TW201829203A - Method for producing FRP precursor, method for producing laminate, method for producing printed circuit board, and method for producing semiconductor package - Google Patents

Abstract

The present invention provides a method for producing an FRP precursor according to which a resin film provided with a support is affixed to an aggregate, the support can be easily peeled from the resin film thereafter, and no resin components will adhere to the separated support side. The present invention further provides a method for producing a laminate involving the use of the FRP precursor obtained by the method for producing an FRP laminate, a method for producing a printed circuit board, and method for producing a semiconductor package. More specifically, the present invention provides a method for producing an FRP precursor according to which a resin film provided with a support is affixed to an aggregate, and the support is peeled from the resin film thereafter, wherein the resin film comprises a thermosetting resin composition containing a siloxane compound (a).

Description

Manufacturing method of fiber-reinforced plastic precursor, manufacturing method of laminated body, manufacturing method of printed wiring board, and manufacturing method of semiconductor package

The invention relates to a method for manufacturing a fiber-reinforced plastic precursor, a method for manufacturing a laminated body, a method for manufacturing a printed wiring board, and a method for manufacturing a semiconductor package.

FRP (Fiber Reniforced Plastics, fiber reinforced plastics) is a composite material that uses a material with a high modulus of elasticity such as fiber as the aggregate and places the aggregate in a matrix such as plastic. It is made by increasing the strength, so it can produce weather resistance, heat resistance, chemical resistance, and light weight, and it is a composite material that is cheap, lightweight, and excellent in durability. Because these properties can be exerted, fiber-reinforced plastics are used in a wide range of technical fields. For example, fiber-reinforced plastics are used in structural materials such as residential equipment, ships, vehicles, and aircraft because of their styling and high strength. In addition, fiber-reinforced plastics are used in the field of electronic components such as electronic devices and printed wiring boards because they can exhibit insulation properties.

Examples of the method for manufacturing fiber-reinforced plastic include the following methods: the RTM (Resin Transfer Molding) method, in which a resin is poured into a mold in which an aggregate is tiled; and a hand lay-up method And spray up method, which is a multi-layer lamination while laying the aggregate and degassing the resin; and SMC (Sheet Molding Compound) compression method, which uses a mold to A sheet-like material made by mixing aggregate and resin is compression-molded.

When using fiber-reinforced plastics for printed circuit boards, the thickness of fiber-reinforced plastics for printed circuit boards is required to be thinner than that of fiber-reinforced plastics for other uses. In addition, fiber-reinforced plastics for printed wiring boards are required to have the following high specifications: the tolerance range of the thickness variation of the fiber-reinforced plastics after molding is small, and there is no void. Therefore, most fiber-reinforced plastics for printed wiring boards are mostly manufactured by the Hand Lay-up (HLU) method. The hand product method is a manufacturing method that uses a coater to apply a varnish obtained by dissolving a resin onto an aggregate material, and then performs drying, solvent removal, and thermal curing (see Patent Document 1). In the manual product method, if a thermosetting resin is applied to the aggregate in advance, workability can be improved, and the load on the surrounding environment can be reduced.

However, when using non-calendered polyaramide nonwoven fabric, thin fiberglass paper, and thin woven fabric as aggregates, these aggregates have low strength as aggregates, so workability is as follows. Poor: When coating varnish and then performing solvent removal, drying, and thermal hardening, the empty weight will increase the load of the aggregate and cause the aggregate to break; or, when the amount of resin to be applied is adjusted, the coating machine is shortened. At the gap, the bones and the like are torn.

In addition, it is necessary for the fiber-reinforced plastic for a printed wiring board to take into consideration both the high precision of the thickness after lamination and the filling property (moldability) of the circuit pattern with the resin to the inner layer. Therefore, it is complicated to produce a plurality of fiber-reinforced plastic precursors in one kind of aggregate. The foregoing plurality of fiber-reinforced plastic precursors are those in which the amount of resin adhered to the aggregate is different by several percent by mass, and the hardening of the thermosetting resin is changed. Time-formers, combinations of them, etc. Furthermore, in order to change various coating conditions for manufacturing, the loss of materials used for manufacturing is also large.

Therefore, there is a method in which instead of directly coating the thermosetting resin on the bone material, a resin film in which the thermosetting resin is made into a thin film is prepared in advance, and then the bone material and the resin film are heated and applied. It is adhered by pressure to form a fiber-reinforced plastic precursor (see Patent Document 2). [Prior Art Literature] (Patent Literature)

Patent Document 1: Japanese Patent Application Laid-Open No. 01-272416. Patent Document 2: Japanese Patent Application Laid-Open No. 2011-132535.

[Problems to be Solved by the Invention] However, in the method described in Patent Document 2, it is sometimes difficult to peel the support from the resin film after the resin film with the support is adhered to the bone material. When the resin component adheres to the side of the peeled support, the resin component will be insufficient on the surface of the fiber-reinforced plastic precursor produced, which will cause warpage of the laminate, printed wiring board, and semiconductor package. The reason is further that problems such as deterioration of heat resistance and poor appearance may easily occur.

In view of such a situation, a problem to be solved by the present invention is to provide a method for manufacturing a fiber-reinforced plastic precursor. The method can easily support a resin film after bonding the resin film with a support to the bone material. The body is peeled from the resin film, and the resin component does not adhere to the peeled support body side. Further, the problem to be solved by the present invention is to provide a method for manufacturing a laminated body, a method for manufacturing a printed wiring board, and a method for manufacturing a semiconductor package. These manufacturing methods use the aforementioned method for manufacturing a fiber-reinforced plastic precursor Obtained fiber-reinforced plastic precursor. [Technical means to solve the problem]

As a result of repeated and diligent researches by the present inventors in order to solve the above-mentioned problem to be solved, it was found that the resin component which is in close contact with the support body contains a siloxane compound and is produced by a specific method, which can solve The aforementioned problems to be solved further complete the present invention.

The present invention relates to the following techniques [1] to [12]. [1] A manufacturing method of a fiber-reinforced plastic precursor, the manufacturing method after bonding a resin film with a support to a bone material, peeling the support from the resin film with a support to form a fiber The reinforced plastic precursor, wherein the resin film is a resin film including a thermosetting resin composition, and the thermosetting resin composition contains a siloxane compound (a). [2] The method for producing a fiber-reinforced plastic precursor according to the above [1], wherein the siloxane compound (a) is represented by the following general formula (1): In the general formula (1), R ^a1 , R ^a2 , R ^a3, and R ^a4 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group, and R ^a5 and R ^a6 are each independently Ground represents an organic group, and m is an integer of 1-50. [3] The method for producing a fiber-reinforced plastic precursor according to [1] or [2], wherein the thermosetting resin composition further contains a thermosetting resin (b). [4] The method for producing a fiber-reinforced plastic precursor according to any one of [1] to [3], wherein the thermosetting resin composition further contains a maleimide compound (c), and The maleimide compound (c) has at least two N-substituted maleimide groups in one molecule. [5] The method for producing a fiber-reinforced plastic precursor according to any one of [1] to [4], wherein the thermosetting resin composition further contains an amine compound (d), and the amine compound (d ) Has at least two primary amine groups in one molecule. [6] The method for producing a fiber-reinforced plastic precursor according to any one of [1] to [5], wherein the thermosetting resin composition further contains a hardening accelerator (e). [7] The method for producing a fiber-reinforced plastic precursor according to any one of the above [1] to [6], wherein the thermosetting resin composition further contains an inorganic filler (f). [8] The method for producing a fiber-reinforced plastic precursor according to any one of the above [1] to [7], wherein the resin film with a support is heated and pressed under normal pressure to It fits on the bone. [9] The method for manufacturing a fiber-reinforced plastic precursor according to any one of the above [1] to [8], wherein the fiber-reinforced plastic precursor is used for a coreless substrate. [10] A method for manufacturing a laminated body, which is implemented by laminating and forming a fiber-reinforced plastic precursor, the fiber-reinforced plastic precursor is obtained by any one of the above [1] to [8] Obtained by the manufacturing method of the fiber-reinforced plastic precursor described above. [11] A method for manufacturing a printed wiring board. The manufacturing method is implemented by forming a circuit on a laminated body obtained by the method for manufacturing a laminated body described in [10] above. [12] A method for manufacturing a semiconductor package, which is implemented by assembling a semiconductor element on a printed wiring board, which is obtained by the method for manufacturing a printed wiring board described in [11] above. [Effect of the invention]

According to the present invention, it is possible to provide a method for manufacturing a fiber-reinforced plastic precursor, which can easily peel the support from the resin film after bonding the resin film with the support to the bone material, and the resin component Does not adhere to the peeled support side. A laminated body, a printed wiring board, and a semiconductor package obtained by using a fiber-reinforced plastic precursor obtained by this manufacturing method can suppress warpage and have excellent heat resistance. According to the present invention, it is possible to provide a method for manufacturing a laminated body, a method for manufacturing a printed wiring board, and a method for manufacturing a semiconductor package. These manufacturing methods use a fiber-reinforced plastic obtained by the aforementioned method for manufacturing a fiber-reinforced plastic precursor. Precursor.

[Manufacturing method of fiber-reinforced plastic precursor] The present invention has a feature of using a thermosetting resin composition containing a siloxane compound (a), and includes the following steps: bonding a resin film with a support After being on the aggregate, the support was peeled from the resin film to which the support was attached. Here, the so-called "bonding" includes the state where the resin component of the resin film with the support is in contact with the bone material, and also includes the resin component in the resin film that fills the voids in the bone material. , Especially the latter. First, an aspect of a specific manufacturing method of the fiber-reinforced plastic precursor is described in detail, and then the thermosetting resin composition is described in detail.

As a preferred aspect of the present invention, a state in which the aforementioned resin film with a support is heated and pressurized under normal pressure to adhere the resin film to the bone material can be cited. Hereinafter, a preferred embodiment of a method for manufacturing a fiber-reinforced plastic precursor and a device 1 for manufacturing a fiber-reinforced plastic precursor in the present invention will be described in detail with reference to FIG. 1. In addition, although the manufacturing apparatus 1 of a fiber-reinforced plastic precursor is set so that a pair of resin film (film made of a thermosetting resin composition) 54 may be melted and adhered to both sides of a sheet-like bone material 40 The above device is described, but it may be a device that melts and adheres only one resin film 54 to one surface of the sheet-like bone material 40. At this time, in FIG. 1, one of the resin feeding device 3, the protective film peeling mechanism 4, and the protective film winding device 5 which are located on the lower side (or upper side) than the aggregate 40 is not necessary. The apparatus 1 for manufacturing a fiber-reinforced plastic precursor is placed under normal pressure. The method for manufacturing a fiber-reinforced plastic precursor in the present invention can be implemented by using a fiber-reinforced plastic precursor manufacturing apparatus 1. Here, in this specification, "under normal pressure" is synonymous with "under atmospheric pressure". In other words, the so-called "heating and pressing the resin film with a support under normal pressure to attach it to the bone material" means "a fiber-reinforced plastic precursor under normal pressure In the manufacturing apparatus 1 of FIG. 1, a resin film with a support is heated and pressed by a heating and pressing device 6 to adhere the resin film to the bone material. When a fiber-reinforced plastic precursor is produced by this method, for example, it is preferable because the workability problem that is easy to occur when a vacuum laminator is used is not likely to occur.

An apparatus 1 for manufacturing a fiber-reinforced plastic precursor includes: an aggregate feeding device 2; a pair of resin film feeding devices 3 and 3; a sheet heating and pressing device 6; and a fiber-reinforced plastic precursor winding device 8. The fiber reinforced plastic precursor manufacturing device 1 preferably further includes: an aggregate heating device (not shown); a sheet pressure cooling device 7; a pair of resin film heating devices (not shown); a pair of protective film peeling Divide mechanisms 4 and 4; and, a pair of protective film winding devices 5 and 5.

The aggregate sending device 2 is a device that rotates the roller wound with the sheet-shaped aggregate 40 in a direction opposite to the winding direction to deliver the aggregate 40 wound on the roller. In FIG. 1, the aggregate feeding device 2 sends the aggregate 40 from the lower side of the roller toward the sheet heating and pressing device 6.

The pair of resin film feeding devices 3 and 3 include a roller that rolls the resin film 50 with a protective film, and a support mechanism that applies a certain tension to the resin film 50 with the protective film that is sent out. Supported so that the roller can rotate; and a pair of resin film feeding devices 3 and 3 is a feeding device that rotates a roller wound with a resin film 50 (with a protective film) in a direction opposite to the winding direction, The resin film 50 with the protective film wound on the roller is sent out. As described later, the resin film 50 with a protective film is a thin film including a resin film 54 and a protective film 52. The protective film 52 is laminated on the surface of the bone-side film on one side of the resin film 54 (in the Among the both sides of the resin film 54, the surface on the side of the aggregate 40) 54 a. Furthermore, in the resin film 50 with a protective film, a support is attached on the opposite side of the protective film 52. That is, it has a structure of a support body, a resin film, and a protective film.

A pair of resin film feeding devices 3 and 3 are each located on the front surface 40a side and the back surface 40b side of the bone material 40 to be fed. One of the resin film feeding devices 3 is located on the surface 40a side of the sent-out bone material 40, and the feeding device is such that the protective film 52 is positioned on the side of the sent-out bone material 40, and one of the resins with the protective film is attached. The film 50 is fed out from the lower side of the roller toward one of the protective film peeling mechanisms 4. Similarly, another resin film sending device 3 is located on the back surface 40b side of the sent-out bone material 40, and the sending-out device is such that the protective film 52 is located on the side of the sent-out bone material 40, and the other is provided with protection. The thin resin film 50 is sent from the upper side of the roller toward the other protective film peeling mechanism 4.

The pair of protective film peeling mechanisms 4 and 4 are rotary rollers located on the front surface 40a side and the back surface 40b side of the fed-out aggregate 40, respectively. One of the protective film peeling mechanisms 4 is a mechanism for peeling one of the protective films 52 from one of the resin films 50 with the protective film attached, and the peeling mechanism is for removing the protective film by The resin film 50 is pressed against the surface of the rotating roller, and then the resin film 54 is advanced toward the sheet heating and pressing device 6, and one of the protection films 52 is advanced toward one of the protection film winding devices 5; The resin film 50 of the film is sent out from one of the resin film feeding devices 3 and advances toward one of the protective film peeling mechanisms 4; the aforementioned resin film 54 is located on the first resin film 50 with a protective film. As a result, the bone-side film surface 54a of one of the resin films 54 is exposed. Similarly, another protective film peeling mechanism 4 is a mechanism for peeling another protective film 52 from another resin film 50 with a protective film attached, and the peeling mechanism is for removing the following: A resin film 50 with a protective film is pressed against the surface of the rotating roller, and then the resin film 54 is advanced toward the sheet heating and pressing device 6, and the other protective film 52 is advanced toward the other protective film winding device 5. ; The aforementioned another resin film 50 with a protective film is sent from another resin film feeding device 3 and advances toward another protective film peeling mechanism 4; the aforementioned resin film 54 is located on another resin with a protective film On the film 50. Thereby, the aggregate-side film surface 54 a of the other resin film 54 is exposed.

A pair of protective film winding devices 5 and 5 are respectively located on the front surface 40a side and the back surface 40b side of the delivered aggregate 40, and are winding devices for winding the protective films 52 and 52. The aforementioned protective films 52 and 52 are used. A pair of protective film peeling mechanisms 4 and 4 are obtained by peeling.

The aggregate heating device (not shown) includes a heating body (not shown), and each of them is located on the front surface 40 a side and the back surface 40 b side of the delivered aggregate 40. As this heating body, a radiation type heating body which heats the surface 40a of the aggregate 40 under normal pressure, and a radiation type heating body which heats the back surface 40b of the aggregate 40 under normal pressure are preferable. In addition, as the heating method of the aggregate, various methods such as radiation, contact, and convection can be used, but a heating method using a resin film described later will be simple and therefore preferable. From the viewpoint of suppressing radiant cooling, the heating position is preferably in front of the heating and compression roller having the sheet heating and pressurizing device 6 and is calculated as a position within 20 seconds from the heating and compression roller at a linear velocity, and more preferably The position within 5 seconds is more preferably a position within 1 to 5 seconds. In the step of heating the surface of the aggregate, the heating temperature of the front surface 40a and the back surface 40b of the aggregate 40 is preferably higher than the heating temperature of 5 to 70 ° C, and more preferably higher than 7 in the subsequent film compression bonding step. The temperature of -60 ° C is more preferably a temperature of 10-50 ° C.

One of the resin film heating devices (not shown) is preferably located on the surface 40a of the bone material 40 to be sent out so as to be able to heat the bone material side film surface 54a of the resin film 54 that is sent out. Between the resin film 54 and the aggregate-side film surface 54 a of the resin film 54. The other resin film heating device is preferably located on the back surface 40b of the sent-out bone material 40 and the other resin film 54 in a manner that can heat the bone-side film surface 54a of the sent-out another resin film 54. Between the aggregate-side film surfaces 54a. These resin film heating devices are heating bodies that heat the bone-side film surface 54a of the resin film 54 under normal pressure. The heating body is, for example, a radiant heating body.

The heat source of the radiation type heating body may be any one, and it is simple to use infrared rays or visible light including infrared rays, and it is easy to perform heating. This makes it possible to suppress deformation of the resin surface, surface variation, and the like caused by variation of the film. From the viewpoint of suppressing radiant cooling, the heating position is preferably in front of the heating and compression roller having the sheet heating and pressurizing device 6 and is calculated as a position within 20 seconds from the heating and compression roller at a linear velocity, and more preferably The position within 5 seconds is more preferably a position within 1 to 5 seconds. The heating temperature is preferably within a range of minus 20 to plus 30 ° C of the lowest melt viscosity temperature of the resin. The lowest melt viscosity temperature is obtained by measuring the thermosetting resin composition with a rheometer. In the film pre-heating step, the heating temperatures of the bone-side film surfaces 54a and 54a of the pair of resin films 54 and 54 are preferably higher than the heating temperatures of 5 to 70 ° C in the subsequent compression bonding step, respectively. The temperature is more preferably a temperature higher than 7 to 60 ° C, and still more preferably a temperature higher than 10 to 50 ° C.

The sheet heating and pressing device 6 includes a pair of heating and compression rollers, and a compression force applying mechanism (not shown) that applies a compression force to the pair of heating and compression rollers. The pair of heating and compression rollers has a heating body inside, and can be heated at a specific temperature set. The sheet heating and pressurizing device 6 uses a pair of rotating heating and compression rollers to press the resin films 54 and 54 on the fed bone material 40 to form a sheet-shaped fiber-reinforced plastic precursor 60 (film compression bonding). Step), and the fiber-reinforced plastic precursor 60 is sent toward the sheet pressure cooling device 7. Specifically, the front surface 40a and the back surface 40b of the aggregate 40 sent from the aggregate sending device 2 are laminated with resin films 54 and 54 sent from a pair of protective film peeling devices 4 and 4, respectively. In the method, the bone material 40 sent from the bone material sending device 2 and the resin films 54 and 54 sent from the pair of protective film peeling mechanisms 4 and 4 are fed between a pair of heated compression rollers. At this time, one of the resin films 54 is laminated on the bone material 40 such that the bone material side film surface 54 a side of the resin film 54 is adhered to the surface 40 a side of the bone material 40, and the other resin film 54 is In the manner that the surface 54a side of the aggregate material side film is adhered to the back surface 40b side of the aggregate material 40, another resin film 54 is laminated on the aggregate material 40 to form a fiber-reinforced plastic precursor 60. The fiber-reinforced plastic precursor 60 sent from the sheet heating and pressing device 6 is in a high temperature state.

The sheet pressure cooling device 7 includes a pair of cooling compression rollers, and a compression force applying mechanism (not shown) that applies a compression force to the pair of cooling compression rollers. A pair of cooling and compression rollers can compress and cool the high-temperature fiber-reinforced plastic precursor 60 sent from the sheet heating and pressurizing device 6 by rotating the pair of cooling and compression rollers, and then send them to the fiber-reinforced plastic precursor roll取 装置 8。 Take device 8.

The fiber-reinforced plastic precursor take-up device 8 includes a take-up roller that takes up a sheet-shaped fiber-reinforced plastic precursor 60 sent from the sheet pressure cooling device 7 and a drive mechanism (not shown) that makes The wheel rotates.

Furthermore, because the fiber-reinforced plastic precursor manufacturing apparatus 1 uses the so-called roller lamination method, the heating temperature of the aggregate 40 and the resin film 54 when the roller lamination is performed in the sheet heating and pressing device 6 is preferable. In the width direction, the central temperature is higher and the end temperature is lower. More specifically, in the width direction, the temperature at the center is preferably 5 to 20 ° C higher than the temperature at the end. The pressing of the roller stack is to apply pressure to the end of the roller to apply linear pressure to the whole by utilizing the rigidity of the roller. At this time, the roller is slightly deformed into an arcuate shape. Therefore, if the viscosity is the same, the bow-shaped deformation is promoted. Therefore, by reducing the viscosity of the central portion of the resin film 54 and increasing the viscosity of the end portion, the difference in the fluidity between the central portion and the end portion can be suppressed. Bow-shaped deformation. In addition, if a difference is applied to the heating temperature in the width direction, there will be a difference in the hardenability of the molten resin in the width direction. Therefore, it is preferable to use the same heating method but different temperatures during rolling. In a method, the heating body is arranged in a V shape to control the distance from the center portion and the end portion to the roller. In addition, it is preferable to cool by a cooling and compression roller after rolling to remove unnecessary heat and flatten the product.

The above-mentioned manufacturing apparatus 1 for a fiber-reinforced plastic precursor operates in the following manner. First, the sheet-shaped bone material 40 is sent out from the bone material feeding device 2 toward the sheet heating and pressing device 6. At this time, the front surface 40a and the back surface 40b of the aggregate 40 are exposed. Then, as needed, the front surface 40a and the back surface 40b of the aggregate 40 are heated by a heating body (not shown) such as an aggregate heating device under normal pressure (the surface heating step of the aggregate). On the other hand, the protective film 52 peels off one of the resin films 50 attached with the protective film from the lower side of the roller of one of the resin film feeding devices 3 toward one of the protective films so as to be positioned on the side of the bone 40 to be sent out. Agency 4 sends out. In addition, the protective film 52 feeds another resin film 50 with a protective film so as to be positioned on the side of the bone material 40 to be fed out from the upper side of the roller of the other resin film feeding device 3 toward the other protective film peeling mechanism 4 .

Then, one of the sent out resin films 50 with a protective film is hung on one of the protective film peeling mechanisms 4, that is, by rotating the roller to rotate, so as to expose the aggregate-side film surface 54a from one of them. The protective film-attached resin film 50 peels off one of the protective films 52 and advances one of the resin films 54 toward the sheet heating and pressing device 6. As a result, the bone-side film surface 54a of one of the resin films 54 is exposed. Similarly, when another sent-out resin film 50 with a protective film is hung on another protective film peeling mechanism 4, that is, by rotating a roller, the exposed film surface 54a of the aggregate-side film is exposed from the other side. A protective film-attached resin film 50 peels off the other protective film 52 and advances the other resin film 54 toward the sheet heating and pressing device 6. Thereby, the bone-side film surface 54a of the other resin film 54 is exposed. The peeled pair of protective films 52 and 52 can be wound up by a pair of protective film winding devices 5 and 5, respectively. Before the resin film 54 that has exposed the bone-side film surface 54a reaches the sheet heating and pressurizing device 6, a resin film heating device (not shown) can be used to radiate from the bone-side film surface 54a side of the resin film 54 The resin film 54 is heated (thin film pre-heating step). Thereby, the aggregate-side film surface 54a of the resin film 54 is melted.

On the aggregated material 40 which is fed out from the aggregated material feeding device 2 and the front surface 40a and the back surface 40b are heated, the aggregate side film surfaces 54a and 54a are laminated with the molten resin films 54 and 54, respectively, from the aggregate material. The aggregate 40 sent out by the sending-out device 2 and the resin films 54 and 54 sent out from each of the pair of protective film peeling mechanisms 4 and 4 are sent between a pair of heated compression rollers 6. Further, under normal pressure, the sheet heating and pressing device 6 is used to press the bone-side film surfaces 54a and 54a of the pair of resin films 54 and 54 to the heated bone material 40 on the front surface 40a and the back surface 40b, respectively. A fiber-reinforced plastic precursor 60 is obtained (film compression bonding step). At this time, by controlling the temperature of the heating bodies inside the pair of heating and compression rollers, the pair of heating and compression rollers can be maintained at a constant temperature, and the film can be pressurized while being heated during the film compression bonding step.

When the resin film is heated and pressurized to adhere to the aggregate, the temperature of the compression roller is preferably in the range of minus 40 ° C to + 20 ° C of the lowest melting viscosity temperature, which is obtained by using a rheometer It is obtained by measuring the thermosetting composition to be used in the formation of a resin film. The pressure may be any linear pressure. However, when the test method of No. 2.3.17.1 of IPC-TM-650 is used to apply heat and pressure using roll pressure, it is preferable that the bleed out of a 1.6 mm punching hole is 50 μm or more and 6.4. The exudation of a mm punch is 1200 μm or less, and more preferably the exudation of a 1.6 mm punch is 100 μm or more and the 6.4 mm punch is 500 μm or less.

The minimum melt viscosity temperature of the thermosetting resin composition is preferably from 60 to 150 ° C, more preferably from 80 to 140 ° C, and even more preferably from 100 to 150 ° C from the viewpoint of the productivity of the fiber-reinforced plastic precursor. 130 ° C.

In the film compression bonding step, the resin film 54 is adhered to the aggregate material 40 in an atmosphere with good workability. At this time, the heating and compression rollers of the sheet heating and pressurizing device 6 are used to heat the aggregate-side film surface 54a through the carrier film. Instead of melting and flowing the resin film 54, the resin film 54 flows. The side of the film 54 to be adhered to the aggregate 40 is heated, or the aggregate 40 is heated in advance. Thereby, the resin component can be made high-temperature on the front surface 40a and the back surface 40b of the bone material 40 to reduce its viscosity, thereby improving the impregnation of the bone material and suppressing the bone from being caused by excessive heating. The resin viscosity of the unrelated portion of the material 40 decreases, and the excessive heating is caused by the heating and compression rollers of the sheet heating and pressing device 6. In other words, it is possible to achieve both the filling property of the resin in the voids in the aggregate 40 and the prevention of resin extrusion from the ends, and the productivity of the fiber-reinforced plastic precursor 60 can be improved. As described above, it is preferable to heat at least one of the facing surfaces of the resin film with a support and the aggregate under normal pressure, and then heat and compress the side of the roller by heating. The both sides are heated and pressurized while being sandwiched, thereby bonding the resin film with a support to the aggregate.

The fiber-reinforced plastic precursor 60 sent out from the sheet heating and pressing device 6 is further pressed and cooled by the sheet pressing and cooling device 7. The fiber-reinforced plastic precursor 60 sent out from the sheet pressure cooling device 7 is wound up by the fiber-reinforced plastic precursor winding device 8.

As described above, the method for producing a fiber-reinforced plastic precursor according to the present invention is not a so-called vacuum lamination method, but an aggregate material to be adhered to a resin film under normal pressure (atmospheric pressure) with good workability. Heating on the other side, or heating the aggregate in advance, can balance the filling of the voids in the aggregate with the resin and prevent the resin from extruding from the ends, and can produce a fiber-reinforced plastic precursor with good productivity.

Next, a thermosetting resin composition used in the production of the resin film used in the present invention will be described. The resin film used in the present invention is a resin film including the thermosetting resin composition, and may be in a state of a "resin film with a support" with a support. [Thermosetting resin composition] The thermosetting resin composition used as a material for a resin film is a thermosetting resin composition containing a siloxane compound (a) (hereinafter, also referred to as "(a) component") Thing. By using a resin film containing such a thermosetting resin composition, after the resin film with a support body is bonded to the aggregate, the support body can be easily peeled from the resin film, and the resin component is not changed. Will attach to the side of the peeled support.

<Siloxane compound (a)> The siloxane compound (a) is not particularly limited as long as it is a compound containing a siloxane skeleton, and it may be used alone or in combination of two or more. The silicone compound (a) is preferably reactive with the component (c) or (d) described below in order to improve the compatibility in the thermosetting resin composition. As the siloxane compound (a), from the viewpoints that the resin residue on the support at the time of peeling is small, the heat resistance is excellent, and the amount of warpage (hereinafter referred to as low warpage) can be reduced, for example, it is preferable It is a siloxane compound represented by the following general formula (1).

In the general formula (1), R ^a1 , R ^a2 , R ^a3, and R ^a4 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group, and R ^a5 and R ^a6 are each independently Ground represents an organic group, and m is an integer of 1-50.

Examples of the alkyl group represented by R ^a1 , R ^a2 , R ^a3, and R ^{a4 in the} general formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Tertiary butyl, n-pentyl, etc. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group. The alkyl group in the substituted alkyl group is the same as the alkyl group represented by R ^a1 , R ^a2 , R ^a3, and R ^a4 , and preferably the same. The substituent in the substituted alkyl group is preferably selected from the group consisting of an amine group, an epoxy group, an alicyclic epoxy group, a polyether residue, a phenyl group, a hydroxyl group, a mercapto group, a carboxyl group, and a (methyl) group. At least one of the group consisting of an acrylic group, and more preferably a hydroxyl group. That is, as the substituted alkyl group, a methylol group (hydroxymethyl) is preferable. Examples of the alicyclic epoxy group include an epoxy cyclohexyl group and the like. Examples of the substituent of the phenyl group in the substituted phenyl group include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an alkynyl group having 2 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include the same alkyl groups as those described above. Examples of the alkenyl group having 2 to 5 carbon atoms include a vinyl group and an allyl group. Examples of the alkynyl group having 2 to 5 carbon atoms include an ethynyl group and a propargyl group. Among the above, as R ^a1 , R ^a2 , R ^a3, and R ^a4 , a methyl group, a phenyl group, and a methanol group are preferable, and all of them are preferably a methyl group. When m is 2, it is preferred that at least one R ^a1 of the plurality of R ^a1 is a methanol group, and R ^a1 and R ^a2 which are not methanol groups, and R ^a3 and R ^a4 are all methyl groups.

The organic group represented by R ^a5 and R ^a6 is preferably a substituted or unsubstituted organic group, preferably a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and more preferably a substituted or unsubstituted alkyl group. Substituted methyl. The substituent when substituted is preferably at least one selected from the group consisting of an amine group, an epoxy group, an alicyclic epoxy group, a hydroxyl group, a mercapto group, a carboxyl group, and a (meth) acrylic group. Examples of the alicyclic epoxy group include an epoxy cyclohexyl group and the like. The organic groups represented by R ^a5 and R ^{a6 are} preferably: a methyl group; an alkyl group substituted with an epoxy group; and an alkyl group substituted with an amine group. Furthermore, the siloxane compound (a) in which the organic group represented by R ^a5 and R ^a6 is an alkyl group substituted with an epoxy group or an alkyl group substituted with an amine group may be referred to as an epoxy group modification, respectively. Siloxane compounds, amine-modified silicone compounds. In addition, a siloxane compound (a) in which R ^a5 and R ^a6 are both alkyl groups substituted with an epoxy group is sometimes referred to as a two-terminal epoxy group modified siloxane compound, and R ^a5 and R ^a6 are siloxane compounds (a) which are alkyl groups substituted with amine groups, and are called amine modified siloxane compounds at both ends. m is an integer of 1 to 50, preferably an integer of 3 to 50, more preferably an integer of 8 to 50, still more preferably an integer of 10 to 40, and particularly preferably an integer of 15 to 40. When m is an integer of 2 or more, the plural R ^a1 and the plural R ^a2 may be the same as or different from each other.

As the siloxane compound (a), at least one of the aforementioned R ^a1 to R ^a6 is preferable from the viewpoints that the resin residue on the support at the time of peeling is small, excellent in heat resistance, and low warpage. These are compounds other than alkyl groups (especially methyl groups), that is, modified silicone compounds are preferred. Among the modified silicone compounds, a silicone compound having two primary amine groups in one molecule (that is, an amino modified silicone compound) and two rings in one molecule are preferred. Oxysiloxane compounds (ie, epoxy-modified silicone compounds). These compounds only need to have a primary amine group or an epoxy group on one or both of the side chain or the terminal of the siloxane skeleton, and from the viewpoints of availability and low warpage, It is preferable to have a primary amine group or epoxy group at the terminal, and it is more preferable to have a primary amine group or epoxy group at both terminals (sometimes referred to as modification at both terminals). The amine-modified silicone compound and the epoxy-modified silicone compound may be used singly or in combination. In addition to the above, as the modified siloxane compound, a siloxane compound having a methyl group in a side chain (hereinafter, referred to as a side chain methanol modified siloxane compound) is preferred.

As (a) component, a commercial item can be used. For example, as a "siloxane compound having two primary amine groups in one molecule" having a methyl group on the side chain, "KF-8010" (functional group equivalent of amine group 430 g / mol), " "X-22-161A" (functional group equivalent of amine group 800g / mol), "X-22-161B" (functional group equivalent of amine group 1500g / mol), "KF-8012" (functional group equivalent of amine group 2200g / mol), "KF-8008" (functional group equivalent of amine group 5700g / mol), "X-22-9409" (functional group equivalent of amine group 700g / mol, the above is manufactured by Shin-Etsu Chemical Industry Co., Ltd.), etc. . Examples of the "siloxane compound having two primary amine groups in one molecule" having a phenyl group on the side chain include "X-22-1660B-3" (the functional group equivalent of an amine group is 2200 g / mol, (Shin-Etsu Chemical Industry Co., Ltd.); "BY-16-853U" (functional group equivalent of amine group 460g / mol), "BY-16-853" (functional group equivalent of amine group 650g / mol), "BY- 16-853B "(the functional group equivalent of an amine group is 2200 g / mol, the above is manufactured by Toray Dow Corning Co., Ltd.) and the like. Examples of the both-terminal epoxy-modified silicone compound include: "X-22-163" (functional group equivalent of epoxy group 200 g / mol), "X-22-163A" (functionality of epoxy group) Group equivalent 1000 g / mol), "X-22-163B" (functional group equivalent of epoxy group 1800 g / mol), "KF-105" (functional group equivalent of epoxy group 490 g / mol), and the like. Examples of the side chain methanol-modified silicone compound include "X-22-4015" (hydroxyl value 30 mg KOH / g), "X-22-4039" (hydroxyl value 58 mg KOH / g), and the like. These compounds may be used individually by 1 type, and may use 2 or more types together. Among these, "X-22-163B" and "X-22-4039" are preferable from the viewpoints of low resin residual property to the support at the time of peeling, excellent heat resistance, and low warpage. , "X-22-161A".

When the component (a) is a siloxane compound having functional groups at both ends, the functional group equivalent is preferably 300 to 3000 g / mol, more preferably 400 to 2500 g / mol, and still more preferably 600 to 1500 g / mol. In the case of a siloxane compound having a hydroxyl group on the side chain, the hydroxyl value is preferably 20 to 100 mg KOH / g, and more preferably 25 to 70 mg KOH / g.

The content of the siloxane compound (a) in the thermosetting resin composition is smaller than that of the thermosetting property from the viewpoints that the resin residue on the support at the time of peeling is small, excellent in heat resistance, and low warpage. The solid content of the resin component in the resin composition is 100 parts by mass, preferably 2 to 30 parts by mass, more preferably 2 to 25 parts by mass, and still more preferably 3 to 20 parts by mass. Here, the solid content in the present embodiment means a component other than volatile materials such as water in a thermosetting resin composition and a solvent described later. That is, the solid content means a component that is liquid, syrupy, or waxy at room temperature of about 25 ° C, and is not necessarily solid. In addition, when referring to the solid content of a resin component, it means that it does not contain (f) inorganic substances, such as an inorganic filler.

<Thermosetting resin (b)> The thermosetting resin composition may further contain a thermosetting resin (b). However, this thermosetting resin (b) does not contain the said (a) component and the (c) component mentioned later. Examples of the thermosetting resin (b) include epoxy resins, phenol resins, unsaturated fluorene imine resins (but not including the component (c) described later), cyanate resins, isocyanate resins, and benzoxane. A benzoxazine resin, a propylene oxide resin, an amine resin, an unsaturated polyester resin, an allyl resin, a dicyclopentadiene resin, a silicone resin, a triazabenzene resin, a melamine resin, and the like. These may be used individually by 1 type, and may use 2 or more types together. Among these, one or more selected from the group consisting of epoxy resin and cyanate resin are preferable from the viewpoint of moldability and electrical insulation and the viewpoint of adhesion strength to a metal circuit. , More preferably epoxy resin.

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, Alpha-naphthol / cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, stilbene epoxy resin, ring containing a triazine skeleton Oxygen resin, epoxy resin containing fluorene skeleton, triphenylmethane epoxy resin, biphenyl epoxy resin, xylene epoxy resin, biphenylarene epoxy resin, naphthalene epoxy resin, dicyclopentane Diene epoxy resins, alicyclic epoxy resins, polyfunctional aromatic phenols, and polycyclic aromatic diepoxypropyl ether compounds such as anthracene, and those containing phosphorus compounds introduced into these epoxy resins Phosphorous epoxy resin, etc. These epoxy resins may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoints of heat resistance and flame retardancy, a biphenylarane-type epoxy resin and an α-naphthol / cresol novolac-type epoxy resin are preferred.

When the thermosetting resin composition contains the thermosetting resin (b), the content thereof is, relative to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition, from the viewpoint of low warpage. It is preferably 1 to 85 parts by mass, more preferably 2 to 80 parts by mass, still more preferably 5 to 80 parts by mass, and particularly preferably 10 to 80 parts by mass.

<Maleimide compound (c) having at least two N-substituted maleimide groups in one molecule> (c) As long as the component is at least two N-substituted maleimides in one molecule The amine-based maleimide compound (hereinafter, sometimes referred to as the maleimide compound (c)) is not particularly limited. As the maleimide compound (c), a maleimide compound having two N-substituted maleimide imino groups in one molecule is preferred, and more preferably, it is represented by the following general formula (c-1) ).

In the general formula (c-1), X ^c1 is a group represented by the following general formula (c1-1), (c1-2), (c1-3), or (c1-4).

In the general formula (c1-1), R ^{c1 is} each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms. p is an integer from 0 to 4.

In the general formula (c1-2), R ^c2 and R ^c3 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X ^c2 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond or A group represented by the following general formula (c1-2-1). q and r are each independently an integer of 0 to 4.

In the general formula (c1-2-1), R ^c4 and R ^c5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X ^c3 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, and a carbonyloxy group [—O—C (= O) — ], Keto, single bond. s and t are each independently an integer of 0 to 4.

In general formula (c1-3), n is an integer of 1-10.

In the general formula (c1-4), R ^c6 and R ^c7 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. u is an integer from 1 to 8.

Examples of the aliphatic hydrocarbon group represented by R ^c1 in the general formula (c1-1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, N-pentyl and so on. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among the above, R ^{c1 is} preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms. p is an integer of 0 to 4, and from the viewpoint of easiness of acquisition, it is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. When p is an integer of 2 or more, the plural R ^c1s may be the same as or different from each other.

In the general formula (c1-2), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and halogen atoms represented by R ^c2 and R ^c3 include the same ones as the above-mentioned R ^c1 . The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group and an ethyl group, and still more preferably an ethyl group. Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^c2 include methylene, 1,2-ethylenyl, 1,3-propylidene, 1,4-butylene, and 1,5. -Pentyl etc. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group, from the viewpoints of heat resistance and low thermal expansion. Examples of the alkylene group having 2 to 5 carbon atoms represented by X ^c2 include ethylene, propylene, isopropylidene, butylene, isobutylene, pentylene, and isopentylene. Among these, from the viewpoints of heat resistance and low thermal expansion, isopropylidene is preferred. As X ^c2 , among the above options, an alkylene group having 1 to 5 carbon atoms, an alkylene group having 2 to 5 carbon atoms, and a group represented by the general formula (c1-2-1) are more preferred. An alkylene group having 1 to 5 carbon atoms and a group represented by the general formula (c1-2-1) are preferred. Further preferred are the same as those described above or later. q and r are each independently an integer of 0 to 4. From the viewpoint of easiness of acquisition, it is preferably an integer of 0 to 2, and more preferably both of 0 or 2. When q or r is 2 or more In the case of an integer, a plurality of R ^c2 or R ^c3 may be the same or different.

In the general formula (c1-2-1), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and halogen atoms represented by R ^c4 and R ^c5 include the same groups as in the case of the aforementioned R ^c2 and R ^c3 . The same goes for the best. Examples of the alkylene group having 1 to 5 carbon atoms and the alkylene group having 2 to 5 carbon atoms represented by X ^c3 include the alkylene groups having 1 to 5 carbon atoms and 2 to 5 carbon atoms represented by X ^c2 The same alkyl group, preferably the same. As X ^c3 , among the above options, an alkylene group having 2 to 5 carbon atoms is preferable, and the more preferable one is as described above. s and t are integers of 0 to 4, and from the viewpoint of easiness of acquisition, they are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0. When s or t is an integer of 2 or more, a plurality of R ^c4 or R ^c5 may be the same as or different from each other. The general formula (c1-2-1) is preferably represented by the following general formula (c1-2-1 ').

X ^c3 , R ^c4 , R ^c5 , s, and t in the general formula (c1-2-1 ′) are the same as the examples in the general formula (c1-2-1), and the same are preferred.

The group represented by the aforementioned general formula (c1-2) is preferably a group represented by the following (c1-2 '), and more preferably represented by the following (c1-i) to (c1-iii) The group is more preferably a group represented by the following (c1-i) or (c1-iii).

X ^c2 , R ^c2 , R ^c3 , q, and r in the general formula (c1-2 ′) are the same as the examples in the general formula (c1-2), and preferably the same.

In the aforementioned general formula (c1-3), n is an integer of 1 to 10, and from the viewpoint of availability, an integer of 1 to 5 is preferable, and an integer of 1 to 3 is more preferable. In the aforementioned general formula (c1-4), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and halogen atoms represented by R ^c6 and R ^c7 are the same as those of R ^c1 in the aforementioned general formula (c1-1). The same goes for the better. u is an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1.

In the aforementioned general formula (c-1), X ^c1 may be any group represented by the aforementioned general formula (c1-1), (c1-2), (c1-3) or (c1-4). Among these, a group represented by (c1-2) is preferable from the viewpoints of low warpage, dimensional stability, heat resistance, and availability.

Specific examples of the maleimide compound (c) include bis (4-maleimideiminophenyl) methane, polyphenylmethane maleimide, and bis (4-maleimide). Phenyl) ether, bis (4-maleimidoiminophenyl) fluorene, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleate Fluorenimine, 4-methyl-1,3-phenylenebismaleimide, m-phenylbismaleimide, 2,2-bis [4- (4-maleimide) Phenoxy) phenyl] propane and the like. These may be used individually by 1 type, and may use 2 or more types together. Among these, bis (4-maleimidoiminophenyl) methane and bis (4-maleimidoimine) are preferred from the viewpoint of being highly reactive and capable of further increasing heat resistance. Phenyl) fluorene, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 2,2-bis [4- (4- Maleimidoiminophenoxy) phenyl] propane is more preferably 3,3'-dimethyl-5,5'-diethyl-4,4 from the viewpoint of solubility in solvents. '-Diphenylmethane bismaleimide, bis (4-maleimideiminophenyl) methane, 2,2-bis [4- (4-maleimideiminophenoxy) phenyl ] Propane is more preferably bis (4-maleimidoimidophenyl) methane and 2,2-bis [4- (4-maleimidoimidophenoxy) from the viewpoint of production cost. ) Phenyl] propane.

When the thermosetting resin composition contains the maleimide compound (c), the content is 100 parts by mass relative to the solid content of the resin component in the thermosetting resin composition from the viewpoint of low warpage. It is preferably 20 to 90 parts by mass, more preferably 30 to 85 parts by mass, and still more preferably 30 to 80 parts by mass.

<Amine compound (d) having at least two primary amine groups in one molecule> Amine compound (d) having at least two primary amine groups in one molecule (hereinafter, sometimes referred to as an amine compound (d)) It has no siloxane bond in the molecule and can be distinguished from the aforementioned component (a). From the viewpoint of heat resistance, the number of primary amine groups of the amine compound (d) is preferably 2 to 4, more preferably 2 or 3, and even more preferably 2. From the viewpoint of heat resistance, the amine compound (d) is preferably a diamine compound represented by any one of the following general formulae (d-1) to (d-3), and more preferably The diamine compound represented by any one of the general formula (d-1) or (d-3) is more preferably a diamine compound represented by the following general formula (d-1).

In the above formula, X ^d1 represents a single bond, an alkylene group having 1 to 5 carbon atoms, an alkylene group having 2 to 5 carbon atoms, -O-, a sulfofluorenyl group, a keto group, a fluoride diyl group, or benzene Phenylenedioxy group. R ^d1 and R ^d2 each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a methoxy group, or a hydroxyl group. v and w are each independently an integer of 0 to 4. X ^d2 to X ^d4 each independently represent a single bond, an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, —O—, or a sulfonyl group.

Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^d1 include methylene, 1,2-ethylenyl, 1,3-propylidene, 1,4-butylene, and 1,5. -Pentyl etc. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group, from the viewpoint of heat resistance. Examples of the alkylene group having 2 to 5 carbon atoms represented by X ^d1 include ethylene, propylene, isopropylidene, butylene, isobutylene, pentylene, and isopentylene. Among these, from the viewpoint of heat resistance, isopropylidene is preferred. As the fluorene diyl represented by X ^d1 , for example, fluorene-1,8-diyl, fluorene-1,7-diyl, fluorene-1,6-diyl, fluorene-1,5-diyl, fluorene -2,7-diyl, fluorene-2,6-diyl, fluorene-2,5-diyl, fluorene-3,6-diyl, fluorene-3,5-diyl, fluorene-4,5- Second base and so on. Examples of the benzenedioxy group represented by X ^d1 include 1,4-benzenedioxy, 1,3-benzenedioxy, and 1,2-benzenedioxy. As X ^d1 , among the above options, an alkylene group having 1 to 5 carbon atoms, —O—, and a sulfonyl group are more preferable, and an alkylene group having 1 to 5 carbon atoms and a sulfonyl group are more preferable.

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^d1 and R ^d2 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and n-butyl. Amyl and others. As the aliphatic hydrocarbon group, from the viewpoint of heat resistance, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, a methyl group and an ethyl group are more preferred, and an ethyl group is more preferred. v and w are integers of 0 to 4, and from the viewpoint of heat resistance, they are each preferably an integer of 0 to 2, more preferably each is 0 or 1, and even more preferably each is 1.

Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^d2 to X ^d4 include methylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 1,5-pentyl and so on. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of heat resistance. As X ^d2 to X ^d4 , among the above options, each is preferably a methylene group or an isopropylidene group.

Examples of the amine compound (d) include m-phenylenediamine, p-phenylenediamine, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,3,5, 6-tetramethyl p-phenylenediamine, 2,4-diamino mesitylene, m-xylene-2,5-diamine, m-diamine, p-diamine, 2,4-diamine toluene, 2,5-diaminetoluene, 2,4-bis (aminotributyl) toluene, 2,4-diaminoxylene, 2,4-diaminepyridine, 2,6-diaminepyridine, 2 , 5-Diaminopyridine, 2,4-Diaminopyrene, 4,5-Diamino-6-hydroxy-2-mercaptopyrimidine, 3-bis (3-aminobenzyl) benzene, 4-bis (4 -Aminobenzyl) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminobenzene) Oxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3-bis (3- (3-aminophenoxy) phenoxy) benzene, 4-bis (4- (4 -Aminophenoxy) phenoxy) benzene, 3-bis (3- (3- (3-aminophenoxy) phenoxy) phenoxy) benzene, 4-bis (4- (4- (4-aminophenoxy) phenoxy) phenoxy) benzene, 3-bis (α, α-dimethyl-3-aminobenzyl) benzene, 1,4-bis (α, α- Dimethyl-3-aminobenzyl) benzene, 3-bis (α, α-dimethyl-4-aminobenzyl) benzene, bis (4-methylaminopentyl) benzene, p-bis (2 -A -4-Aminopentyl) benzene, 1,4-bis (3-aminopropyldimethylsilyl) benzene, bis [(4-aminephenyl) -2-propyl] 1,4-benzene, 2 5,5-diaminobenzenesulfonic acid, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diamine Diphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenyl Methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-methylene-bis (2-chloroaniline), 3 , 3'-diaminodiphenylethane, 4,4'-diaminodiphenylethane, 2,2'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4 , 4'-Diaminodiphenylpropane, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [4- (4-aminophenoxy Phenyl) hexafluoropropane, 3- (2 ', 4'-diaminophenoxy) propanesulfonic acid, bis (4-aminophenyl) diethylsilane, 3,3'-diamine Diphenyl ketone, 4,4'-diamino diphenyl ketone, 3,3'-diamino diphenyl ether, 4,4'-diamino diphenyl ether, 3,3'-di Methyl-4,4'-diaminodiphenyl ether, bis (4-aminotributylphenyl) ether, 4,4'-diamine Diphenyl ether-2,2'-disulfonic acid, 3,3'-diaminodiphenylsulfonium, 4,4'-diaminodiphenylsulfonium, bis [4- (4-aminophenoxy) (Phenyl) phenyl] hydrazone, bis [4- (3-aminophenoxy) phenyl] hydrazone, benzidine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3, 3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4, 4'-diaminobiphenyl-6,6'-disulfonic acid, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 3,3'-dichloro- 4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 4, 4'-diaminodiphenyl sulfide, 4,4'-diamino-3,3'-biphenyldiol, 1,5-diamine naphthalene, 1,4-diamine naphthalene, 2,6- Diamine naphthalene, 9,9'-bis (4-aminophenyl) fluorene, 9,9'-bis (4-aminephenyl) fluorene-2,7-disulfonic acid, 9,9'-bis (4 -Aminophenoxyphenyl) fluorene, diamine anthraquinone, 3,7-diamino-2,8-dimethyldibenzothiophene fluorene and the like containing aromatic groups;

Ethylenediamine, butanediamine, hexylenediamine, hexylenediamine, heptanediamine, hexamethylenediamine, hexamethylenediamine, hexamethylenediamine, 2,5-dimethylmethylenehexane Amine, 3-methoxyheptanediamine, 2,5-dimethylheptanediamine, 3-methylheptanediamine, 4,4'-dimethylheptanediamine, 5-methylheptanediamine Nonanediamine, 1,4-diaminocyclohexane, 1,3-bis (3-aminopropyl) tetramethyldisilazane, 2,5-diamino-1,3,4-oxazine Aliphatic amines such as diazoles, bis (4-aminocyclohexyl) methane; melamine, benzoguanamine, acetoguanamine, 2,4-diamino-6-vinyl-s-triazabenzene, 2,4-diamino-6-allyl-s-triazabenzene, 2,4-diamino-6-propenyloxyethyl-s-triazabenzene, 2,4-di Guanidine amine compounds such as amino-6-methacrylfluorenyloxyethyl-s-triazabenzene and the like.

Among these, m-phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 4,4'-diaminodiphenylmethane, and 3,3 are preferred. '-Dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2'-bis [4- (4 -Aminophenoxy) phenyl] propane, 4,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylhydrazone, 4,4'-diaminodiphenylhydrazone, bis [4- (4-aminophenoxy) phenyl] hydrazone, benzidine, 4,4'-bis (4-aminophenoxy) biphenyl , 4,4'-diaminodiphenyl sulfide, 4,4'-diamino-3,3'-biphenyldiol, benzoguanamine, more preferably 3,3'-diethyl- 4,4'-diaminodiphenylmethane, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane. The amine compound (d) may be used singly or in combination of two or more kinds.

When the thermosetting resin composition contains an amine compound (d), the content thereof is preferably 100 parts by mass based on 100 parts by mass of the solid content of the resin component in the thermosetting resin composition from the viewpoint of low warpage. 1 to 40 parts by mass, more preferably 2 to 35 parts by mass, still more preferably 2 to 30 parts by mass, and also 7 to 30 parts by mass.

<Hardening accelerator (e)> The thermosetting resin composition may further contain a hardening accelerator (e). Examples of the hardening accelerator (e) include organometallic salts such as zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, cobalt (II) acetoacetate, and cobalt (III) acetoacetate; Imidazoles and their derivatives; organic phosphorus compounds; secondary amines; tertiary amines; quaternary ammonium salts. Among these, from the viewpoints of heat resistance, flame retardancy, and adhesion strength to metal circuits, imidazoles and their derivatives are preferred, and from the viewpoint of low thermal expansion, organic phosphorus compounds are preferred. . A hardening accelerator (e) may be used individually by 1 type, and may use 2 or more types together. As the hardening accelerator (e), a commercially available product can be used. Examples of commercially available products include isocyanate-masked imidazole (made by Daiichi Kogyo Co., Ltd., product model G-8009L), triphenylphosphine-triphenylborane (made by Beixing Chemical Industry Co., Ltd., Product model TPP-S) and so on. When the thermosetting resin composition contains a hardening accelerator (e), its content is preferably from 0.05 to 10 parts by mass relative to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition, and more preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 1 part by mass. As long as the content of the hardening accelerator (e) is 0.05 parts by mass or more, there is a tendency that the heat resistance, flame retardancy, and copper foil adhesion are excellent, and as long as it is 10 parts by mass or less, heat resistance and stability over time And it tends to be excellent in press formability.

<Inorganic Filler (f)> The thermosetting resin composition may further contain an inorganic filler (f). Examples of the inorganic filler include silicon dioxide, aluminum oxide, titanium oxide, mica, beryllite, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, and aluminum hydroxide. Clay, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay, talc, aluminum borate, silicon carbide, quartz powder, short glass fiber, glass fine powder (glass fine powder), insulating glass, etc. Preferred examples of the glass include E-type glass, T-type glass, and D-type glass. Among these, silicon dioxide is preferred from the viewpoints of dielectric characteristics, heat resistance, and low thermal expansion. Examples of the silicon dioxide include precipitated silicon dioxide having a high water content prepared by a wet method, and dry method silicon dioxide containing almost no bound water and the like prepared by a dry method, as the dry method. Silicon, by its different manufacturing methods, can be classified into broken silica, fumed silica, fused spherical silica, and so on. Among these, from the viewpoint of low thermal expansion and fluidity when filled in a resin, fused spherical silica is preferred. The inorganic filler (f) may be used singly or in combination of two or more kinds.

The average particle diameter of the inorganic filler is preferably 0.1 to 10 μm, more preferably 0.3 to 8 μm, and still more preferably 0.3 to 3 μm. If the average particle diameter is 0.1 μm or more, the resin tends to maintain good fluidity when it is highly filled into the resin. If it is 10 μm or less, the mixing probability of coarse particles can be reduced, and the generation of coarse particles can be suppressed. Bad tendency. Here, the average particle diameter is a particle diameter corresponding to 50% of the volume when the cumulative particle size distribution curve derived from the particle diameter is obtained by setting the total volume of the particles to 100%. The measurement is performed by a particle size distribution measuring device or the like using a laser diffraction scattering method. The inorganic filler (f) can be surface-treated with a coupling agent. The surface treatment by the coupling agent may be a dry or wet surface treatment of the inorganic filler (f) before preparation, or an integral blending treatment, which is After the non-surface-treated inorganic filler (f) is formulated into other components to form a composition, a silane coupling agent is added to the composition. Examples of the coupling agent include a silane-based coupling agent, a titanate-based coupling agent, and a siloxane oligomer.

When the thermosetting resin composition contains the inorganic filler (f), its content is preferably 20 to 400 parts by mass, and more preferably 20 to 400 parts by mass, relative to 100 parts by mass of the solid content of the resin component in the thermosetting resin composition. 50 to 350 parts by mass, and more preferably 70 to 230 parts by mass. When the content of the inorganic filler (f) is within the aforementioned range, moldability and low thermal expansion properties are good.

<Other components> The thermosetting resin composition of the present invention may contain an organic filler, a flame retardant, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, and a fluorescent compound to the extent that the thermosetting properties are not impaired. Light brightener, adhesion improver, etc.

Examples of the organic filler include: a resin filler composed of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, or the like; and a core shell structure A resin filler and the like, the core-shell structure has a rubber-like core layer and a glass-like shell layer, and the core layer is composed of an acrylate resin, a methacrylate resin, a conjugated diene resin, and the like. It is composed of an acrylate resin, a methacrylate resin, an aromatic vinyl resin, a vinyl cyanide resin, and the like.

Examples of the flame retardant include halogen-containing flame retardants such as bromine and chlorine; and triphenyl phosphate, tricresyl phosphate, ginsyl dichloropropyl phosphate, phosphate compounds, and red phosphorus. Combustion agents; nitrogen-based flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, and melamine cyanurate; azo-azo systems such as cyclophosphazene and polyphosphazene Flame retardants; inorganic flame retardants such as antimony trioxide.

Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber. Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, and the like. Examples of the photopolymerization initiator include photopolymerization of diphenyl ketones, benzyl ketals, and 9-oxysulfide [口 + 山] [口 + 星] 系 (thioxanthone). Starting agent. Examples of the fluorescent whitening agent include a fluorescent whitening agent of a stilbene derivative. Examples of the adhesiveness-improving agent include urea compounds such as urea silane, and the aforementioned coupling agents.

The thermosetting resin composition may be in a varnish state, it is easy to use in the production of prepregs, and the like, and each component is dissolved or dispersed in an organic solvent.

Examples of the organic solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, methylcellulose, butylcellulose, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, and methyl alcohol Ketone solvents such as isobutyl ketone and cyclohexanone; ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene ; A solvent containing a nitrogen atom, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; a solvent containing a sulfur atom, such as dimethylsulfine. These solvents may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoint of the solubility of each component, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellulose, and propylene glycol monomethyl ether are more preferable. It is methyl ethyl ketone, and from the viewpoint of low toxicity, methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferable. The solid content concentration of the varnish is preferably 40 to 90% by mass, and more preferably 50 to 80% by mass. When the solid content concentration of the varnish is within the aforementioned range, a prepreg can be obtained which maintains the coating property well and has an appropriate content of the thermosetting resin composition.

[Aggregate] Aggregates that can be used in the present invention include inorganic fiber substrates such as glass and carbon; organic fiber substrates such as polyaramide and cellulose; iron, copper, aluminum, alloys of these metals, etc. Composition of a metal fiber substrate and the like. These may be used individually by 1 type, and may use 2 or more types together. In particular, from the viewpoint of dielectric properties, inorganic fibers are preferred, and low dielectric glass and Q-type glass are more preferred. As the aggregate material, for example, those having a shape such as a woven fabric, a non-woven fabric, a roving, a chopped strand mat, or a surfacing mat can be used. Among these, a woven fabric or a non-woven fabric is preferred. The material and shape of the aggregate material can be appropriately selected according to the purpose, performance, etc. of the intended shaped article. As required, it can be a fibrous base material composed of one material and one shape, or two or more types. The bone material composed of the material may be a bone material having two or more shapes. The thickness of the aggregate material is, for example, 5 μm to 0.5 mm. From the viewpoint of making low warpage and high-density lines, it is preferably 5 μm to 100 μm, more preferably 8 μm to 60 μm, and still more preferably 10 to 30 μm. From the viewpoints of heat resistance, moisture resistance, processability and the like, these aggregates are preferably those obtained by surface treatment using a silane coupling agent or the like, or those obtained by mechanical fiber opening treatment.

The content of the solid content of the thermosetting resin composition in the fiber-reinforced plastic precursor is preferably 20 to 90% by mass.

[Resin film with support] In the present invention, the resin film with a support used in the manufacture of a fiber-reinforced plastic precursor can be coated with a thermosetting resin composition on a support, for example, It is produced by drying at 90 to 130 ° C for 1 to 10 minutes. The support is not particularly limited, and examples thereof include organic resin films, metal foils, and release paper. Examples of the material of the organic resin film include polyolefins such as polyethylene and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter, also referred to as "PET") and polyethylene naphthalate ; Polycarbonate, polyimide, etc. Among these, PET is preferable from a viewpoint of price and handling property. That is, the organic resin film is preferably a PET film. Examples of the metal foil include copper foil and aluminum foil. When a copper foil is used on a support, the copper foil can be directly used as a conductor layer and can also form a circuit. In this case, as the copper foil, a rolled copper foil, an electrolytic copper foil, or the like can be used. The thickness of the copper foil is not particularly limited, and for example, a thickness of 2 to 36 μm can be used. When a thin copper foil is used, a copper foil with a carrier can be used from the viewpoint of improving workability. The thickness of the support is not particularly limited. From the viewpoint of handleability, it is preferably 10 to 120 μm, more preferably 15 to 80 μm, and still more preferably 15 to 70 μm. The support does not need to be a single component as described above, and may be formed using a plurality of layers (two or more layers) of different materials.

The fiber-reinforced plastic precursor obtained by the present invention is useful for a coreless substrate. The coreless substrate is manufactured, for example, by using a prepreg of the present invention on a core substrate to form a build-up layer in which a conductor layer and an insulating layer are alternately laminated. ), The core substrate is separated and removed. The method for forming the layer is not particularly limited, and a known method can be adopted. For example, the build-up layer can be formed by the following method. First, a prepreg 1 is placed on a core substrate. Furthermore, after the adhesive layer is disposed on the core substrate, a prepreg 2 may be disposed. After that, the prepreg 2 is heat-hardened to form an insulating layer. Then, a via hole is formed by a perforation cutting method or a laser processing method such as a YAG laser or a carbon dioxide laser, and then a surface roughening treatment and a desmear treatment are performed as needed. . Then, it is formed by a subtractive process, a fully-additive process, a semi-additive process, a modified semi additive process (mSAP), and the like. Circuit pattern. By repeating the above process, a build-up can be formed. The formed build-up layer can be separated from the core substrate to obtain a coreless substrate.

[Manufacturing method of laminated body and manufacturing method of printed wiring board] The present invention also provides a manufacturing method of a laminated body. The laminated body is formed by laminating and forming a fiber-reinforced plastic precursor, and the fiber-reinforced plastic precursor is borrowed. Obtained from the aforementioned manufacturing method. More specifically, one piece of the fiber-reinforced plastic precursor (for example, a prepreg) obtained by using the present invention or a fiber-reinforced plastic precursor obtained by superposing 2 to 20 pieces of the fiber-reinforced plastic precursor is prepared. One or both sides are laminated and formed with a structure in which metal foils such as copper and aluminum are arranged, thereby forming a laminated body (also referred to as a laminated board). The metal foil is not particularly limited as long as it can be used for electrical insulation materials, and copper foil is preferred. When the metal foil is a copper foil, the obtained laminated body (laminated board) is generally referred to as a copper-clad laminated board. As a molding condition at the time of manufacturing a laminated body, the molding conditions of the laminated board for electrical insulation materials, and a multilayer board can be applied, for example. Specifically, molding can be performed under conditions of a temperature of 100 to 250 ° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours using a multi-stage pressurization, a multi-stage vacuum pressurization, continuous forming, and a hot press forming machine. In addition, a fiber-reinforced plastic precursor and a wiring board for an inner layer can be combined and laminated to form a laminated body. Further, a printed wiring board can be manufactured by forming a circuit on the laminated body, and more specifically, by performing circuit processing on the metal foil.

[Semiconductor Package] The present invention also provides a method for manufacturing a semiconductor package. The semiconductor package is formed by assembling a semiconductor element on a printed wiring board obtained by the aforementioned manufacturing method. A semiconductor package can be manufactured by assembling a semiconductor element such as a semiconductor wafer, a memory, and the like at a specific position on the printed wiring board, and sealing the semiconductor element with a sealing resin or the like. [Example]

Then, the present invention is described in further detail by the following examples, but these examples are not intended to limit the present invention. In addition, regarding the fiber-reinforced plastic precursors obtained by the following examples, the physical properties or characteristics were measured and evaluated by the following methods.

(1) Resin residue on the support during peeling After the fiber-reinforced plastic precursor is manufactured, the support is manually peeled from the fiber-reinforced plastic precursor with the support attached, and the state of the support is visually observed. Evaluation was performed based on the following evaluation criteria. In addition, when the evaluation was A, the resin was sufficiently transferred to the aggregate, and the peelability from the support was good, and the product was acceptable. When evaluated as B and C, it failed as a product. A: No resin was adhered to the support at all. B: Some resin is attached to the support. C: A lot of resin is adhered to the support.

(2) Heat resistance (soldering heat resistance) After the evaluation substrate was floated in a solder bath at 288 ° C for one minute, the appearance heat resistance was evaluated by visual observation. The evaluation substrate was made of each example. The copper-clad laminate is cut to a size of 5 cm square. Those who could not be confirmed to be inflated were evaluated as “good”, and those who were inflated were to be evaluated as “inflated”.

(3) Amount of warpage According to the following procedure, a substrate for evaluation was prepared from the copper-clad laminated board prepared in each example, and a surface shape measuring device (manufactured by AKROMETRIX Corporation, product model TherMoire PS200, and shadow moire) was used. Analysis) to measure the amount of warpage of the substrate for evaluation. First, a circuit pattern having a copper residual rate of 40% is formed on both sides of a copper-clad laminated board, and a resist is coated on both sides and fired, and then a size of 40 mm × 40 mm is cut out. A 20 mm × 20 mm silicon wafer was fixed at the center with an epoxy-based conductive adhesive mixed with silver powder, and then sealed with an epoxy-based sealing material to prepare a substrate for evaluation. The substrate for evaluation at room temperature was heated to 260 ° C, and then the amount of warpage when cooled to 50 ° C was measured. The amount of warpage measured by this method is preferably 70 μm or less, and more preferably 65 μm or less. The smaller the amount of warpage, the better.

[Examples 1 to 7 and Comparative Examples 1 to 4] Each of the components shown below was mixed at a blending ratio shown in Table 1 (the unit of numerical values in the table is mass parts), and methyl ethyl ketone was used as a solvent. A varnish having a solid content concentration of 65% by mass was prepared. Then, each varnish was coated on a support, that is, a PET film (manufactured by Teijin DuPont Film Co., Ltd., product number G2), and heated and dried at 90 to 130 ° C for 3 minutes to obtain a resin film with a support ( Resin thickness: 60 μm). Then, it arrange | positioned so that the resin side of each of the two resin films with a support body might face a bone material (E-type glass fiber cloth of 25 micrometers in thickness). The resin composition was pressed and impregnated into the bone material by pressing the rollers under the conditions of a roller temperature of 100 ° C, a linear pressure of 0.2 MPa, and a speed of 2.0 m / min. Thereafter, winding is performed, and then the PET film is manually peeled from both sides, thereby obtaining a fiber-reinforced plastic precursor (prepreg). Using one piece of this fiber-reinforced plastic precursor, 12 μm electrolytic copper foil was arranged above and below the fiber-reinforced plastic precursor, and pressure was applied at a pressure of 2.5 MPa and a temperature of 200 to 240 ° C. for 60 minutes to obtain a copper-clad laminate. board. Using the obtained copper-clad laminated board, each physical property was evaluated according to the aforementioned measurement method. The results are shown in Table 1.

[Siloxanes compound (a)] (a-1): Both end epoxy modified silica (made by Shin-Etsu Chemical Industry Co., Ltd., product model X-22-163A, functional group equivalent of epoxy group 1000 g / mol) (a-2): Side chain methanol modified silica (manufactured by Shin-Etsu Chemical Co., Ltd., product model X-22-4039, hydroxyl value 58 mg KOH / g) (a-3): both terminal amines Modified Siloxane (made by Shin-Etsu Chemical Industry Co., Ltd., product model X-22-161A, functional group equivalent of amine group 800g / mol)

[Thermosetting resin (b)] (b-1) α-naphthol / cresol novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product model NC-7000L, epoxy equivalent 223 to 238 g / eq) (b-2) Biphenylarane type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product model NC-3000-H, epoxy equivalent 280-300 g / eq) (b-3) phenol resin ( Manufactured by DIC Corporation, phenol novolac resin, product model PHENOLITE (registered trademark) TD-2090, hydroxyl equivalent 105g / eq)

[Maleimidoimine compound (c)] (c-1) Bis (4-maleimidoimidophenyl) methane (manufactured by KI Kasei Corporation, product model BMI) (c-2) 2,2 -Bis [4- (4-maleimidophenoxy) phenyl] propane (manufactured by Daiwa Chemical Industry Co., Ltd., product model BMI-4000)

[Amine compound (d)] (d-1) 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., product model KAYAHARD AA) (d-2 ) 2,2'-bis [(4- (4-aminophenoxy) phenyl) propane] (manufactured by Wakayama Seika Chemical Co., Ltd., product model BAPP)

[Hardening accelerator (e)] (e-1) Isocyanate-shielding imidazole (manufactured by Daiichi Kogyo Co., Ltd., product model G-8009L) (e-2) tetraphenylphosphonium tetraborate tetra-p-tolyl ester (Beixing Chemical Industry Co., Ltd. (Manufactured by Co., Ltd., product model TPP-MK)

[Inorganic filler (f)] (f-1) Spherical fused silica (manufactured by Admatechs Co., Ltd., average particle diameter: 0.5 μm)

[Table 1] The numerical unit indicating the content of each component is parts by mass.

As can be seen from Table 1, in Examples, the resin remaining on the support at the time of peeling was small, the heat resistance was excellent, and the amount of warpage of the substrate could be reduced. On the other hand, in Comparative Example, at least one of the evaluations of the resin residual property, heat resistance, and warpage of the substrate at the time of peeling was inferior. Therefore, it can be seen that according to the method for manufacturing a fiber-reinforced plastic precursor of the present invention, a fiber-reinforced plastic precursor having good appearance can be obtained, and further, a laminated board having good heat resistance and suppressing warpage can be obtained. [Industrial availability]

Since the thermosetting resin composition obtained by the present invention can obtain a laminated board having good heat resistance and suppressing warpage, it is useful for the manufacturing use of a printed wiring board that has been made dense and highly multilayered. Furthermore, it can be suitably used in a circuit board of an electronic device, such as a computer and an information device terminal, which process a large amount of data at a high speed.

1‧‧‧ fiber reinforced plastic precursor

2‧‧‧ Aggregate delivery device

3‧‧‧Resin film feeding device

4‧‧‧ protective film peeling mechanism

5‧‧‧ protective film winding device

6‧‧‧ Sheet heating and pressing device (film compression bonding means)

7‧‧‧ sheet pressure cooling device

8‧‧‧ fiber-reinforced plastic precursor winding device

40‧‧‧ Aggregate

40a‧‧‧ Surface of the aggregate (one of the surfaces of the aggregate, one of the two surfaces of the aggregate)

40b ‧‧‧ Back side of the aggregate (the other surface of the aggregate, the other side of the two surfaces of the aggregate)

50‧‧‧Resin film with protective film

52‧‧‧ protective film

54‧‧‧Resin film (film)

54a‧‧‧ Resin film surface on aggregate side (surface of aggregate side film)

60‧‧‧ Fiber-reinforced plastic precursor

FIG. 1 is a schematic diagram showing an aspect of a manufacturing apparatus for a fiber-reinforced plastic precursor that can be used in the present invention.

Domestic hosting information (please note in order of hosting institution, date, and number) None

Information on foreign deposits (please note in order of deposit country, institution, date, and number) None

Claims (12)

A manufacturing method of a fiber-reinforced plastic precursor. The manufacturing method is a method of manufacturing a fiber-reinforced plastic precursor by attaching a resin film with a support to a bone material and peeling the support from the resin film with the support. The resin film is a resin film including a thermosetting resin composition, and the thermosetting resin composition contains a siloxane compound (a). The method for producing a fiber-reinforced plastic precursor according to claim 1, wherein the siloxane compound (a) is represented by the following general formula (1): In the general formula (1), R ^a1 , R ^a2 , R ^a3, and R ^a4 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group, and R ^a5 and R ^a6 are each independently Ground represents an organic group, and m is an integer of 1-50. The method for producing a fiber-reinforced plastic precursor according to claim 1 or 2, wherein the thermosetting resin composition further contains a thermosetting resin (b). The method for producing a fiber-reinforced plastic precursor according to any one of claims 1 to 3, wherein the thermosetting resin composition further contains a maleimide compound (c), which is a maleimide compound (c) having at least 2 N-substituted maleimidine imino groups in one molecule. The method for producing a fiber-reinforced plastic precursor according to any one of claims 1 to 4, wherein the thermosetting resin composition further contains an amine compound (d), and the amine compound (d) has At least 2 primary amine groups. The method for producing a fiber-reinforced plastic precursor according to any one of claims 1 to 5, wherein the thermosetting resin composition further contains a hardening accelerator (e). The method for producing a fiber-reinforced plastic precursor according to any one of claims 1 to 6, wherein the thermosetting resin composition further contains an inorganic filler (f). The method for manufacturing a fiber-reinforced plastic precursor according to any one of claims 1 to 7, wherein the resin film with a support is heated and pressed under normal pressure to adhere the resin film to the bone material. on. The method for manufacturing a fiber-reinforced plastic precursor according to any one of claims 1 to 8, wherein the fiber-reinforced plastic precursor is used for a coreless substrate. A method for manufacturing a laminated body, which is implemented by laminating and forming a fiber-reinforced plastic precursor, the fiber-reinforced plastic precursor is produced by the fiber-reinforced plastic precursor according to any one of claims 1 to 8. Obtained by the manufacturing method of the material. A method for manufacturing a printed wiring board. The manufacturing method is implemented by forming a circuit on a multilayer body obtained by the method for manufacturing a multilayer body according to claim 10. A method for manufacturing a semiconductor package. The manufacturing method is implemented by assembling a semiconductor element on a printed wiring board. The printed wiring board is obtained by the method for manufacturing a printed wiring board according to claim 11.