinforcing fibers, the strength of the molded product, the heat resistance, etc. are well balanced. The above mass ratio may be in the range of 40/60 to 70/30.

The vinyl ester resin composition may contain a polyisocyanate compound. The polyisocyanate compound can be a reactive component with the hydroxyl group that the vinyl ester resin has. Further, one type of polyisocyanate compound may be used alone, or two or more types may be used in combination.

Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid diisocyanate. ; Alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, toridine diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene Aromatic diisocyanate compounds such as diisocyanate and polymethylene polyphenyl polyisocyanate; Modified products of these isocyanate compounds such as isocyanurate modified products, biuret modified products, allophanate modified products, carbodiimide modified products, urethanimine modified products, diethylene glycol, dipropylene Examples include polyol modified products modified with polyols having a number average molecular weight of 1,000 or less, such as glycol. The polyisocyanate compound may be an aromatic polyisocyanate compound.

From the viewpoint of film removability, less tack during B-staging, etc., the ratio of the number of moles of isocyanate groups contained in the polyisocyanate compound to the number of moles of hydroxyl groups contained in the vinyl ester resin (NCO/OH) is as follows: The range may be from 0.5 to 0.95, or from 0.55 to 0.85.

The vinyl ester resin composition may contain a polymerization initiator. Although general polymerization initiators can be used without particular limitation, organic peroxides are particularly preferred. Examples of the organic peroxide include diacyl peroxide compounds, peroxy ester compounds, hydroperoxide compounds, ketone peroxide compounds, alkyl perester compounds, percarbonate compounds, peroxyketals, and the like. These polymerization initiators may be used alone or in combination of two or more. From the viewpoint of the balance between storage stability and curability, the amount of the polymerization initiator added may range from 0.3 to 3% by mass based on the total mass of the vinyl ester resin and the polymerizable unsaturated group-containing compound. good.

The vinyl ester resin composition may contain other components in addition to the vinyl ester resin, the polymerizable unsaturated group-containing compound, the polyisocyanate compound, and the polymerization initiator. Other ingredients include, for example, thermoplastic resins, polymerization inhibitors, curing accelerators, fillers, low shrinkage agents, mold release agents, thickeners, thinners, pigments, antioxidants, plasticizers, and flame retardants. , antibacterial agents, ultraviolet stabilizers, reinforcing materials, photocuring agents, etc.

Examples of thermoplastic resins include polyamide resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polycarbonate resins, urethane resins, polypropylene resins, polyethylene resins, polystyrene resins, acrylic resins, polybutadiene resins, polyisoprene resins, and copolymers of these resins. Examples include those modified by. These may be used alone or in combination of two or more.

Examples of the polymerization inhibitor include hydroquinone, trimethylhydroquinone, pt-butylcatechol, t-butylhydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, copper naphthenate, copper chloride, etc. . These may be used alone or in combination of two or more.

Examples of hardening accelerators include metal soaps such as cobalt naphthenate, cobalt octenoate, vanadyl octenoate, copper naphthenate, and barium naphthenate, and metal chelate compounds such as vanadyl acetylacetate, cobalt acetylacetate, and iron acetylacetonate. can be mentioned. In addition, as amines, N,N-dimethylamino-p-benzaldehyde, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N-ethyl-m-toluidine, triethanol Examples include amine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, diethanolaniline, and the like. These may be used alone or in combination of two or more.

Fillers can be broadly divided into inorganic compounds and organic compounds. A filler is a component added mainly for the purpose of adjusting physical properties such as strength, elastic modulus, impact strength, and fatigue durability of a molded article.

Inorganic compounds include, for example, calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, barite, barite, silica, silica sand, dolomite limestone, gypsum, aluminum fine powder, hollow balloon, alumina, Examples include glass powder, aluminum hydroxide, agarite, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, and iron powder. Examples of organic compounds include natural polysaccharide powders such as cellulose and chitin, synthetic resin powders, and the like. Examples of the synthetic resin powder include organic powder made of hard resin, soft rubber, elastomer, or polymer (copolymer), and particles having a multilayer structure such as core-shell type. Specific examples of the synthetic resin powder include particles made of butadiene rubber, acrylic rubber, urethane rubber, silicone rubber, etc., polyimide resin powder, fluororesin powder, phenol resin powder, and the like. These may be used alone or in combination of two or more.

Examples of the mold release agent include zinc stearate, calcium stearate, paraffin wax, polyethylene wax, and carnauba wax. Preferred examples include paraffin wax, polyethylene wax, carnauba wax, and the like. These may be used alone or in combination of two or more.

Examples of the thickener include metal oxides and metal hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide, and calcium hydroxide, and acrylic resin-based fine particles. These thickeners can be used alone or in combination of two or more.

<Epoxy resin composition>
The epoxy resin composition is a thermosetting resin composition containing an epoxy resin and a curing agent or curing accelerator. Examples of the epoxy resin include phenylglycidyl ether, diglycidyloxybenzene, diglycidyloxynaphthalene, aliphatic epoxy resin, biphenol type epoxy resin, bisphenol type epoxy resin, novolak type epoxy resin, alicyclic epoxy resin, and glycidylamine type. Epoxy resin, heterocyclic epoxy resin, glycidyl ester type epoxy resin, triphenolmethane type epoxy resin, phenol or naphthol aralkyl type epoxy resin, phenylene or naphthylene ether type epoxy resin, oxodoridone modified epoxy resin, brominated epoxy resin Examples include resins, epoxy resins obtained by elongating these epoxy resins with an elongating agent, and the like. These epoxy resins may be used alone or in combination of two or more.

Examples of aliphatic epoxy resins include various aliphatic polyol compounds and those obtained by polyglycidyl etherification of one or more of these alkylene oxide adducts with epihalohydrin. Examples of aliphatic polyol compounds include ethylene glycol, propylene glycol, 1,3-propanediol, 2-methylpropanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3 -isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl 1,5-pentane Aliphatic diol compounds such as diol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, 2,2,4-trimethyl-1,3-pentanediol; 2,2-bis Alicyclic diol compounds such as (4-hydroxyphenyl)propane; tri- or higher functional aliphatic polyol compounds such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, etc. Can be mentioned.

Specific examples of biphenol-type epoxy resin, bisphenol-type epoxy resin, novolac-type epoxy resin, alicyclic epoxy resin, glycidylamine-type epoxy resin, and heterocyclic epoxy resin contained in the epoxy resin composition are as described above, for example. be. The epoxy equivalent of the bisphenol-type epoxy resin may be, for example, in the range of 170 to 360 g/eq, or may be in the range of 170 to 280 g/eq. Further, as the glycidylamine type epoxy resin, tetraglycidyldiaminodiphenylmethane or the like may be used. The above-mentioned extender may be used in the epoxy resin composition.

From the viewpoint of the strength of the molded product, etc., an epoxy resin having an aromatic ring in its molecular structure may be used as the epoxy resin. For example, a bifunctional epoxy resin and a trifunctional or higher functional epoxy resin may be used together. In this case, the mass ratio of both (bifunctional epoxy resin having an aromatic ring in its molecular structure)/(trifunctional or higher functional epoxy resin having an aromatic ring in its molecular structure) may be in the range of 20/80 to 80/20. It may range from 40/60 to 60/40.

From the viewpoint of impregnation into the reinforcing fiber RF, the epoxy resin may include an epoxy resin having an aromatic ring in its molecular structure and an aliphatic epoxy resin. In this case, the mass ratio of both (epoxy resin having an aromatic ring in its molecular structure)/(aliphatic epoxy resin) is, for example, in the range of 70/30 to 95/5.

As the curing agent or curing accelerator contained in the epoxy resin composition, various compounds commonly used for curing epoxy resins can be used without particular limitation. Moreover, one type of curing agent or curing accelerator may be used alone, or two or more types may be used in combination. Examples of the curing agent or curing accelerator include amine compounds, amide compounds, acid anhydrides, phenolic hydroxyl group-containing resins, phosphorus compounds, imidazole compounds, imidazoline compounds, urea compounds, organic acid metal salts, Lewis acids, Examples include amine complex salts.

Examples of amine compounds include aliphatic amine compounds such as ethylenediamine, tetramethylethylenediamine, diethylenetriamine, hexamethylenediamine, triethylenetetramine, and guanidine derivatives; piperidine, piperazine, isophoronediamine, 1,8-diazabicyclo-[5.4. 0]-Alicyclic and heterocyclic amine compounds such as undecene (DBU); aromatic amine compounds such as phenylene diamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzylmethylamine, dimethylbenzylamine, xylene diamine, pyridine; Examples include boron amine complexes.

Examples of the amide compound include dicyandiamide, polyamide amine, and the like. Polyamide amines include, for example, aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid, fatty acids, carboxylic acid compounds such as dimer acids, and aliphatic polyamines or polyoxyalkylene chains. It is a reaction product with polyamine, etc.

Examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydro Examples include phthalic anhydride.

Examples of phenolic hydroxyl group-containing resins include various novolac resins, dicyclopentadiene phenol addition type resins, phenol or naphthol aralkyl resins, triphenolmethane resins, phenol or naphthol aralkyl resins, phenylene or naphthylene ether resins, amino Examples include triazine-modified phenolic resins.

Examples of phosphorus compounds include alkyl phosphines such as ethylphosphine and butylphosphine, primary phosphines such as phenylphosphine; dialkylphosphines such as dimethylphosphine and dipropylphosphine; secondary phosphines such as diphenylphosphine and methylethylphosphine; and trimethylphosphine. , tertiary phosphines such as triethylphosphine, triphenylphosphine, and the like.

Examples of imidazole compounds include imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4 -ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutyl Imidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4- Methylimidazole, 1-phenylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl- 2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole Isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4, Examples include 5-di(2-cyanoethoxy)methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, and 1-benzyl-2-phenylimidazole hydrochloride.

Examples of the imidazoline compound include 2-methylimidazoline and 2-phenylimidazoline.

Examples of urea-based compounds include p-chlorophenyl-N,N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-N,N-dimethylurea, N-( Examples include 3-chloro-4-methylphenyl)-N',N'-dimethylurea and 4,4'-methylenebisphenyldimethylurea.

From the viewpoint of early curing, physical properties of the molded product, etc., an amine compound, an amide compound, an imidazole compound, or a urea-based compound may be used as a curing agent or curing accelerator.

When a compound having a functional group that can react with an epoxy group, such as an amine compound, amide compound, acid anhydride, or phenolic hydroxyl group-containing compound, is used as a curing agent or curing accelerator, the curing agent in the epoxy resin composition Alternatively, the amount of the curing accelerator is adjusted, for example, such that the functional group in the curing agent is in the range of 0.5 to 1.1 mol per 1 mol of the epoxy group in the epoxy resin component. Further, when a phosphorus compound, an imidazole compound, an imidazoline compound, a urea compound, etc. is used as a curing agent or curing accelerator, the amount of the curing agent or curing accelerator in the epoxy resin composition is, for example, 100% of the epoxy resin component. It is adjusted at a ratio of 0.5 to 20 parts by mass based on parts by mass.

The epoxy resin composition may contain other components in addition to the epoxy resin, the curing agent, or the curing accelerator. Other components include, for example, thermoplastic resins, polymerization inhibitors, fillers, low shrinkage agents, mold release agents, thickeners, thinners, pigments, antioxidants, plasticizers, flame retardants, antibacterial agents, Examples include ultraviolet stabilizers, reinforcing agents, and photocuring agents. Specific examples of these include the same ones as mentioned above.

From the viewpoint of moldability, the epoxy resin composition may contain a thermoplastic resin. In this case, the thermoplastic resin is, for example, a polymer obtained by polymerizing at least one compound selected from (meth)acrylic esters, diene compounds, and other compounds copolymerizable with these. be. Further, it is preferable that the thermoplastic resin is in the form of a powder, and it is particularly preferable that the thermoplastic resin powder, which is composed of a core layer and a shell layer, is used as an active ingredient. Examples of (meth)acrylic esters include ethyl (meth)acrylate, n-butyl (meth)acrylate, methyl methacrylate, butyl (meth)acrylate, n-propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-decyl methacrylate, isobutyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, etc. can be mentioned.

Examples of the diene compound include conjugated diene compounds such as butadiene, isoprene, 1,3-pentadiene, cyclopentadiene, and dicyclopentadiene, and non-conjugated diene compounds such as 1,4-hexadiene and ethylidene norbornene.

Examples of other compounds include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, pt-butylstyrene, and chlorostyrene; (meth)acrylamide, N-methylol(meth)acrylamide, and N-butoxy Examples include (meth)acrylamide-based compounds such as methyl (meth)acrylamide; glycidyl (meth)acrylate, allylglycidyl (meth)acrylate, and the like. Among these, aromatic vinyl compounds are preferred.

The amount of thermoplastic resin powder added to the epoxy resin composition may be, for example, 1 to 20 parts by mass, or 3 to 9.5 parts by mass, based on a total of 100 parts by mass of the epoxy resin composition.

From the viewpoint of resin impregnation into reinforcing fibers RF, the viscosity (measured value at 25° C.) of the epoxy resin composition is, for example, in the range of 1 to 50 Pa·s.

[Reinforced fiber RF]
The reinforcing fiber RF is not particularly limited as long as it is a fiber commonly used for SMC. Specific examples of reinforcing fiber RF include glass fiber, carbon fiber, silicon carbide fiber, pulp, hemp, cotton, nylon, polyester, acrylic, polyurethane, polyimide, polyamide fiber (e.g., aramid such as Kevlar and Nomex), etc. It will be done. The reinforcing fiber RF may contain one type of fiber, or may contain two or more types of fiber. From the viewpoint of mechanical strength, durability, etc. of the molded product, the reinforcing fiber RF is carbon fiber. Examples of carbon fibers include various types such as polyacrylonitrile fibers, pitch fibers, and rayon fibers. From the viewpoint of obtaining high-strength reinforcing fibers RF, the carbon fibers may be RF polyacrylonitrile fibers.

As the reinforcing fiber RF, for example, carbon fiber cut into a length of 2.5 to 50 mm is used. Carbon fibers cut into lengths of 5 to 40 mm may be used, since the fluidity in the mold during molding, the appearance and mechanical properties of the molded product are further improved. From the viewpoint of resin impregnation properties and mechanical properties of the molded article, the number of filaments in the fiber bundle used as carbon fibers is, for example, 1,000 to 60,000.

From the viewpoint of the mechanical strength of the molded product, the impregnability of the reinforcing fibers RF, etc., the content of the reinforcing fibers RF in the SMC is, for example, 20 to 80% by mass, but may be 40 to 70% by mass. Note that if the impregnating properties of the reinforcing fibers RF are insufficient, there is a risk that the molded product will swell and a weak portion will be formed.

[Method for manufacturing molded products]
A molded product is manufactured by molding the SMC manufactured by the manufacturing apparatus 1 described above. From the viewpoints of productivity, appearance, etc., heat compression molding is an example of a molding method for SMC. In hot compression molding, for example, first, SMC is put into a mold that has been heated to 110 to 180° C., and then the mold is clamped using a compression molding machine. Here, the SMC is cured by maintaining a molding pressure of 0.1 to 30 MPa. Thereby, it is possible to manufacture a molded product according to the shape of the mold.

In the fiber-reinforced composite sheet manufacturing apparatus 1 according to the present embodiment described above, the pressure unit 8 that presses the first carrier film F1 and the second carrier film F2 sandwiching the laminate S is arranged perpendicularly to the transport direction MD. It has a crown roll 22 extending in the axial direction AD. As a result, when the laminate S is pressurized by the crown roll 22, the gas present between the first carrier film F1 and the second carrier film F2 is directed toward both ends of the laminate S in the axial direction AD. It is extruded to the crown roll 22. Therefore, by applying the manufacturing method using the manufacturing apparatus 1 described above, the laminate S can be degassed with high precision through both ends.

In this embodiment, the taper angle of the crown roll 22 is 0.1° or more and 1.3° or less, and the dimension of the crown roll 22 along the axial direction AD is 2000 mm or less. Alternatively, the difference between the outer diameter OD1 of the crown roll 22 and the outer diameter OD2 of the end portion 22a of the crown roll 22 is 0.5 mm or more and 8 mm or less. In these cases, the gas is well extruded by the crown roll 22.

In this embodiment, the pressurizing section 8 has a smooth receiving roll 30a corresponding to the crown roll 22. For this reason, the gas is extruded well by the crown roll 22.

In the present embodiment, the pressure unit 8 has a smooth roll 27 that presses the laminate S, and the smooth roll 27 is located at the most downstream of the pressure unit 8 in the transport direction MD. Therefore, a flat fiber-reinforced composite sheet can be manufactured satisfactorily.

In the present embodiment, the pressurizing unit 8 has

rolls

23 and 24 that are adjacent to each other in the transport direction MD and located on substantially the same plane. A plurality of convex portions 23b are provided on the surface 24a of the roll 24, and a plurality of convex portions 24b are provided intermittently along the axial direction AD. The portions 23b and the plurality of convex portions 24b are provided alternately. Therefore, the pressure applied to the laminate S by the

rolls

23 and 24 is dispersed, so that the laminate S can be sufficiently pressurized while suppressing the occurrence of uneven patterns caused by the

rolls

23 and 24.

Next, a modification of the above embodiment will be described with reference to FIG. 4. In the following, descriptions that overlap with the above embodiments will be omitted, and portions that are different from the above embodiments will be described. That is, within the technically possible range, the description of the above embodiment may be appropriately used in the modification.

In this modification, the fiber-reinforced composite sheet manufacturing device according to one aspect of the present disclosure is a combination device of the manufacturing device 1 of the above embodiment and another device other than the manufacturing device 1 described below. An example will be explained. FIG. 4 is a schematic diagram showing the configuration of a degassing device included in a manufacturing apparatus for a fiber-reinforced composite sheet according to a modification. The degassing device 100 shown in FIG. 4 is another part of the fiber-reinforced composite sheet manufacturing device, and is a separate device from the manufacturing device 1 of the above embodiment. In this modification, the pressurizing section 8 of the manufacturing apparatus 1 is part of the pressurizing section included in the manufacturing apparatus for fiber-reinforced composite sheets, and the deaerator 100 is included in the manufacturing apparatus for fiber-reinforced composite sheets. This is another part of the pressurizing section. In other words, the fiber-reinforced composite sheet manufacturing device according to this modification is a combination device that includes the pressurizing section 8 of the manufacturing device 1 and the deaerator 100.

The deaerator 100 includes a delivery roll 101, a deaerator 102, and a take-up roll 103. Although not shown, the deaerator 100 may further include a smooth roll located between the deaerator 102 and the take-up roll 103. The delivery roll 101 corresponds to, for example, the first delivery roll 2 and/or the second delivery roll 5 described in the above embodiments.

The deaeration unit 102 is a part for removing gas existing between the first carrier film F1 and the second carrier film F2, and is located downstream of the delivery roll 101. The degassing section 102 includes a crown roll 22A and a smooth receiving roll 30g. When the first carrier film F1 and the second carrier film F2 sandwiching the laminate S1 pass through the degassing section 102, the laminate S1 is pressurized by the degassing section 102. The crown roll 22A and the smooth receiving roll 30g are respectively the same as the crown roll 22 and the smooth receiving roll 30a of the above embodiment, but are not limited thereto.

The winding roll 103 is a member that winds up the first carrier film F1 and the second carrier film F2 sandwiching the laminate S1, and is located at the most downstream side of the deaerator 100. The laminate S1 wound up by the winding roll 103 corresponds to SMC.

Even in the modified example described above, the same effects as in the above embodiment are exhibited. In addition, since the laminate S can be degassed with higher precision by the deaerator 100, higher quality SMC can be manufactured.

The manufacturing apparatus for a fiber-reinforced composite sheet and the method for manufacturing a fiber-reinforced composite sheet according to one aspect of the present disclosure are, for example, as described in [1] to [7] below, and include the above-mentioned embodiments and the above-mentioned modifications. These have been explained in detail based on.
[1]
a first delivery roll that sends out the first carrier film;
a first application section that applies a first resin composition onto the first carrier film;
a reinforcing fiber supply section that supplies cut pieces of reinforcing fibers onto the first resin composition;
a second delivery roll that sends out a second carrier film;
a second application section that applies a second resin composition onto the second carrier film;
a conveyance unit that conveys the first carrier film and the second carrier film;
a pressurizing unit that presses the first carrier film and the second carrier film that sandwich a laminate including the first resin composition and the second resin composition to which the cut pieces have been supplied;
Equipped with
The pressure unit has a crown roll extending in an axial direction perpendicular to the conveyance direction of the first carrier film and the second carrier film.
Manufacturing equipment for fiber-reinforced composite sheets.
[2]
The taper angle of the crown roll is 0.1° or more and 1.3° or less,
The manufacturing device for a fiber-reinforced composite sheet according to [1], wherein a dimension of the crown roll along the axial direction is 2000 mm or less.
[3]
The fiber-reinforced composite sheet according to [1] or [2], wherein the difference between the center diameter of the crown roll and the diameter of the end of the crown roll in the axial direction is 0.5 mm or more and 8 mm or less. Manufacturing equipment.
[4]
The manufacturing apparatus for a fiber-reinforced composite sheet according to any one of claims [1] to [3], wherein the pressurizing section has a smooth receiving roll corresponding to the crown roll.
[5]
The pressing section has a smooth roll that presses the laminate,
The fiber-reinforced composite sheet manufacturing apparatus according to any one of [1] to [4], wherein the smooth roll is located most downstream of the pressure section in the conveyance direction.
[6]
The pressure unit includes a first uneven roll and a second uneven roll that are adjacent to each other in the conveyance direction and located on substantially the same plane,
The surface of the first uneven roll is provided with a plurality of first convex portions arranged intermittently along the axial direction,
The surface of the second uneven roll is provided with a plurality of second convex portions arranged intermittently along the axial direction,
The manufacturing device for a fiber-reinforced composite sheet according to any one of [1] to [5], wherein the plurality of first convex portions and the plurality of second convex portions are provided alternately in the axial direction.
[7]
a step of applying a first resin composition onto the first carrier film being transported;
supplying cut pieces of reinforcing fibers onto the first resin composition;
a step of applying a second resin composition onto the second carrier film being transported;
a step of bringing the first carrier film and the second carrier film close to each other to form a laminate containing the first resin composition and the second resin composition to which the cut pieces have been supplied;
a step of pressurizing the laminate with a pressurizing section;
Equipped with
The pressure unit has a crown roll extending in an axial direction perpendicular to the conveyance direction of the first carrier film and the second carrier film.
A method for manufacturing a fiber-reinforced composite sheet.

However, one aspect of the present disclosure is not limited to the above embodiment, the above modification, and [1] to [7] above. One aspect of the present disclosure can be further modified without departing from the gist thereof. For example, in the embodiment and the modified example described above, the crown roll included in the pressure section is located upstream of the other rolls, but the present invention is not limited thereto. For example, in the pressure section, the crown roll may be located downstream of the other rolls. Moreover, the pressurizing part may have a plurality of crown rolls. In this case, for example, crown rolls may be disposed upstream and downstream of the pressure section, respectively.

In the above embodiment and the above modification, the pressure section includes other rolls in addition to the crown roll, but is not limited to this. The pressure section does not need to have any other rolls as long as it has at least one crown roll. Alternatively, the pressure section may include a crown roll and a member that presses the laminate, such as a mesh belt, instead of the other rolls.

In the above modification, the pressure section of the manufacturing device does not need to have a crown roll. Even in this case, the laminate is well pressurized by the crown roll included in the deaerator, and the gas existing between the first carrier film and the second carrier film is transferred to both ends of the laminate in the axial direction. Pushed out towards the crown roll. Therefore, even if the pressure section of the manufacturing device does not have a crown roll, the above-described method for manufacturing a fiber-reinforced composite sheet can be carried out due to the presence of the deaeration device used in conjunction with the manufacturing device, and , the same effects as in the above embodiment can be achieved. In addition, in the said modification, a deaerator may have several crown rolls.

The present disclosure will be explained in more detail with reference to the following examples, but the present disclosure is not limited to these examples.

[Hydroxyl value]
The hydroxyl value of the resin was measured based on the specified method of JIS K 0070:1992. Specifically, the hydroxyl value of the resin was obtained by adding an acetylation reagent to 1 g of a resin sample, reacting at a specified temperature and time, and then performing neutralization titration with a potassium hydroxide ethanol solution.

[viscosity]
The viscosity of the resin was measured at 25° C. using a digital viscometer (manufactured by Atago Co., Ltd., VISCO (registered trademark)).

[Manufacture of resin composition (1)]
In a 2L flask equipped with a thermometer, nitrogen inlet tube, and stirrer, 667 parts by mass of epoxy resin ("Epicron 850" manufactured by DIC Corporation, bisphenol A type epoxy resin, epoxy equivalent 188 g/eq) and 96.9 parts by mass of bisphenol A were added. , 0.38 parts by mass of 2-methylimidazole were charged, the temperature was raised to 120°C, and the mixture was reacted for 3 hours to obtain an epoxy resin having an epoxy equivalent of 283 g/eq. Next, the inside of the reaction system was cooled to around 60° C., and 228 parts by mass of methacrylic acid and 0.29 parts by mass of t-butylhydroquinone were added. After the temperature was raised to 90° C. while flowing a gas containing a 1:1 mixture of nitrogen and air, 0.23 parts by mass of 2-methylimidazole was added. The temperature was raised to 110° C. and the reaction was carried out for 10 hours, and the end point of the reaction was defined as the point where the acid value became 6 or less, to obtain a vinyl ester resin (1) having a hydroxyl value of 206 mgKOH/g.

55 parts by mass of vinyl ester resin (1), 45 parts by mass of phenoxyethyl methacrylate, 20 parts by mass of polyisocyanate ("Cosmonate LL" manufactured by Mitsui Chemicals Fine Co., Ltd.), and a polymerization initiator ("Kayacarbon" manufactured by Kayaku Nourion Co., Ltd.). AIC-75" and 1 part by mass of organic peroxide were mixed to obtain a resin composition (1). The viscosity of the resin composition (1) was 3 Pa·s.

[Manufacture of resin composition (2)]
40 parts by mass of tetraglycidyldiaminodiphenylmethane (manufactured by Sigma-Aldrich), 40 parts by mass of bisphenol A epoxy resin ("EPICLON 840LV", manufactured by DIC Corporation, epoxy equivalent weight 178 g/eq), 1,4-butanediol diglycidyl ether (ANHUI XINYUAN) Chemical Co., Ltd. "XY-622") 5 parts by mass, glycerol polyglycidyl ether (Nagase Sangyo Co., Ltd. "EX-313", epoxy equivalent 141 g/eq) 15 parts by mass, fluorine mold release agent (Daikin Industries, Ltd. "EX-313") Daifree FB-962”) 2 parts by mass, dicyandiamide (“DDA5” manufactured by PTI Japan Co., Ltd.) 8 parts by mass, 4,4'-methylenebis(phenyldimethylurea) (PTI Japan Co., Ltd.) 6 parts by mass of Omicure 52 (manufactured by Co., Ltd.) were mixed using three rolls. 7 parts by mass of thermoplastic resin particles ("F303" manufactured by Aica Kogyo Co., Ltd., poly(meth)acrylic acid ester organic fine particles) were further mixed into the obtained mixture to obtain a resin composition (2). The viscosity of the resin composition (2) was 12 Pa·s.

[Example 1]
(Manufacturing equipment for sheet molding compound)
A manufacturing apparatus 1 shown in FIG. 1 was prepared. One crown roll, four uneven rolls, and one smooth roll were installed in order from the front of the process as a pressurizing part for passing the laminate. All receiving rolls installed under the conveyor belt for each roll were smooth rolls. In addition, the four uneven|corrugated rolls were arrange|positioned so that the convex part of adjacent uneven|corrugated rolls may be mutually located alternately in the axial direction. Details of each role are as follows.
Crown roll (1): center outer diameter 136 mm, both ends outer diameter 130 mm, axial length 1300 mm, made of silicone rubber.
Concave and convex roll: Maximum axis diameter 160mm, length in direction 1300mm, width of protrusions 3mm, interval between protrusions 9mm, height of protrusions 10mm, made of stainless steel.
Smooth roll: diameter 100mm, axial length 1300mm, made of stainless steel.
Receiving roll: diameter 80mm, axial length 1300mm, made of stainless steel.

(Manufacture of sheet molding compound)
A sheet molding compound was manufactured using the manufacturing apparatus 1 according to the manufacturing method described in the above embodiment. Here, a laminate film of a polyethylene film and a polypropylene film was used as the first carrier film F1 and the second carrier film F2 shown in FIG. Further, the resin composition was applied to each of the first carrier film F1 and the second carrier film F2 at a coating amount of 0.5 kg/m ² . In addition, carbon fiber roving ("T700SC-12000-50C" manufactured by Toray Industries, Inc.) was used as the reinforcing fiber RF, and the reinforcing fiber RF was cut into 25 mm by the cutting device 12 to form cut pieces CC. Then, the cut piece CC was dropped from the air so that the sheet molding compound obtained had no fiber directionality and had a uniform thickness. Here, the cut piece CC was dropped so that the carbon fiber content in the obtained sheet molding compound was 60% by mass.

Subsequently, the first carrier film F1 and the second carrier film F2 are brought close to each other, and a laminate S containing the first resin composition 3a and the second resin composition 6a in which the cut pieces CC, which are carbon fibers, are arranged. was formed. This laminate S was conveyed by a transfer belt, passed through a pressurizing section 8, and then wound up by a winding roll 9. Then, the rolled-up laminate S was left standing in a constant temperature machine set at 45° C. for 24 hours to obtain a sheet molding compound (basis weight: 2 kg/m ² ).

(Manufacture of molded products)
The sheet molding compound (SMC) obtained above was cooled to 25° C., and two test pieces of 225 mm×225 mm were cut out. Two of the test pieces were stacked and set in the center of a 300 mm x 300 mm flat plate mold, and press-molded for 5 minutes at a mold temperature of 140°C and a pressure of 10 MPa to form a flat plate-shaped molded product with a thickness of about 2 mm. Obtained.

[Examples 2 to 10 and Comparative Examples 1 and 2]
SMCs and molded products were obtained in the same manner as in Example 1, except that the type of resin composition and the type and number of rolls were changed as shown in Tables 1 and 2 below. The crown roll (2) shown in Tables 1 and 2 is a silicone rubber roll having an outer diameter of 136 mm at the center, an outer diameter of 106 mm at both ends, and an axial length of 1300 mm.

[Various evaluations]
Various evaluations were made for Examples 1 to 10 and Comparative Examples 1 and 2 based on the following criteria. The results of each evaluation are listed in Tables 1 and 2 below.

(Evaluation of bubble removal effect)
The SMC manufacturing process was visually confirmed, and the presence or absence of air bubbles before passing through the pressurizing section 8 and the bubble removal effect after passing through the pressurizing section 8 were evaluated based on the following criteria.

(Surface smoothness of SMC)
The surface of the obtained SMC was visually confirmed and the smoothness of the surface was evaluated.

(Evaluation of resin impregnation in SMC)
First, the mass of 1000 carbon fiber bundles cut to 12.5 mm was measured, the average value was calculated, and this was defined as the unimpregnated average fiber mass. Further, a 30 cm x 30 cm test piece was cut out from the SMC obtained in each Example and each Comparative Example. The SMC was cut into two pieces at the center in the thickness direction to expose the inside. One hundred carbon fiber bundles were taken out from arbitrary locations on the exposed internal surface, their total mass was measured, and the average mass per carbon fiber bundle was calculated. This operation was performed on five test pieces. The average value of the average mass of the five points was calculated, and this was taken as the average fiber mass after impregnation. An analytical electronic balance GR-202 (manufactured by A&D Co., Ltd., weighing unit: 0.01 mg) was used to measure each mass.

The mass ratio between the average fiber mass after impregnation and the average unimpregnated fiber mass was calculated and evaluated based on the following criteria.
5: The fiber mass after impregnation increases by 40% or more compared to the unimpregnated fiber mass. 4: The fiber mass after impregnation increases by 20% or more and less than 40% compared to the unimpregnated fiber mass. 3: The fiber mass after impregnation increases by 40% or more compared to the unimpregnated fiber mass. 2: The fiber mass after impregnation increases by 3% or more and less than 10% compared to the unimpregnated fiber mass. 1: The fiber mass after impregnation increases by less than 3% compared to the unimpregnated fiber mass.

(Surface smoothness of molded product)
The surface of the obtained molded product was visually confirmed and the smoothness of the surface was evaluated.

(Evaluation of resin impregnation in molded product)
Using a digital microscope VHX-5000 (manufactured by Keyence Corporation), the cross section of the molded product obtained above was observed at a magnification of 50 times, and the impregnability was evaluated according to the following criteria. Two types of cross sections of the molded product were prepared to be observed. The first type of cross section is a cross section that extends in any one direction in the surface direction of the molded product and is perpendicular to the surface of the molded product. The second type of cross section is a cross section perpendicular to the first type of cross section and the surface of the molded article. The number of unimpregnated areas was the sum of the unimpregnated areas observed in each of the two types of cross sections.
5: 2 or less unimpregnated areas 4: 3 or 4 unimpregnated areas 3: 5 unimpregnated areas 2: 6 to 10 unimpregnated areas 1: 11 or more unimpregnated areas

DESCRIPTION OF SYMBOLS 1... Manufacturing device (manufacturing device for fiber reinforced composite sheet), 2... First delivery roll, 3... First application section, 3a... First resin composition, 4... Reinforced fiber supply section, 5... Second delivery roll , 6... Second application section, 6a... Second resin composition, 7... Conveyance section, 8... Pressure section, 9... Winding roll, 11... Pulling roll, 12... Cutting device, 21... Receiving roll, 21a... First smooth roll, 21b... Second smooth roll, 22, 22A... Crown roll, 22a... End, 23... Roll (first uneven roll), 23a... Surface, 23b... Convex part (first convex part), 24 ...roll (second uneven roll), 24a...surface, 24b...convex part (second convex part), 27...smooth roll, 30a to 30g...smooth receiving roll, 100...deaerator, 101...feeding roll, 102... Deaeration section, 103... Winding roll, 110... Crown roll, CC... Cut piece, F1... First carrier film, F2... Second carrier film, OD1... Outer diameter (center diameter), OD2... Outer diameter (edge) diameter), RF...Reinforced fiber, S, S1...Laminated body.

Claims

a first delivery roll that sends out the first carrier film;
a first application section that applies a first resin composition onto the first carrier film;
a reinforcing fiber supply section that supplies cut pieces of reinforcing fibers onto the first resin composition;
a second delivery roll that sends out a second carrier film;
a second application section that applies a second resin composition onto the second carrier film;
a conveyance unit that conveys the first carrier film and the second carrier film;
a pressurizing unit that presses the first carrier film and the second carrier film that sandwich a laminate including the first resin composition and the second resin composition to which the cut pieces have been supplied;
Equipped with
The pressure unit has a crown roll extending in an axial direction perpendicular to the conveyance direction of the first carrier film and the second carrier film.
Manufacturing equipment for fiber reinforced composite sheets.
The taper angle of the crown roll is 0.1° or more and 1.3° or less,
The manufacturing apparatus for a fiber-reinforced composite sheet according to claim 1, wherein a dimension of the crown roll along the axial direction is 2000 mm or less.
The manufacturing device for a fiber-reinforced composite sheet according to claim 1 or 2, wherein the difference between the center diameter of the crown roll and the diameter of the end portion of the crown roll in the axial direction is 0.5 mm or more and 8 mm or less. .
The fiber reinforced composite sheet manufacturing apparatus according to claim 1 or 2, wherein the pressurizing section has a smooth receiving roll corresponding to the crown roll.
The pressing section has a smooth roll that presses the laminate,
The fiber-reinforced composite sheet manufacturing apparatus according to claim 1 or 2, wherein the smooth roll is located at the most downstream position of the pressure section in the conveyance direction.
The pressure unit includes a first uneven roll and a second uneven roll that are adjacent to each other in the conveyance direction and located on substantially the same plane,
A plurality of first convex portions arranged intermittently along the axial direction are provided on the surface of the first uneven roll,
The surface of the second uneven roll is provided with a plurality of second convex portions arranged intermittently along the axial direction,
The manufacturing device for a fiber-reinforced composite sheet according to claim 1 or 2, wherein the plurality of first convex portions and the plurality of second convex portions are provided alternately in the axial direction.
a step of applying a first resin composition onto the first carrier film being transported;
supplying cut pieces of reinforcing fibers onto the first resin composition;
a step of applying a second resin composition onto the second carrier film being transported;
a step of bringing the first carrier film and the second carrier film close to each other to form a laminate containing the first resin composition and the second resin composition to which the cut pieces have been supplied;
a step of pressurizing the laminate with a pressurizing section;
Equipped with
The pressure unit has a crown roll extending in an axial direction perpendicular to the conveyance direction of the first carrier film and the second carrier film.
A method for manufacturing a fiber reinforced composite sheet.