JP2021028137A - Production method for frp precursor, frp precursor, laminated board, multilayer printed wiring board and semiconductor package - Google Patents

Abstract

To provide a production method for an FRP precursor having excellent productivity, an FRP precursor produced by the production method, and a laminated board, a multilayer printed wiring board, and a semiconductor package using the FRP precursor.SOLUTION: A production method for an FRP precursor in which a sheet-like aggregate is impregnated with a thermosetting resin film by pressure welding includes a step of performing pressure welding impregnation of the thermosetting resin film from only one surface of the sheet-like aggregate. The FRP precursor is produced by the production method. The FRP precursor is used for a laminated board, a multilayer printed wiring board, and a semiconductor package.SELECTED DRAWING: None

Description

The present invention relates to a method for producing an FRP precursor, a method for producing an FRP precursor, a laminated board, a multilayer printed wiring board, and a semiconductor package.

FRP (Fiber Reinforced Plastics) is a composite in which a fiber material with a high elastic modulus such as fiber is used as an aggregate, and this aggregate is placed in a base material (matrix) such as plastic to improve the strength. It is a material that is inexpensive, lightweight, and has excellent durability, taking advantage of weather resistance, heat resistance, chemical resistance, and light weight.
Taking advantage of these performances, FRP is used in a wide range of fields. For example, FRP is used as a structural material for housing equipment, ships, vehicles, aircraft, etc. because of its formability and high strength. It is also used in the field of electronic components such as electric devices and printed wiring boards by taking advantage of its insulating properties.

When FRP is used for a printed wiring board, the thickness of FRP is required to be thinner than the thickness of FRP for other uses. Further, FRP for printed wiring boards is required to have high specifications such as a narrow range of thickness variation after molding and no voids.
Therefore, most FRPs for printed wiring boards are manufactured by the Hand Lay-up (HLU) method. The hand lay-up method is a manufacturing method in which a varnish in which a resin is dissolved in a solvent is applied to an aggregate using a coating machine or the like, and the resin is heat-dried to remove the solvent and heat-cure the resin (for example, a patent). Reference 1).

However, when aramid non-woven fabric without calender treatment, thin glass paper, thin woven cloth, etc. are used as the aggregate, these aggregates have low strength, so when the gap of the coater is narrowed to adjust the amount of resin to be applied. The workability is poor because the weight of the material may exceed the load capacity of the aggregate when it is dried or heat-cured after application.
Further, in FRP for printed wiring boards, it is necessary to achieve both high accuracy of the thickness after lamination and resin filling property (moldability) in the inner layer circuit pattern. Therefore, a plurality of types of FRP precursors are produced from one type of aggregate, such as those in which the amount of resin adhered to the aggregate differs by several mass percent, those in which the curing time of the thermosetting resin is changed, and those in which they are combined. It has to be done and is complicated. Further, since the coating conditions are changed for each production, the loss of the material used for production is large.

Therefore, instead of directly applying the thermosetting resin to the aggregate, a resin film in which the thermosetting resin is formed into a film is prepared in advance, and the sheet-shaped aggregate and the resin film are heated and pressurized. A method for producing an FRP precursor to be pressure-welded and impregnated has been studied (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 01-272416 Japanese Unexamined Patent Publication No. 2011-132535

In the method of impregnating an aggregate with a resin film by pressure welding, a method of impregnating a pair of resin films with pressure welding from both sides of a sheet-shaped aggregate (hereinafter, also referred to as "double-sided pressure welding impregnation method") is the mainstream.
However, according to the double-sided pressure welding impregnation method, as a resin film to be pressure-welded on both sides, two resin films prepared with half the amount of resin finally required are required. That is, it is necessary to prepare a resin film having twice the length of the FRP precursor to be produced, which is inferior in productivity and yield. Further, when a resin film is produced with a small amount of resin, heat during drying is easily transferred to the resin and curing is easily promoted, so that the drying conditions of the applied varnish must be strictly controlled, which complicates the work.

The resin film is usually produced by applying a varnish in which a thermosetting resin is dissolved in an organic solvent to a support and then drying the film. At this time, in order to improve the productivity of the FRP precursor, it is desirable to dry the FRP precursor at a temperature higher than the boiling point of the solvent and perform the drying in a short time. On the other hand, from the viewpoint of impregnation property into the aggregate, it is desirable to dry the varnish at a low temperature to appropriately suppress the progress of curing of the resin film and keep the minimum melt viscosity low. That is, in order to improve the productivity of the FRP precursor, it is necessary to keep the minimum melt viscosity of the obtained resin film low and to quickly remove the solvent during drying, which are achieved. The heating conditions required for this are contradictory and difficult to achieve.

The present invention has been made in view of the above problems, and a method for producing an FRP precursor having excellent productivity, an FRP precursor produced by the production method, and a laminated board and a multilayer using the FRP precursor. The purpose is to provide printed wiring boards and semiconductor packages.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following invention, and have completed the present invention. That is, the present invention relates to the following [1] to [12].
[1] A method for producing an FRP precursor in which a thermosetting resin film is heated and pressure-welded to impregnate a sheet-shaped aggregate, wherein the thermosetting resin film is pressure-welded and impregnated on one surface of the sheet-shaped aggregate. A method for producing an FRP precursor, which comprises a step performed solely from.
[2] The method for producing an FRP precursor according to the above [1], wherein the thermosetting resin film is pressure-welded and impregnated by laminating.
[3] The method for producing an FRP precursor according to the above [1] or [2], wherein the minimum melt viscosity of the thermosetting resin film is 500 to 000 mPa · s.
[4] The method for producing an FRP precursor according to any one of [1] to [3] above, wherein the air permeability of the aggregate is 110 cc / cm ^{2 / sec or more.}
[5] The method for producing an FRP precursor according to any one of [1] to [4] above, wherein the thermosetting resin film is pressure-welded and impregnated into the sheet-shaped aggregate at a linear pressure of 0.1 to 1 MPa.
[6] Ratio of the thickness of the thermosetting resin film to the thickness of the sheet-shaped aggregate The above-mentioned [thermosetting resin film / sheet-shaped aggregate] is 1.1 to 2.5, and the above [1]. ] To [5], the method for producing an FRP precursor.
[7] The thermosetting resin film is a thermosetting resin film with a first support having a first support on one surface.
The thermosetting resin film with the first support is arranged on the one surface of the sheet-shaped aggregate so that the thermosetting resin film is on the one surface side of the sheet-shaped aggregate. ,
With the second support placed on the other surface of the sheet-shaped aggregate,
The method for producing an FRP precursor according to any one of the above [1] to [6], wherein the thermosetting resin film is pressure-welded and impregnated.
[8] The method for producing an FRP precursor according to the above [7], wherein the material of the first support and the material of the second support are the same.
[9] An FRP precursor produced by the method for producing an FRP precursor according to any one of the above [1] to [8].
[10] A laminated board obtained by laminating and molding the FRP precursor according to the above [9].
[11] A multilayer printed wiring board manufactured by using the laminated board according to the above [10].
[12] A semiconductor package in which a semiconductor is mounted on the multilayer printed wiring board according to the above [11].

According to the present invention, a method for producing an FRP precursor having excellent productivity, an FRP precursor produced by the production method, and a laminated board, a multilayer printed wiring board, and a semiconductor package using the FRP precursor are provided. Can be done.

It is a conceptual diagram of the manufacturing method of the FRP precursor and the manufacturing apparatus of the FRP precursor which concerns on this invention.

[Method for producing FRP precursor]
The method for producing an FRP precursor of the present embodiment is a method for producing an FRP precursor in which a sheet-shaped aggregate is impregnated with a thermosetting resin film by pressure welding, and the sheet-shaped aggregate is impregnated with a thermosetting resin film by pressure welding. This is a method for producing an FRP precursor, which is carried out from only one surface of the aggregate.
Hereinafter, the sheet-shaped aggregate may be simply abbreviated as "aggregate", and the thermosetting resin film may be simply abbreviated as "resin film". The "resin film" does not include the protective film and the support described later.
Further, a method of performing pressure welding impregnation of a thermosetting resin film from only one surface of a sheet-shaped aggregate may be referred to as a "single surface pressure welding impregnation method".
Further, in the present invention, "pressure welding" means applying pressure in a state of contact.

In the method for producing an FRP precursor of the present embodiment, the thermosetting resin film is a thermosetting resin film with a first support having a first support on one surface.
The thermosetting resin film with the first support is arranged on the one surface of the sheet-shaped aggregate so that the thermosetting resin film is on the one surface side of the sheet-shaped aggregate. ,
With the second support placed on the other surface of the sheet-shaped aggregate,
It is preferable that the thermosetting resin film is impregnated by pressure welding.
Hereinafter, the method for producing the FRP precursor of the present embodiment will be described with reference to FIG.

In the FRP precursor manufacturing apparatus 1, the resin film 54 is pressure-welded and impregnated from one surface of the aggregate 40, and the second support 56 is pressure-welded from the other surface of the aggregate 40.
The purpose of the second support 56 is to prevent the resin from seeping out from the surface of the aggregate 40 on the side where the resin film 54 is not arranged when the resin film 54 is pressure-welded and impregnated, and the obtained FRP precursor. It is used for the purpose of stabilizing the surface condition of.
The FRP precursor manufacturing apparatus 1 is placed under normal pressure. The method for producing an FRP precursor of the present embodiment can be performed by the FRP precursor manufacturing apparatus 1.

The FRP precursor manufacturing apparatus 1 includes an aggregate delivery device 2, a resin film delivery device 3, a second support delivery device 3', a sheet heating and pressurizing device 6, a sheet pressurizing and cooling device 7, and the sheet pressurizing and cooling device 7. The FRP precursor winding device 8 is provided. The FRP precursor manufacturing apparatus 1 preferably further includes a protective film peeling mechanism 4 and a protective film winding apparatus 5. Further, the FRP precursor manufacturing apparatus 1 is an aggregate heating apparatus (not shown) for heating the aggregate before being sent to the sheet heating and pressurizing apparatus 6, and before being sent to the sheet heating and pressurizing apparatus 6. It may have a resin film heating device (not shown) for heating the resin film.

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

The resin film delivery device 3 applies a predetermined tension to the roll on which the first support and the resin film 50 with a protective film (hereinafter, also simply referred to as “multilayer film 50”) are wound and the multilayer film 50 to be fed out. However, it has a support mechanism that rotatably supports the roll, and is a device that rotates the roll on which the multilayer film 50 is wound in the direction opposite to the winding direction and sends out the multilayer film 50 wound on the roll. The multilayer film 50 is the first surface of the resin film 54 and the resin film 54, which is laminated on the surface 54a on the aggregate 40 side and the surface 54b on the opposite side of the aggregate 40. It is a sheet-like multilayer film including the support 53 of the above.
The resin film delivery device 3 is located on the surface 40a side of the delivered aggregate 40, and protects the multilayer film 50 from the lower side of the roller so that the protective film 52 is on the side of the delivered aggregate 40. It is a device that feeds the film to the film peeling mechanism 4.

The second support sending device 3'has a roll around which the second support 56 is wound, and a support mechanism that rotatably supports the roll while applying a predetermined tension to the second support 56 to be sent out. The second support 56 wound around the roll is rotated in the direction opposite to the winding direction, and the second support 56 wound around the roll is sent out.
The second support delivery device 3'is a device located on the back surface 40b side of the delivered aggregate 40 and feeds the second support 56 from the upper side of the roller toward the sheet heating / pressurizing device 6.

The protective film peeling mechanism 4 is a turning roller located on the surface 40a side of the delivered aggregate 40. The protective film peeling mechanism 4 receives the multilayer film 50 sent out from the resin film delivery device 3 and advancing toward the protective film peeling mechanism 4 on the surface of the rotating turning roller. Further, the first resin film 55 with a support of the multilayer film 50 is advanced toward the sheet heating / pressurizing device 6, and the protective film 52 is advanced toward the protective film winding device 5. It is a mechanism for peeling the protective film 52 from 50. As a result, the aggregate side film surface 54a of the resin film 54 is exposed.

The protective film winding device 5 is located on the surface 40a side of the delivered aggregate 40, and is a winding device that winds the protective film 52 peeled off by the protective film peeling mechanism 4.

The sheet heating and pressurizing device 6 has a pair of heating and compression rollers and a compressive force applying mechanism (not shown) that applies a compressive force to the pair of heating and compressing rollers. The pair of heating and compression rollers have a heating body inside so that they can be heated at a predetermined set temperature.
The sheet heating and pressurizing device 6 impregnates the aggregate 40 with a resin film 54 by pressure welding with a pair of rotating heating and compression rollers to form a sheet-shaped FRP precursor 60 (film pressure welding step), and the FRP precursor. 60 is sent out toward the sheet pressure cooling device 7.
At this time, the first resin film 55 with a support is laminated on the aggregate 40 so that the aggregate side film surface 54a side of the resin film 54 adheres to the surface 40a side of the aggregate 40, and the second support The FRP precursor 60 is formed by laminating the body 56 on the aggregate 40 so as to adhere to the back surface 40b side of the aggregate 40.
The temperature of the heat and pressure welding roller is preferably in the range of + 2 to 30 ° C., more preferably in the range of + 4 to 20 ° C., which is the minimum melt viscosity temperature of the resin film to be used. The method for measuring the minimum melt viscosity temperature of the resin film is as described later.
The linear pressure when the resin film is pressure-welded and impregnated into the sheet-shaped aggregate is preferably 0.1 to 1 MPa, more preferably 0.2 to 0.7 MPa, and even more preferably 0.3 to 0.5 MPa.
The FRP precursor 60 sent out from the sheet heating and pressurizing device 6 is in a high temperature state.

The sheet pressure cooling device 7 has a pair of cooling compression rollers and a compression force applying mechanism (not shown) that applies a compressive force to the pair of cooling compression rollers. The pair of cooling compression rollers compresses and cools the high-temperature FRP precursor 60 sent out from the sheet heating and pressurizing device 6 by the pair of rotating cooling compression rollers, and sends it out to the FRP precursor winding device 8.

The FRP precursor winding device 8 has a roll for winding the sheet-shaped FRP precursor 60 sent out from the sheet pressurizing cooling device 7, and a drive mechanism (not shown) for rotating the roll.

The above-mentioned FRP precursor manufacturing apparatus 1 operates as follows.

First, the sheet-shaped aggregate 40 is sent out from the aggregate delivery device 2 toward the sheet heating and pressurizing device 6. At this time, the front surface 40a and the back surface 40b of the aggregate 40 are exposed.
The front surface 40a and the back surface 40b of the delivered aggregate 40 may be heated by an aggregate heating device (not shown) under normal pressure, respectively.

On the other hand, the resin film delivery device 3 protects the first support and the resin film 50 with a protective film (multilayer film 50) from the lower side of the roller so that the protective film 52 is on the side of the aggregate 40 to which the protective film 52 is sent. It is sent out toward the film peeling mechanism 4.
Further, the second support sending device 3'sends the second support 56 from the upper side of the roller toward the sheet heating / pressurizing device 6.

The delivered multilayer film 50 is hung on a turning roller which is a protective film peeling mechanism 4, and when the film is turned, the protective film 52 is peeled off so that the aggregate side film surface 54a is exposed. The peeled protective film 52 is wound by the protective film winding device 5. The first resin film 55 with a support from which the protective film 52 has been peeled off is sent out toward the sheet heating and pressurizing device 6.

The sheet heating and pressurizing device 6 is the aggregate 40 sent from the aggregate sending device 2, the resin film 55 with the first support sent out from the protective film peeling mechanism 4, and the second support 56. It gets in between a pair of heat compression rollers provided. At this time, of the first resin film 55 with a support, the aggregate side film surface 54a of the resin film 54 is laminated on the surface 40a of the aggregate 40, and the second support 56 is on the back surface 40b of the aggregate 40. Laminate.
Then, under normal pressure, the resin film 54 is impregnated with the aggregate 40 by pressure welding with the sheet heating and pressurizing device 6 to obtain the FRP precursor 60. At this time, by controlling the temperature of the heating body inside the pair of heating and compressing rollers, the pair of heating and compressing rollers are maintained at a predetermined temperature, and pressure is applied while heating during the film pressure welding step.
According to the above embodiment, an FRP precursor 60 having a support on both sides is obtained in which the first support 53, the FRP precursor 60, and the second support 56 are laminated in this order.

The FRP precursor 60 sent out from the sheet heating and pressurizing device 6 is further pressurized and cooled by the sheet pressurizing and cooling device 7.
The FRP precursor 60 sent out from the sheet pressure cooling device 7 is wound by the FRP precursor winding device 8.

In the above example, an example in which one resin film is laminated on the aggregate is shown, but two or more resin films may be laminated on the aggregate. At this time, two or more resin films may be used in combination with different thermosetting degrees, compounding compositions, and the like.

The obtained FRP precursor may be cut into an arbitrary size, adhered to a predetermined product, and thermoset. Further, the FRP precursor may be used in a roll-to-roll manner.

The FRP precursor manufactured by the FRP precursor manufacturing apparatus 1 will be described.

<Sheet-shaped aggregate>
As the aggregate used in the manufacturing method of the present embodiment, well-known materials used for various laminated plates for electrical insulating materials can be used. The aggregate is preferably a fiber base material, and the material of the fiber base material is natural fibers such as paper and cotton linter; inorganic fibers such as glass fiber and asbestos; aramid, polyimide, polyvinyl alcohol, polyester and tetrafluoroethylene. , Organic fibers such as acrylic; examples thereof include mixtures thereof. Among these, glass cloth is preferable from the viewpoint of flame retardancy. Examples of the glass cloth include a glass cloth using E glass, C glass, D glass, S glass and the like, or a glass cloth in which short fibers are bonded with an organic binder; a mixture of glass fibers and cellulose fibers.
These fibrous substrates have shapes such as woven fabrics, non-woven fabrics, robinks, chopped strand mats or surfaced mats. The material and shape of the aggregate are selected according to the intended use and performance of the molded product, and one type may be used alone, or two or more types of materials and shapes may be combined as necessary. May be good.

The thickness of the sheet-like aggregate is preferably 3 to 50 μm, more preferably 5 to 20 μm, still more preferably 7 to 15 μm, from the viewpoint of thinning the printed wiring board and the strength of the obtained FRP precursor.

The air permeability (cc / cm ^{2 / sec) of the sheet-shaped aggregate is preferably 110 cc / cm 2} / sec or more, more preferably 200 cc / cm ² / sec or more, and 260 cc / cm from the viewpoint of impregnation property of the resin film. ² / sec or more is more preferable. Further, from the viewpoint of the strength of the obtained FRP precursor, it may be 500 cc / cm ² / sec or less.
The air permeability of the sheet-shaped aggregate is measured by a Frazier-type air permeability tester manufactured by Toyo Seiki Seisakusho Co., Ltd. using a sheet-shaped aggregate of 300 mm × 1260 mm as a sample.

<Thermosetting resin film>
The thermosetting resin film used in the method for producing an FRP precursor of the present embodiment is a film containing a thermosetting resin, and is a composition containing a thermosetting resin or a thermosetting resin (hereinafter, "thermosetting"). It is also called a "resin composition") in the form of a film.

Examples of the thermosetting resin include epoxy resin, phenol resin, urea resin, furan resin and the like. Among these, epoxy resin is preferable from the viewpoint of workability, handleability and price. One type of thermosetting resin may be used alone, or two or more types may be used in combination.
As the epoxy resin, a bifunctional or higher functional epoxy resin is preferable. Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin and other bisphenol type epoxy resin; alicyclic epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin , Bisphenol A novolac type epoxy resin, novolac type epoxy resin such as aralkyl novolac type epoxy resin; diglycidyl etherified product of polyfunctional phenol; these hydrogenated additives and the like.

When an epoxy resin is used as the thermosetting resin, an epoxy resin curing agent may be used. One type of epoxy resin curing agent may be used alone, or two or more types may be used in combination.
Examples of the epoxy resin curing agent include phenol resins, amine compounds, acid anhydrides, boron trifluoride monoethylamine, isocyanates, dicyandiamides, urea resins and the like, and among these, phenol resins are preferable.
Examples of the phenol resin include novolak-type phenol resins such as phenol novolac resin and cresol novolak resin; naphthalene-type phenol resin, high ortho-type novolak phenol resin, terpene-modified phenol resin, terpene phenol-modified phenol resin, aralkyl-type phenol resin, and dicyclopentadiene-type Examples thereof include phenol resin, salicylaldehyde type phenol resin, and benzaldehyde type phenol resin.
The amount of the epoxy resin curing agent to be blended is preferably such that the reaction group equivalent ratio of the curing agent is 0.3 to 1.5 equivalents with respect to the epoxy equivalent of 1 of the epoxy resin. When the blending amount of the epoxy resin curing agent is within the above range, the degree of curing can be easily controlled and the productivity becomes good.

The thermosetting resin composition used for forming the resin film may further contain a curing accelerator. As the curing accelerator, one type may be used alone, or two or more types may be used in combination.
Examples of the curing accelerator include imidazole compounds, organophosphorus compounds, tertiary amines, and quaternary ammonium salts. The imidazole compound may be an imidazole compound having a potential by masking the secondary amino group of imidazole with acrylonitrile, isocyanate, melamine, acrylate or the like. Examples of the imidazole compound used here include imidazole, 2-methylimidazole, 4-ethyl-2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, and 2-heptadecylimidazole. , 4,5-Diphenylimidazole, 2-methylimidazoline, 2-ethyl-4-methylimidazoline, 2-undecylimidazoline, 2-phenyl-4-methylimidazoline and the like. Alternatively, a photoinitiator that generates radicals, anions or cations by photodecomposition and initiates curing may be used.
The amount of the curing accelerator to be blended is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the thermosetting resin. When it is 0.01 part by mass or more, a sufficient curing accelerating effect can be obtained, and when it is 20 parts by mass or less, the thermosetting resin composition is excellent in storage stability and physical properties of the cured product, and is also excellent in economy.

The thermosetting resin composition may further contain a filler for improving impermeableness and abrasion resistance and increasing the amount. As the filler, one type may be used alone, or two or more types may be used in combination.
As the filler, oxides such as silica, aluminum oxide, zirconia, mulite, and magnesia; hydroxides such as aluminum hydroxide, magnesium hydroxide, and hydrotalcite; nitride ceramics such as aluminum nitride, silicon nitride, and boron nitride. Natural minerals such as talc, montmorillonite, and saponite; metal particles, carbon particles, and the like.

Since the filler has a wide range from a material having a specific gravity smaller than that of a resin to a material having a larger specific gravity, it is preferable to consider the amount of the filler added in terms of volume fraction rather than parts by mass.
The blending amount of the filler varies greatly depending on the purpose of addition, but is preferably in the range of 0.1 to 65% by volume based on the solid content volume of the thermosetting resin composition. When it is 0.1% by volume or more, it exerts a sufficient effect when added for the purpose of coloring and impermeable. Further, when it is 65% by volume or less, the increase in viscosity can be suppressed and the amount can be increased without deteriorating workability and adhesiveness.
Here, the solid content in the present specification refers to a component in the composition other than a volatile substance such as water and an organic solvent described later. That is, the solid content includes liquids, starch syrup-like and wax-like substances at room temperature around 25 ° C., and does not necessarily mean that they are solid.

In addition to the above components, the thermosetting resin composition may contain other components, if necessary, as long as the effects of the present invention are not impaired. For example, a flexible material may be added in order to impart the tackiness of the resin to the cured resin product and improve the adhesion at the time of adhesion. Flexible materials include polystyrene, polyolefin, polyurethane, acrylic resin, acrylic nitrile rubber, polyvinyl alcohol, those modified with epoxy or carboxy group to incorporate them into the curing system, and epoxy resin that is reacted in advance to increase the molecular weight. Epoxy and the like.

The thermosetting resin composition is preferably in the form of a varnish dissolved and / or dispersed in an organic solvent in order to achieve homogenization. As the organic solvent, one type may be used alone, or two or more types may be used in combination.
Organic solvents include acetone, methyl ethyl ketone, toluene, xylene, cyclohexanone, 4-methyl-2-pentanone, ethyl acetate, ethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and tripropylene glycol monomethyl ether. , N, N-dimethylformamide, N, N-dimethylacetamide and the like.

The resin film can be produced by applying a thermosetting resin composition obtained by blending each of the above components to a support, removing an unnecessary organic solvent, and heat-curing the resin film.
The thermosetting here is intended to bring the thermosetting resin composition into a so-called semi-cured (B-staged) state, and is thermoset so that the workability of the laminate has a good viscosity. It is preferable to semi-cure the sex resin composition.
The minimum melt viscosity of the resin film is preferably 500 to 3,000 mPa · s, more preferably 600 to 2,000 mPa · s, and further preferably 700 to 1,000 mPa · s from the viewpoint of improving the impregnation property of the resin film. preferable.
The minimum melt viscosity temperature of the resin film is preferably 60 to 150 ° C., more preferably 80 to 130 ° C., and even more preferably 100 to 120 ° C. from the viewpoint of productivity of the FRP precursor.
The minimum melt viscosity and the minimum melt viscosity temperature can be measured by the method described in Examples.

The thickness of the resin film is preferably 5 to 40 μm, more preferably 10 to 30 μm, still more preferably 15 to 25 μm, from the viewpoint of thinning the printed wiring board and the strength of the obtained FRP precursor.

When laminating the resin film and the aggregate, the thickness of the resin film is preferably thicker than the thickness of the aggregate in consideration of the target thickness of the FRP precursor and the moldability at the time of press molding. The ratio of the thickness of the resin film to the thickness of the aggregate [thermosetting resin film / sheet-like aggregate] is preferably 1.1 to 2.5, preferably 1.3 to 2.2, from the viewpoint of moldability. More preferably, 1.5 to 2.0 is even more preferable.

<Support>
Examples of the resin film support (first support) include organic films such as polyethylene terephthalate (PET), biaxially stretched polypropylene (OPP), polyethylene, polyvinylfluorate, and polyimide; copper, aluminum, and alloys of these metals. Film; Examples thereof include a film in which the surface of these organic films or metal films is subjected to a mold release treatment with a mold release agent.

The second support may be the same as the first support described above.
It is preferable that the first support and the second support are made of the same material. When the materials of the first support and the second support are the same, the behavior during thermocompression bonding becomes uniform on the front and back of the FRP precursor, and the thermal shrinkage and dimensional change rate of the support during thermocompression bonding It is possible to suppress an increase in residual stress on the product and appearance defects such as wrinkles due to the difference.

[Laminated board]
The laminated board of this embodiment is a laminated board obtained by laminating and molding the FRP precursor obtained by the method for producing the FRP precursor of this embodiment.
Examples of the laminated board of the present embodiment include the FRP precursor or a laminated board containing FRP obtained by curing the FRP precursor, and a metal-clad laminated board having a metal foil on the laminated board. The FRP obtained by curing the FRP precursor is an FRP obtained by C-stage (curing) the FRP precursor in a B-staged (semi-cured) state, and the present invention also includes the FRP. provide.

Specifically, the laminated board of the present embodiment can be manufactured by laminating and molding one FRP precursor or two or more (preferably 2 to 20) FRP precursors under predetermined conditions. it can. A substrate on which the inner layer circuit is processed may be sandwiched between the FRP precursors. By the laminated molding, the FRP precursor is cured (C-staged) to become FRP.
Further, by laminating one or more (preferably 2 to 20) FRP precursors and arranging metal foils on one side or both sides, preferably both sides thereof, a metal-clad laminate is formed. Can be manufactured.

As the lamination condition, a known condition used for manufacturing a laminate used for a printed wiring board can be adopted. For example, a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, or the like can be used, and conditions of laminating at 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 can be adopted.

The thickness of the metal foil is preferably 40 μm or less, more preferably 1 to 40 μm, further preferably 5 to 40 μm, further preferably 5 to 35 μm, particularly preferably 5 to 25 μm, and most preferably 5 to 17 μm.

The metal of the metal foil includes copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or at least one of these metal elements from the viewpoint of conductivity. It is preferably an alloy. As the alloy, copper-based alloys, aluminum-based alloys, and iron-based alloys are preferable. Examples of copper-based alloys include copper-nickel alloys. Examples of the iron-based alloy include an iron-nickel alloy (42 alloy). Among these, copper, nickel, and 42 alloy are more preferable as the metal, and copper is further preferable from the viewpoint of availability and cost.

[Printed circuit board]
The printed wiring board of this embodiment is a printed wiring board manufactured by using the laminated board of this embodiment.
The printed wiring board of the present embodiment can be manufactured, for example, by forming a wiring pattern on the laminated board of the present embodiment. Examples of the wiring pattern forming method include known methods such as a subtractive method, a full additive method, a semi-additive method (SAP: Semi Additive Process), or a modified semi-additive method (m-SAP: modified Semi Additive Process). Be done.

[Semiconductor package]
The semiconductor package of this embodiment is a semiconductor package in which a semiconductor is mounted on a printed wiring board of this embodiment.
The semiconductor package of the present embodiment can be manufactured by mounting a semiconductor element such as a semiconductor chip or a memory at a predetermined position on the printed wiring board of the present embodiment and sealing the semiconductor element with a sealing resin or the like.

Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
The performance of the thermosetting resin and FRP precursor produced in each example was measured by the following method.

[Minimum melt viscosity of resin film]
Using the resin film obtained in each example as a measurement sample, the minimum melt viscosity and the minimum melt viscosity temperature were measured under the following conditions.
-Measuring equipment: AR2000ex (manufactured by TA Instruments)
-Measurement temperature range: 50 to 200 ° C
・ Temperature rise rate: 3 ° C / min
-Test piece: 20 mm circular tablet compressed with resin of resin-attached film-Load: 0.20 N

[Implantability of thermosetting resin in aggregate]
The surface of the FRP precursor obtained in each example was observed at 100 times using an optical microscope, and the impregnation property was evaluated based on the following criteria.
(Evaluation criteria)
A: There is no resin-unimpregnated part in the aggregate.
B: There is a very small amount of resin-unimpregnated portion in the aggregate.
C: There is a small amount of resin-unimpregnated portion in the aggregate.
D: There are many non-resin-impregnated parts in the aggregate, the resin is not impregnated in the aggregate, or the aggregate is exposed.

[Appearance of FRP precursor]
The surface of the FRP precursor obtained in each example was observed at 100 times using an optical microscope, and the appearance was evaluated based on the following criteria.
(Evaluation criteria)
A: There is no abnormality in appearance.
B: There is a slight appearance abnormality.
C: There are many abnormal appearances.

[Preparation of thermosetting resin varnish]
Preparation Example 1
Add 15 parts by mass of cyclohexane and 130 parts by mass of methyl ethyl ketone to 100 parts by mass of phenol novolac type epoxy resin (N-660; manufactured by DIC Corporation) and 60 parts by mass of cresol novolak resin (KA-1165; manufactured by DIC Corporation) and stir. And dissolved. There, 180 parts by mass of aluminum hydroxide (CL-303; manufactured by Sumitomo Chemical Co., Ltd.) as an inorganic filler, 1 part by mass of a coupling agent (A-187; manufactured by Momentive Performance Materials), and an isocyanate mask as a curing accelerator. 2.5 parts by mass of imidazole (G8009L; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added and stirred to dissolve and disperse to obtain a thermosetting resin varnish having a solid content concentration of 70% by mass.

[Manufacturing of FRP precursor 1]
Examples 1-9
(1) Preparation of Resin Films A to C The thermosetting resin varnish obtained above is dried on a 580 mm wide PET film (G-2; manufactured by Teijin DuPont Film Co., Ltd.) as a support with a coating width of 540 mm. After the resin film was applied so as to have a thickness of 20 μm, it was dried under predetermined conditions to prepare resin films A to C with a support.
Drying was carried out until the amount of residual solvent in the resin film was 1.0% by mass or less, and the minimum melt viscosity of the resin film A was 1,500 mPa · s, and the minimum melt viscosity of the resin film B was 700 mPa · s. The drying conditions were adjusted so that the minimum melt viscosity of the resin film C was 2,500 mPa · s.

(2) Step of impregnating aggregate with pressure welding Next, the resin films obtained above were combined with a glass cloth (air permeability: as shown in Table 1) with a basis weight of 10.2 g / m ² . IPC # 1010, width 550 mm, thickness 11 μm, manufactured by Unitika Co., Ltd.) A heating and pressurizing roll with the same support as the above-mentioned support applied to the other surface of the glass cloth. The glass cloth was pressure-impregnated with a resin film under the laminating conditions shown in Table 1. Then, it cooled with a cooling roll and wound up to obtain an FRP precursor. Lamination was performed from roll to roll, and the line speed was constant at 1.0 m / min.

The evaluation results of the FRP precursors obtained in each example are shown in Table 1.

From Examples 1 to 3 in Table 1, from Example 3 using a resin film having a minimum melt viscosity of 2,500 mPa · s, Example 1 using a resin film having a minimum melt viscosity of 1,500 mPa · s or 750 mPa · s. It can be seen that 2 and 2 are more excellent in impregnation into the aggregate.
Further, from Examples 4 to 7 in Table 1, the aggregates were impregnated in Examples 5 to 7 having a pressure of 0.3 to 0.7 MPa as compared with Example 4 in which the pressure at the time of pressure welding was 0.15 MPa. It can be seen that the properties are excellent, and among them, Example 5 in which the pressure at the time of pressure welding is 0.3 MPa and Example 6 in which the pressure at the time of pressure welding is 0.5 MPa are also excellent in the appearance of the FRP precursor.
Further, from Examples 1, 8 and 9 in Table 1, Example 9 having an aggregate air permeability of 110 cc / cm ² / sec is 200 cc / cm ² / sec, and further 260 cc / sec, as compared with Example 8. It can be seen that Example 1 having a cm of ² / sec is more excellent in impregnating the aggregate.

Next, the productivity of the FRP precursor by the production method of this embodiment was evaluated.

[Manufacturing of FRP precursor 2]
Examples 10 to 13
(1) Preparation of Resin Films D to G The thermosetting resin varnish prepared in Preparation Example 1 was applied to a PET film having a width of 580 mm (G-2; manufactured by Teijin DuPont Film Co., Ltd.) with a coating width of 540 mm and a resin after drying. The film was applied so as to have a thickness of 20 μm or 10 μm, and dried under the conditions shown in Table 2 to obtain resin films D to G.
(2) Step of impregnating aggregate with pressure welding The resin films D to G obtained above were mixed with glass cloth (air permeability: 260 cc / cm ² / sec, basis weight 10.2 g / m ² , IPC # 1010, width 550 mm, (Thickness 11 μm, manufactured by Unitika Co., Ltd.) With the same support as the above-mentioned support applied to the other surface of the glass cloth, it is sandwiched between heating and pressurizing rolls, and the pressure during pressure welding is applied. The glass cloth was pressure-impregnated with a resin film by laminating under the conditions of 0.4 MPa and a heating roll temperature of 140 ° C. Then, it cooled with a cooling roll and wound up to obtain an FRP precursor. Lamination was performed from roll to roll, and the line speed was constant at 1.0 m / min.

Table 2 shows the evaluation results of the FRP precursors obtained in each example.

In Table 2, from Example 10, the resin film having a thickness of 20 μm was sufficiently dried and removed from the solvent under high temperature and short-time drying conditions of 150 ° C. for 2 minutes, and the minimum melt viscosity was kept low. It can be seen that excellent impregnation property into the aggregate can be obtained.
On the other hand, from Example 11, the resin film having a thickness of 10 μm has a high minimum melt viscosity and a relatively low impregnation property in the aggregate under high temperature of 150 ° C. for 2 minutes and a short drying condition. It has become. Further, from Example 13, the resin film having a thickness of 10 μm needs to be dried for 5 minutes in order to bring the residual solvent amount to a predetermined value under a low temperature condition of 120 ° C., and the thickness is 20 μm. It can be seen that it takes more time to prepare the resin film than a certain resin film.
From this, the case where the pressure welding impregnation of the resin film is performed from only one surface of the aggregate and the case where the pressure welding impregnation of the resin film is performed from both sides of the aggregate is better when the pressure welding impregnation is performed from only one surface. It can be seen that since the thickness of the film can be increased, a resin film having excellent impregnation property into the aggregate can be produced in a short time, and the productivity is excellent.

[Manufacturing of FRP precursor 3]
Example 14, Comparative Example 1
Next, using the resin film D obtained above, the production time when the resin film is pressure-welded and impregnated from only one surface of the aggregate to prepare an FRP precursor, and the resin film F obtained above are obtained. It was compared with the production time in the case where the resin film was pressure-welded and impregnated from both sides of the aggregate to prepare an FRP precursor. The glass cloth, laminating conditions, etc. used here are the same as those in the first embodiment. The results are shown in Table 3.

From Table 3, the single-sided pressure-welding impregnation method of the present embodiment has a shorter time required for coating during the production of the resin film than the conventional double-sided pressure-welding impregnation method, and the production time of the FRP precursor can be significantly shortened. I understand.

1 FRP precursor manufacturing device 2 Aggregate delivery device 3 Resin film delivery device 3'Second support delivery device 4 Protective film peeling mechanism 5 Protective film winding device 6 Sheet heating and pressurizing device (film pressure welding means)
7 Sheet pressurizing cooling device 8 FRP precursor winding device 40 Aggregate 40a Surface of aggregate (one surface of aggregate, one of both surfaces of aggregate)
40b Back side of aggregate (the other surface of the aggregate, the other of both surfaces of the aggregate)
50 Resin film with first support and protective film (multilayer film)
52 Protective film 53 First support 54 Resin film 54a Surface of the resin film on the aggregate side (surface of the film on the aggregate side)
55 Resin film with first support 56 Second support 60 FRP precursor

Claims (12)

A method for producing an FRP precursor in which a thermosetting resin film is heated and pressure-welded impregnated in a sheet-shaped aggregate, and the thermosetting resin film is pressure-welded and impregnated only from one surface of the sheet-shaped aggregate. A method for producing an FRP precursor, which comprises a step. The method for producing an FRP precursor according to claim 1, wherein the thermosetting resin film is pressure-welded and impregnated by laminating. The method for producing an FRP precursor according to claim 1 or 2, wherein the minimum melt viscosity of the thermosetting resin film is 500 to 3,000 mPa · s. The method for producing an FRP precursor according to any one of claims 1 to 3, wherein the air permeability of the aggregate is 110 cc / cm ^{2 / sec or more.} The method for producing an FRP precursor according to any one of claims 1 to 4, wherein the thermosetting resin film is pressure-welded and impregnated into the sheet-shaped aggregate at a linear pressure of 0.1 to 1 MPa. Any of claims 1 to 5, wherein the ratio of the thickness of the thermosetting resin film to the thickness of the sheet-shaped aggregate [thermosetting resin film / sheet-shaped aggregate] is 1.1 to 2.5. The method for producing an FRP precursor according to item 1. The thermosetting resin film is a thermosetting resin film with a first support having a first support on one surface.
The thermosetting resin film with the first support is arranged on the one surface of the sheet-shaped aggregate so that the thermosetting resin film is on the one surface side of the sheet-shaped aggregate. ,
With the second support placed on the other surface of the sheet-shaped aggregate,
The method for producing an FRP precursor according to any one of claims 1 to 6, wherein the thermosetting resin film is pressure-welded and impregnated. The method for producing an FRP precursor according to claim 7, wherein the material of the first support and the material of the second support are the same. An FRP precursor produced by the method for producing an FRP precursor according to any one of claims 1 to 8. A laminated board obtained by laminating and molding the FRP precursor according to claim 9. A multilayer printed wiring board manufactured by using the laminated board according to claim 10. A semiconductor package in which a semiconductor is mounted on the multilayer printed wiring board according to claim 11.