JPWO2008123248A1 - Insulating sheet with substrate, multilayer printed wiring board, semiconductor device, and method for manufacturing multilayer printed wiring board - Google Patents

Abstract

When used for an insulating layer of a multilayer printed wiring board, the base material can be easily peeled from the insulating sheet, and the insulating sheet with the base material that does not cause cracking or falling off of the insulating layer, the multilayer printed wiring board, A semiconductor device is provided. An insulating sheet with a base material used for forming an insulating layer of a multilayer printed wiring board, wherein an insulating layer made of a resin composition is provided on a base material, and the insulating layer is heated on an adherend surface. After the adhesive layer is pressed and bonded, and the insulating layer is heated and cured, the peel strength for peeling the substrate from the insulating layer is 0.2 kN / m or less, and the insulating layer is peeled from the substrate after heat curing. An insulating sheet with a base material characterized by being used as a base material, and an insulating layer made of a resin composition is provided on the base material, and the insulating layer is attached to the adherend surface at 60 to 160 ° C., When heated and pressurized at 0.2 to 5 MPa for 0.5 to 15 minutes, the peeling strength for peeling the substrate from the insulating layer at 20 ° C. is 0.05 kN / m or less. Insulating sheet with substrate.

Description

  The present invention relates to an insulating sheet with a substrate, a multilayer printed wiring board, a semiconductor device, and a method for producing a multilayer printed wiring board.

  In recent years, with the demand for higher functionality of electronic devices, etc., high-density integration of electronic components, and further high-density mounting, etc. are progressing. Compared to the conventional technology, miniaturization and high density are progressing. As a measure for increasing the density of printed wiring boards and the like, a multilayer printed wiring board using a build-up method is often employed (for example, see Patent Document 1).

  A multilayer printed wiring board by a build-up method is usually manufactured by laminating an insulating sheet made of a resin composition and having a thickness of 100 μm or less and a conductor circuit layer. In addition, as a connection method between conductor circuit layers, a method such as forming a via hole by processing such as a laser method or a photo method instead of conventional drilling, and conducting conduction between insulating layers by a metal plating process, etc. It is done. These methods achieve high density by freely arranging small-diameter via holes, and various build-up interlayer insulating materials corresponding to each method have been proposed.

  These insulating sheets with base materials for build-up systems are heat-bonded to the conductor circuit layer, insulating the base material before semi-curing the insulating layer, after semi-curing or after curing, and before forming via holes. Although it peels from a sheet | seat, when the adhesive force of an insulating sheet and a base material was too strong, there existed a problem that the process of peeling will become difficult and the crack of an insulating layer, or dropping off would be caused. In particular, when the insulating layer is cured without peeling off the substrate, and then the substrate is peeled off, there is an advantage that the curing of the insulating layer proceeds uniformly and the flatness of the insulating layer is improved. Due to this heating, the adhesion between the insulating sheet and the substrate becomes too strong, making the peeling process difficult, and causing problems such as cracking of the insulating layer and residual adhesion of the substrate.

Japanese Patent Laid-Open No. 07-106767

  The present invention provides an insulating sheet with a base material, a multilayer printed wiring board, a semiconductor device, and a semiconductor device capable of producing a multilayer printed wiring board having good workability and high reliability when used for an insulating layer of a multilayer printed wiring board A method for producing a multilayer printed wiring board is provided.

Such an object is achieved by the following present inventions [1] to [26].
[1] An insulating sheet with a base material used for forming an insulating layer of a multilayer printed wiring board, wherein an insulating layer made of a resin composition is provided on a base material, and the insulating layer is attached to a surface to be bonded After being heated and pressed to adhere and the insulating layer is heat-cured, the peel strength for peeling the substrate from the insulating layer at 20 ° C. is 0.2 kN / m or less, and the insulating layer is An insulating sheet with a base material, which is used after peeling from the base material after heat curing.
[2] The insulating layer is adhered to the adherend surface by heating and pressing the adherend surface at 60 to 160 ° C. and 0.2 to 5 MPa for 0.5 to 15 minutes, and [1] The peel strength at which the base material is peeled off from the insulating layer after heating and curing the insulating layer by heating at 140 to 240 ° C. for 30 to 120 minutes is 0.2 kN / m or less. The insulating sheet with a base material according to Item.
[3] The insulating sheet with a base material according to [1] or [2], wherein the base material is subjected to a peeling treatment with a peeling treatment agent.
[4] The insulating sheet with a base material according to [3], wherein the release treatment agent is a non-silicone release treatment agent.
[5] The insulating sheet with a base material according to [3] or [4], wherein the release treatment agent includes a compound having a urethane bond.
[6] The insulating sheet with a base material according to any one of [1] to [5], wherein the base material is a polyester resin film.
[7] The insulating sheet with base material according to [6], wherein the polyester resin film is a polyethylene terephthalate film or a polyethylene naphthalate film.
[8] The insulating sheet with base material according to any one of [1] to [7], wherein the resin composition contains an epoxy resin.
[9] The insulating sheet with a base material according to any one of [1] to [8], wherein the resin composition contains an inorganic filler.
[10] The insulating sheet with a base material according to any one of [1] to [9], wherein the resin composition contains an imidazole compound.

  [11] A multilayer printed wiring board formed by heating and press-molding the insulating sheet with base material according to any one of items [1] to [10] on one or both surfaces of the inner layer circuit board.

  [12] A semiconductor device using the multilayer printed wiring board according to the item [11] as a package substrate.

[13] The insulating sheet with base material according to any one of items [1] to [10] and an inner layer circuit board are overlapped with the insulating layer of the insulating sheet with base material facing the inner layer circuit board, Heating and pressurizing at a temperature lower than the curing temperature of the resin composition to produce a multilayer printed wiring board precursor, and heating the multilayer printed wiring board precursor to a temperature equal to or higher than the curing temperature of the resin composition to form the insulating layer. A method of producing a multilayer printed wiring board, comprising: a step of peeling the substrate and producing a multilayer printed wiring board after curing.
[14] An insulating sheet with a base material used for forming an insulating layer of a multilayer printed wiring board, wherein an insulating layer made of a resin composition is provided on the base material, and the insulating layer is attached to the surface to be bonded When the film is heated and pressurized at 60 to 160 ° C. and 0.2 to 5 MPa for 0.5 to 15 minutes, the peel strength at which the substrate is peeled from the insulating layer at 20 ° C. is 0.05 kN / m or less. An insulating sheet with a base material, characterized in that there is.
[15] The insulating sheet with a base material according to item [14], wherein the base material has been subjected to a release treatment with a release treatment agent.
[16] The insulating sheet with base material according to [15], wherein the release treatment agent is a non-silicone release treatment agent.
[17] The insulating sheet with base material according to [15] or [16], wherein the release treatment agent includes a compound having a urethane bond.
[18] The insulating sheet with a base material according to any one of [14] to [17], wherein the base material is a polyester resin film.
[19] The insulating sheet with base material according to [18], wherein the polyester resin film is a polyethylene terephthalate film or a polyethylene naphthalate film.
[20] The insulating sheet with a base material according to any one of [14] to [19], wherein the resin composition contains an epoxy resin.
[21] The insulating sheet with base material according to any one of [14] to [20], wherein the resin composition contains an inorganic filler.
[22] The insulating sheet with base material according to any one of [14] to [21], wherein the resin composition contains an imidazole compound.
[23] The item according to items [14] to [22], wherein the peel strength before curing the insulating layer is 0.05 kN / m or less, and the layer is peeled off from the base material before curing the insulating layer. The insulating sheet with a base material according to any one of the above.

  [24] A multilayer printed wiring board obtained by heating and press-molding the insulating sheet with a base material according to any one of items [14] to [23] on one or both surfaces of the inner circuit board.

  [25] A semiconductor device using the multilayer printed wiring board according to the item [24] as a package substrate.

  [26] The insulating sheet with base material according to any one of items [14] to [23] and the inner layer circuit board are overlapped with the insulating layer of the insulating sheet with base material facing the inner layer circuit board, In the step of producing a multilayer printed wiring board precursor by heating and pressing at a temperature lower than the curing temperature of the resin composition, and in the multilayer printed wiring board precursor, after peeling the substrate from the insulating layer, the resin composition A method of producing a multilayer printed wiring board, comprising: heating the above-described curing temperature to cure the insulating layer to produce a multilayer printed wiring board.

The present invention is an insulating sheet with a base material used for forming an insulating layer of a multilayer printed wiring board, wherein an insulating layer made of a resin composition is provided on the base material, and the insulating layer is adhered After the surface is heated and pressed to adhere and the insulating layer is heat-cured, the peel strength for peeling the substrate from the insulating layer is 0.2 kN / m or less, and the insulating layer is heat-cured An insulating sheet with a base material, which is used by being peeled from the base material, and an insulating sheet with a base material used for forming an insulating layer of a multilayer printed wiring board, wherein the resin composition When the insulating layer is provided on a base material, and the insulating layer is heated and pressed at 60 to 160 ° C. and 0.2 to 5 MPa for 0.5 to 15 minutes at 20 ° C., The peel strength at which the substrate is peeled from the insulating layer is 0. There is provided an insulating sheet with the substrate to equal to or less than 5 kN / m.
By using the insulating sheet with a substrate of the present invention for an insulating layer of a multilayer printed wiring board, a multi-layer printed wiring board capable of forming a high-density and fine circuit without causing troubles and having good workability is manufactured. Can do. In particular, it can be suitably used for a substrate called a package substrate used for system-in-package (SiP) or the like. Since the package substrate serves as an intermediary for signal transmission between the printed wiring board and the semiconductor element between the printed wiring board and the semiconductor element, high-density fine circuit formation is required. By using the insulating sheet, it is possible to form a high-density fine circuit required for the package substrate. Furthermore, a semiconductor device in which a semiconductor element is mounted on a package substrate manufactured using the insulating sheet with a base material of the present invention is excellent in reliability.

Below, the insulating sheet with a base material of the present invention, a multilayer printed wiring board, and a semiconductor device are explained in detail.
The first insulating sheet with a base material of the present invention is an insulating sheet with a base material used for forming an insulating layer of a multilayer printed wiring board, and an insulating layer made of a resin composition is provided on the base material. The peel strength at which the base material is peeled off from the insulating layer at 20 ° C. after the insulating layer is heated and pressurized to adhere to the adherend surface and the insulating layer is heat-cured is 0.degree. It is 2 kN / m or less, and the insulating layer is used after being heat-cured and peeled off from the base material.

Moreover, the 1st multilayer printed wiring board of this invention superposes the said 1st insulating sheet with a base material of this invention on one side or both surfaces of an inner-layer circuit board, and heat-press-molds it.
Further, in the first semiconductor device of the present invention, the first multilayer printed wiring board of the present invention can be suitably used as a package substrate constituting a semiconductor device such as a system-in-package. A semiconductor device in which a semiconductor element is mounted on the package substrate is excellent in reliability.
Moreover, the manufacturing method of the 1st multilayer printed wiring board of this invention WHEREIN: The said 1st insulating sheet with a base material of this invention and an inner-layer circuit board are used for the insulating layer of this insulating sheet with a base material, and this inner-layer circuit. Overlaying on the board side, heating and pressing below the curing temperature of the resin composition to produce a multilayer printed wiring board precursor, and the multilayer printed wiring board precursor at a temperature equal to or higher than the curing temperature of the resin composition Heating and curing the insulating layer, and then peeling the base material to produce a multilayer printed wiring board.

  The second insulating sheet with a base material of the present invention is an insulating sheet with a base material used for forming an insulating layer of a multilayer printed wiring board, and an insulating layer made of a resin composition is provided on the base material. Peeling that peels off the substrate from the insulating layer at 20 ° C. when the insulating layer is heated and pressed at 60 to 160 ° C. and 0.2 to 5 MPa for 0.5 to 15 minutes on the surface to be bonded. The strength is 0.05 kN / m or less.

Moreover, the second multilayer printed wiring board of the present invention is formed by heating and press-molding the above-mentioned second insulating sheet with a base material of the present invention on one side or both sides of the inner layer circuit board.
Furthermore, in the second semiconductor device of the present invention, the second multilayer printed wiring board of the present invention can be suitably used as a package substrate constituting a semiconductor device such as a system-in-package. A semiconductor device in which a semiconductor element is mounted on the package substrate is excellent in reliability.
The second multilayer printed wiring board manufacturing method of the present invention includes the second insulating sheet with a base material of the present invention and an inner layer circuit board, and the insulating layer of the insulating sheet with a base material of the inner layer circuit. Laminating on the board side, heating and pressing below the curing temperature of the resin composition to produce a multilayer printed wiring board precursor, and peeling the substrate from the insulating layer in the multilayer printed wiring board precursor And then heating to a temperature equal to or higher than the curing temperature of the resin composition to cure the insulating layer and producing a multilayer printed wiring board.

First, the insulating sheet with a base material of the present invention will be described.
The insulating sheet with a substrate of the present invention can be obtained by forming an insulating layer made of a resin composition on a substrate. The “base material” used in the present invention means a metal foil or a resin film, which will be described later with specific examples.
In the present invention, the peel strength can be measured using, for example, a precision universal testing machine (Autograph AG-IS, manufactured by Shimadzu Corporation). Peel strength is a direction in which the end of the substrate having a width of 1 cm is partially peeled off at 20 ° C., the tip is held with a gripping tool, and the pulling direction is perpendicular to the insulating layer bonded to the adherend surface. The average value (n = 2 or more) when peeling 30 mm continuously at a speed of 5 mm / min was used.
Further, in the present invention, the bonded surface is a surface to be bonded to the insulating layer of the insulating sheet with a base material, and the insulating layer has a peeling strength that does not peel from the insulating layer when the insulating layer and the base material are peeled off. Glue. In addition to the inner layer circuit board constituting the multilayer printed wiring board, the surface to be bonded can be used without particular limitation. In order to measure the peel strength between the insulating layer and the base material, a test piece substrate that provides an adherend surface that satisfies the above conditions can also be used.

  The first insulating sheet with a base material of the present invention is an insulating sheet with a base material used for forming an insulating layer of a multilayer printed wiring board, and an insulating layer made of a resin composition is provided on the base material. The peel strength at which the base material is peeled off from the insulating layer at 20 ° C. after the insulating layer is heated and pressurized to adhere to the adherend surface and the insulating layer is heat-cured is 0.degree. It is 2 kN / m or less, and the insulating layer is used after being heat-cured and peeled off from the base material.

In an insulating sheet with a base material in which an insulating layer made of a resin composition is provided on a base material, the insulating layer is bonded to the surface to be bonded by heating and pressing, and the insulating layer is heated and cured, When the substrate is peeled from the insulating layer, if the peel strength exceeds the upper limit (0.2 kN / m), the substrate and the insulating layer can be peeled off when the multilayer printed wiring board is manufactured. It may be difficult to peel the substrate from the insulating layer, or the insulating layer may be cracked during peeling.
On the other hand, the first insulating sheet with a base material of the present invention adheres the insulating layer to the adherend surface by heating and pressurization, and after the insulating layer is heat-cured, the insulating layer is formed from the insulating layer. Since the material can be peeled without difficulty, the workability is excellent and the insulating layer is not easily cracked or dropped off. That is, an insulating layer with high surface smoothness can be provided. Therefore, a fine wiring circuit can be accurately formed on the surface of the insulating layer provided by the present invention, and a large number of fine concavo-convex shapes can be formed on the surface in a roughening process described later with high uniformity. Can be formed.

In the first insulating sheet with a base material of the present invention, the peel strength is preferably in the range of 0.001 to 0.1 kN / m, and preferably in the range of 0.005 to 0.05 kN / m. Most preferred. When the peel strength is less than the lower limit, the adhesion between the base material and the insulating layer is weak.For example, when manufacturing a multilayer printed wiring board, an insulating sheet with a base material is laminated on the inner layer circuit board and then heat-cured. Before performing, a base material peels and a foreign material adheres to the surface of an insulating layer, and a malfunction may arise.
In the first insulating sheet with a base material of the present invention, the insulating layer is heated and pressed on the adherend surface at 60 to 160 ° C. and 0.2 to 5 MPa for 0.5 to 15 minutes. The peel strength between the insulating layer and the substrate before heat curing is preferably in the range of 0.001 to 0.05 kN / m, and more preferably in the range of 0.005 to 0.03 kN / m.

In the first insulating sheet with a substrate of the present invention, the conditions for pressurizing and heating the insulating layer to the adherend surface are not particularly limited, but at a heating temperature of 60 to 160 ° C. and a pressure of 0.2 to 5 MPa, It is preferable to hold for 0.5 to 15 minutes, and it is particularly preferable to hold for 1 to 5 minutes at a heating temperature of 80 to 120 ° C. and a pressure of 1 to 3 MPa.
Moreover, the curing temperature condition for heat-curing the insulating layer is not particularly limited, but it is preferable to cure the insulating layer at 140 to 240 ° C, more preferably 150 to 200 ° C, and most preferably 160 to 180 ° C. It is. The heating time is not particularly limited, but is preferably 30 to 120 minutes, and particularly preferably 45 to 90 minutes.

  On the other hand, the second insulating sheet with a base material of the present invention is an insulating sheet with a base material used for forming an insulating layer of a multilayer printed wiring board, and the insulating layer made of a resin composition is formed on the base material. When the insulating layer is heated and pressed at 60 to 160 ° C. and 0.2 to 5 MPa for 0.5 to 15 minutes at 20 ° C., the base material is peeled from the insulating layer. The peel strength to be applied is 0.05 kN / m or less. The second insulating sheet with a substrate typically has a peel strength of 0.05 kN / m or less before the insulating layer is cured, and is used by peeling the insulating layer from the substrate before curing. It is.

In the insulating sheet with a base material in which the insulating layer made of the resin composition is provided on the base material, the insulating layer is heated on the surface to be bonded at 60 to 160 ° C. and 0.2 to 5 MPa for 0.5 to 15 minutes. When the peel strength when pressed, in particular, the peel strength for peeling the substrate from the insulating layer before curing exceeds the upper limit (0.05 kN / m), the substrate and It is very difficult to peel off the insulating layer, and the base material cannot be peeled from the insulating layer, or cracks may occur in the insulating layer during peeling.
On the other hand, the second insulating sheet with a base material of the present invention is such that the insulating layer is heated and pressed on the adherend surface at 60 to 160 ° C. and 0.2 to 5 MPa for 0.5 to 15 minutes, and then the insulating layer. Since the base material can be peeled off without difficulty, the workability is excellent and the insulating layer is not easily cracked or dropped off. That is, an insulating layer with high surface smoothness can be provided. Therefore, a fine wiring circuit can be accurately formed on the surface of the insulating layer provided by the present invention, and a large number of fine concavo-convex shapes can be formed on the surface in a roughening process described later with high uniformity. Can be formed.

In the second insulating sheet with a base material of the present invention, the peel strength is preferably in the range of 0.001 to 0.03 kN / m, and preferably in the range of 0.005 to 0.02 kN / m. Most preferred. In addition, the second insulating sheet with a base material has the above peel strength within the above range even when the heating and pressing conditions between the insulating layer and the contacted surface are 80 to 120 ° C. and 1 to 3 MPa for 1 to 5 minutes. It is preferable that
When the peel strength is less than the above lower limit, the adhesion between the base material and the insulating layer is weak. For example, when a multilayer printed wiring board is manufactured, the insulating layer is heated on the inner layer circuit board after being laminated. Prior to curing, the substrate may be peeled off, and foreign matter may adhere to the surface of the insulating layer, causing problems. Moreover, when the peel strength is less than the above lower limit value, the base material is peeled off before storage of the insulating sheet with the base material, and problems such as deterioration in handleability and adhesion of foreign matter to the surface of the insulating layer are likely to occur.

Hereinafter, the base material and the insulating layer constituting the first and second insulating sheets with base material of the present invention will be described.
It is preferable that the base material used for the insulating sheet with a base material of the present invention is subjected to release treatment with a release treatment agent. When the peeling treatment is not performed, depending on the resin composition constituting the insulating layer, the peeling strength between the base material and the insulating layer may become too large, and the base material cannot be peeled from the insulating layer. In the case of peeling, the insulating layer may crack.

  The release treatment agent is not particularly limited. For example, a non-silicone release treatment agent can be suitably used. Non-silicone release treatment agents are preferred because the peel strength does not increase too much and does not become too small. Non-silicone release treatment agents include thermosetting polyester resins, aminoalkyl red resins, urethane resins and the like.

  Among these, it is preferable to include a compound having a urethane bond as the non-silicone release treatment agent. A compound having a urethane bond does not react with the components of the insulating sheet to cause a problem, and the change in adhesion with time is small. Examples of the compound having a urethane bond include a reaction product of an ethylene / vinyl alcohol copolymer and an alkyl isocyanate, a reaction product of an ethylene oxide-added polyethyleneimine and an alkyl isocyanate, and the like.

The method for releasing the substrate with the release agent is not particularly limited. For example, a coating solution in which the release agent is dissolved or dispersed in an appropriate organic solvent is prepared, and the coating solution is applied to a roll coater. And a method of coating and drying on the surface to be peeled by an appropriate coating means such as a kiss coater, a gravure coater, a slot die coater, or a squeeze coater.
Processing amount of release treatment layer is not particularly limited, for example, 0.01-5 g / ^{m 2,} preferably in the range of 0.1-2 g / ^{m 2.} If it is this range, it is easy to form a peeling process layer uniformly, can also prevent stickiness, and is easy to handle.

Although the base material used for the insulating sheet with a base material of the present invention is not particularly limited, for example, a thermoplastic resin film having heat resistance such as a polyester resin, a fluororesin, a polyimide resin, or copper and / or copper Metal foils such as aluminum alloys, aluminum and / or aluminum alloys, iron and / or iron alloys, silver and / or silver alloys, and the like can be used. Among these, a polyester resin film is most preferable. Polyester resin has properties suitable as a base material for insulating sheets, such as high strength and heat resistance, and low hygroscopicity. Examples of the polyester resin film include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate.
Although the thickness of the said base material is not specifically limited, When the thing of 10-70 micrometers is used, the handleability at the time of manufacturing an insulating sheet with a base material is favorable, and is preferable.
In manufacturing the insulating sheet with a substrate of the present invention, it is preferable that the unevenness on the surface of the insulating substrate on the side to be joined to the insulating sheet is as small as possible. Thereby, the effect | action of this invention can be expressed effectively.

  The resin composition forming the insulating layer of the insulating sheet with a substrate of the present invention preferably contains one or more epoxy resins. As a result, heat resistance and thermal decomposability can be imparted, and film formability when manufacturing an insulating sheet with a base material and adhesion to an inner circuit board when manufacturing a multilayer printed wiring board can be improved. it can.

  The epoxy resin is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy Resin, dicyclopentadiene type epoxy resin, epoxidized product of condensate of phenol and aromatic aldehyde having phenolic hydroxyl group, triglycidyl isocyanurate, alicyclic epoxy resin, etc., one or more known ones Can be used in combination. Moreover, you may contain the monofunctional epoxy resin as a reactive diluent. Among these, phenol novolac type epoxy resins, alkylphenol novolac type epoxy resins, biphenyl type epoxy resins, and naphthalene type epoxy resins are particularly preferable. Thereby, a flame retardance and moisture absorption solder heat resistance can be improved.

Although it does not specifically limit as content of the said epoxy resin, It is preferable that it is 5 to 80 weight% with respect to the whole resin composition. More preferably, it is 10 to 60% by weight.
If the content of the epoxy resin is less than the lower limit, the effect of improving moisture-absorbing solder heat resistance and adhesion may be small. Moreover, since the dispersibility may worsen when the said upper limit is exceeded, it is unpreferable. By setting the content of the epoxy resin within the above range, it is possible to achieve an excellent balance of these characteristics.

  It is preferable that the resin composition which forms the insulating layer of the insulating sheet with a substrate of the present invention contains one or more kinds of inorganic fillers. The inorganic filler is not particularly limited, and examples thereof include silica, talc, alumina, glass, mica, and aluminum hydroxide. As the inorganic filler, one of these can be used alone, or two or more can be used in combination. Of these, silica is preferable. More preferred is fused silica. Fused silica is superior in low expansion compared to other inorganic fillers. Examples of the shape of silica include a crushed shape and a spherical shape, and a spherical shape is preferable. When it is spherical, the content of the inorganic filler in the resin composition can be increased, and even in that case, the fluidity is excellent. Moreover, another inorganic filler can also be contained as needed.

  Although content of the said inorganic filler is not specifically limited, It is preferable that it is a ratio of 20 to 80 weight% in a resin composition. A more preferable content is 25% by weight or more and 70% by weight or less, and most preferably 30% by weight or more and 60% by weight or less. If the inorganic filler content exceeds the above upper limit, the fluidity of the resin composition may be extremely poor, which may be undesirable, and if it is less than the lower limit, the strength of the insulating layer made of the resin composition is not sufficient, It may not be preferable.

The resin composition forming the insulating layer of the insulating sheet with a substrate of the present invention preferably contains an imidazole compound as a curing accelerator. More preferably, it is an imidazole compound compatible with the resin component contained in the resin composition. By using such an imidazole compound, the reaction of the epoxy resin can be effectively promoted, and equivalent characteristics can be imparted even if the amount of the imidazole compound is reduced.
Furthermore, a resin composition using such an imidazole compound can be cured with high uniformity from a minute matrix unit with a resin component. Thereby, the insulation of the resin layer formed in the multilayer printed wiring board, and heat resistance can be improved.

  The imidazole compound is not particularly limited, but examples thereof include 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2 , 4-Diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- (2'-undecylimidazolyl) -ethyl-s-triazine, 2, , 4-diamino-6- [2′-ethyl-4-methylimidazolyl- (1 ′)]-ethyl-s-triazine and the like.

  Among these, an imidazole compound selected from 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 2-ethyl-4-methylimidazole is preferable. These imidazole compounds have a particularly excellent compatibility, so that a highly uniform cured product can be obtained and a fine and uniform roughened surface can be formed on the surface of the insulating layer. A fine conductor circuit can be easily formed, and high heat resistance can be expressed in the multilayer printed wiring board. Although it does not specifically limit as content of an imidazole compound, 0.01 to 5 weight% is preferable with respect to the sum total of the resin component in an insulating layer, and 0.05 to 3 weight% is especially preferable. Thereby, especially heat resistance can be improved.

The resin composition forming the insulating layer of the insulating sheet with a substrate of the present invention can contain a phenoxy resin as necessary. The phenoxy resin is a high molecular weight epoxy resin having a molecular weight of 1.0 × 10 ⁴ or more, and has a good compatibility and a good adhesive property because the structure is similar to that of the epoxy resin. As the molecular weight increases, film formability can be obtained more easily, and the melt viscosity that affects the fluidity during bonding can be set in a wide range. The molecular weight is preferably in the range of 1.0 × 10 ^{4 to} 7.0 × 10 ⁴ . When the molecular weight exceeds the upper limit, the solubility in a solvent is deteriorated, and it becomes difficult to prepare a resin varnish, which is not preferable.
Although it does not specifically limit as content of a phenoxy resin, It is preferable that it is 1 to 40 weight% of the whole resin composition. More preferably, it is 5 to 30% by weight. Thereby, a film-forming property is good and an insulating sheet that is uniform in appearance can be obtained.

  The resin composition which forms the insulating layer of the insulating sheet with a base material of the present invention can contain a cyanate resin and / or a prepolymer thereof as necessary. These components are effective for improving the flame retardancy of the resin composition. The method for obtaining the cyanate resin and / or its prepolymer is not particularly limited. For example, the cyanate resin can be obtained by reacting a cyanogen halide with a phenol and prepolymerizing it by a method such as heating as necessary. it can. Moreover, the commercial item prepared in this way can also be used.

The cyanate resin and / or prepolymer thereof is not particularly limited, and examples thereof include novolak type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, and bisphenol type cyanate resin such as tetramethylbisphenol F type cyanate resin. Can be mentioned.
In the insulating sheet with a substrate of the present invention, the content of the cyanate resin is not particularly limited, but is preferably 5 to 50% by weight with respect to the entire resin composition. More preferably, it is 10 to 40% by weight. Thereby, the heat resistance and flame retardance of the cyanate resin can be expressed more effectively.

  The resin composition which forms the insulating layer of the insulating sheet with a base material of the present invention can contain a phenolic curing agent as necessary. The phenolic curing agent is not particularly limited. For example, a phenolic novolak resin, an alkylphenol novolak resin, a bisphenol A novolak resin, a dicyclopentadiene type phenol resin, a terpene-modified phenol resin, a polyvinylphenol, or the like can be used alone or Two or more types can be used in combination. Use of a phenolic curing agent improves flame retardancy and adhesion.

  In addition to the components described above, the resin composition forming the insulating layer of the insulating sheet with a substrate of the present invention provides adhesion as required, such as imidazole, thiazole, triazole, and silane coupling agents. Additives such as colorants such as agents, silicone-based, fluorine-based, polymer-based antifoaming agents and / or leveling agents, titanium oxide, and carbon black can be contained.

Here, the method for forming the insulating layer made of the resin composition on the substrate is not particularly limited. For example, the resin composition is dissolved and dispersed in a solvent to prepare a resin varnish, and various coater apparatuses are used. Examples thereof include a method in which a resin varnish is applied to a substrate and then dried, and a method in which the resin varnish is spray-coated on a substrate with a spray device and then dried.
As a method of preparing the resin varnish, for example, using various mixers such as an ultrasonic dispersion method, a high-pressure collision dispersion method, a high-speed rotation dispersion method, a bead mill method, a high-speed shear dispersion method, and a rotation and revolution dispersion method, The method of mixing and stirring a resin composition and a solvent is mentioned. The coater is not particularly limited, and for example, a roll coater, a bar coater, a knife coater, a gravure coater, a die coater, a comma coater, a curtain coater, or the like can be used. Among these, it is preferable to use a die coater, a knife coater, and a comma coater. Thereby, the insulating sheet with a base material which does not have a void and has a uniform thickness of the insulating resin layer can be efficiently produced.

The solvent used for the preparation of the resin varnish is not particularly limited. For example, alcohols, ethers, acetals, ketones, esters, alcohol esters, ketone alcohols, ether alcohols, ketone ethers, ketones Esters and ester ethers can be used.
Although it does not specifically limit as solid content in the said resin varnish, 30 to 80 weight% is preferable and especially 40 to 70 weight% is preferable.

  In the insulating sheet with a substrate of the present invention, the thickness of the insulating layer composed of the resin composition is not particularly limited, but is preferably 10 to 100 μm. More preferably, it is 20-80 micrometers. Thereby, when manufacturing a multilayer printed wiring board using this insulating sheet with a base material, while being able to fill and shape the unevenness | corrugation of an inner-layer circuit, suitable insulation layer thickness can be ensured. Moreover, in an insulating sheet with a base material, generation | occurrence | production of the crack of an insulating layer can be suppressed and powder fall at the time of cutting can be decreased.

Next, the multilayer printed wiring board using the insulating sheet with a substrate of the present invention will be described.
The multilayer printed wiring board is formed by heating and press-molding the insulating sheet with a base material on one or both surfaces of the inner layer circuit board.

Specifically, the insulating layer side of the first or second insulating sheet with a base material of the present invention and the inner layer circuit board are combined and vacuum-heated and pressure-molded using a vacuum-pressurizing laminator apparatus or the like, and then A multilayer printed wiring board can be obtained by heat-curing the insulating layer with a hot air dryer or the like.
Although it does not specifically limit as conditions to heat-press form here, if an example is given, it can implement at the temperature of 60-160 degreeC, and the pressure of 0.2-5 MPa. At this time, the heating and pressing time may be, for example, about 0.5 to 15 minutes. Moreover, it is although it does not specifically limit as conditions for heat-hardening an insulating layer, If an example is given, it can implement in temperature 140-240 degreeC and time 30-120 minutes.
As described above, in the manufacturing process of a multilayer printed wiring board, when the insulating layer is heated and cured after the insulating sheet with the base material and the inner circuit board are vacuum-heated and pressed, the second insulating material with the base material is used. In the case of using a sheet, typically, the substrate is peeled from the insulating layer after the vacuum heating and pressure forming and before the heat curing of the insulating layer.

  Or the 1st or 2nd insulating sheet with a base material of the present invention (when the second insulating sheet with a base material is used, typically, the base material is peeled from the insulating sheet with a base material) The insulating layer side is superimposed on the inner circuit board, and this is heated and pressed using a flat plate press or the like, whereby the insulating layer is cured and a multilayer printed wiring board can be obtained. Although it does not specifically limit as conditions to heat-press form here, For example, it can implement at the temperature of 140-240 degreeC, and the pressure of 1-4 MPa.

  As the inner circuit board used when obtaining the multilayer printed wiring board, for example, a predetermined conductor circuit is formed on both surfaces of a copper clad laminate by etching or the like, and the conductor circuit portion is blackened. be able to.

  The multilayer printed wiring board obtained above further peels and removes the substrate before or after the insulating layer is cured, and the insulating resin layer surface is oxidized with an oxidizing agent such as permanganate or dichromate. After the roughening treatment, a new conductive wiring circuit can be formed by metal plating. The insulating resin layer formed from the insulating sheet with a base material of the present invention can form a large number of fine irregularities on the surface thereof with high uniformity in the roughening treatment step. Since the smoothness is high, a fine wiring circuit can be formed with high accuracy.

Next, a semiconductor device using the multilayer printed wiring board of the present invention as a package substrate will be described.
The semiconductor device is manufactured by mounting a semiconductor chip on a package substrate in which a wiring circuit is formed on the multilayer printed wiring board obtained above, and sealing with a sealing resin. The semiconductor chip mounting method and sealing method are not particularly limited. For example, using a semiconductor element and a package substrate, and using a flip chip bonder or the like to align the connection electrode portion on the substrate and the metal bump of the semiconductor element, an IR reflow device, a hot plate, and other heating devices The solder bumps are heated to the melting point or higher by using, and the multilayer printed wiring board on the substrate and the solder bumps are connected by fusion bonding, and a liquid sealing resin is filled between the substrate and the semiconductor element and cured. Thus, a semiconductor device can be obtained.
Since the multilayer printed wiring board of the present invention can be easily processed into fine wiring during production, a semiconductor device having excellent mounting reliability and thermal shock resistance can be manufactured by using it as a package substrate.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.
The raw materials used in Examples and Comparative Examples are as follows.
(1) Release treatment agent A / non-silicone release treatment agent: manufactured by Otsuka Kogyo Co., Ltd., “Pyroyl 1050”
(2) Release agent B / silicone release agent: Shin-Etsu Chemical Co., Ltd. “KS-776A”
(3) Inorganic filler / manufactured by Admatechs Co., Ltd. “SO-25H”, average particle size 0.5 μm
(4) Epoxy resin A / Biphenyldimethylene type epoxy resin: Nippon Kayaku Co., Ltd. “NC-3000”, epoxy equivalent 275, weight average molecular weight 1000
(5) Epoxy resin B / tetramethylbiphenyl type epoxy resin: “YX-4000” manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 185, weight average molecular weight 700
(6) A copolymer of phenoxy resin / bisphenol A type epoxy resin and bisphenol F type epoxy resin, and the terminal part has an epoxy group: Japan Epoxy Resin Co., Ltd. “jER4275” weight average molecular weight 60000
(7) Cyanate resin / Novolac type cyanate resin: Lonza Japan Co., Ltd. “Primerset PT-30”, weight average molecular weight 700
(8) Phenol-based curing agent / biphenylalkylene type novolak resin: “MEH-7851-3H” manufactured by Meiwa Kasei Co., Ltd., hydroxyl equivalent 220
(9) Curing Accelerator / Imidazole Compound: “Corazole 1B2PZ (1-benzyl-2-phenylimidazole)” manufactured by Shikoku Kasei Kogyo Co., Ltd.
(10) Coupling agent A: Epoxysilane type coupling agent (GE Toshiba Silicone Co., Ltd., A-187)

<Example 1>
(1) Exfoliation treatment of substrate Using a gravure coater, a solution of exfoliation treatment agent A diluted with acetone is applied to one side of a polyethylene terephthalate (PET) film (Mitsubishi Chemical Polyester Film, thickness 38 μm) as a substrate. It applied so that it might become 0.5 g / m < ² >, and it dried for 1 minute with the 90 degreeC drying apparatus, and performed the peeling process of the base material.

(2) Preparation of resin varnish 40.0 parts by weight of epoxy resin A, 19.8 parts by weight of phenoxy resin, and 0.2 parts by weight of a curing accelerator were dissolved and dispersed in methyl ethyl ketone. Furthermore, 40.0 parts by weight of the inorganic filler and 0.2 part by weight of the coupling agent A were added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 50% by weight.

(3) Production of Insulating Sheet with Substrate The thickness of the insulating film after drying the resin varnish obtained above on the release-treated surface of the substrate surface-treated above using a comma coater device is 40 μm. Then, this was dried with a drying apparatus at 150 ° C. for 5 minutes to produce an insulating sheet with a substrate.

(4) Manufacture of multilayer printed wiring board Overlaid on the front and back of the inner layer circuit board on which the predetermined inner layer circuit is formed on both sides with the insulating layer surface of the insulating sheet with the base material obtained above inside, Using a pressurizing laminator apparatus, vacuum heating and pressing were performed for 1 minute at a temperature of 100 ° C. and a pressure of 1 MPa, and the substrate was peeled from the insulating sheet. This was heated at 170 ° C. for 60 minutes with a hot air dryer to cure the insulating layer.
In addition, the following were used as the inner layer circuit board.
-Insulating layer: Halogen-free FR-4 material, thickness 0.4mm
Conductor layer: copper foil thickness 18 μm, L / S = 120/180 μm, clearance holes 1 mmφ, 3 mmφ, slit 2 mm

(5) Manufacture of package substrate An opening is provided in the insulating layer of the multilayer printed wiring board using a carbonic acid laser device, and an outer layer circuit is formed on the surface of the insulating layer by electrolytic copper plating, so that the outer layer circuit and the inner layer circuit are electrically connected. planned. Note that the outer layer circuit was provided with a connection electrode part for mounting a semiconductor element.
After that, a solder resist (PSR4000 / AUS308 manufactured by Taiyo Ink Co., Ltd.) is formed on the outermost layer, the connection electrode part is exposed so that a semiconductor element can be mounted by exposure and development, and nickel gold plating is performed, and the size is 50 mm × 50 mm. To obtain a package substrate.

(6) Manufacture of Semiconductor Device A semiconductor element (TEG chip, size 15 mm × 15 mm, thickness 0.8 mm) has a solder bump formed of an eutectic of Sn / Pb composition, and a circuit protective film formed of a positive photosensitive resin (Sumitomo). What was formed by Bakelite CRC-8300) was used. In assembling the semiconductor device, first, a flux material was uniformly applied to the solder bumps by a transfer method, and then mounted on the package substrate by thermocompression bonding using a flip chip bonder device. Next, after solder bumps were melt-bonded in an IR reflow furnace, a liquid sealing resin (manufactured by Sumitomo Bakelite Co., Ltd., CRP-4152S) was filled and the liquid sealing resin was cured to obtain a semiconductor device. The liquid sealing resin was cured at a temperature of 150 ° C. for 120 minutes.

<Example 2>
35.0 parts by weight of epoxy resin A, 15.0 parts by weight of epoxy resin B, 14.9 parts by weight of phenol curing agent and 0.1 part by weight of curing accelerator were dissolved and dispersed in methyl ethyl ketone. Furthermore, 35.0 parts by weight of an inorganic filler was added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 50% by weight.
Using this resin varnish, an insulating sheet with a substrate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 1.

<Example 3>
The solution of the release treatment agent A diluted with acetone is 0.5 g / m ² using a gravure coater on one side of a polyethylene naphthalate (PEN) film (made by Teijin DuPont Film, thickness 38 μm) as a base material. The substrate was peeled off by drying at 90 ° C. for 1 minute.
50.0 parts by weight of epoxy resin A, 15.0 parts by weight of phenoxy resin, 4.7 parts by weight of phenol curing agent, and 0.3 parts by weight of curing accelerator were dissolved and dispersed in methyl ethyl ketone. Further, 30.0 parts by weight of an inorganic filler was added and stirred for 10 minutes using a high-speed stirring device to prepare a resin varnish having a solid content of 50% by weight.
Thereafter, an insulating sheet with a substrate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 1 using the resin varnish and the substrate subjected to the release treatment with the release treatment agent A.

<Example 4>
Coating the solution of release treatment agent B diluted with acetone on one side of a polyethylene terephthalate film (Mitsubishi Chemical Polyester Film, thickness 38 μm) as a base material using a gravure coater to 0.5 g / m ² Then, the substrate was dried for 1 minute with a drying apparatus at 90 ° C., and the substrate was peeled off.
Thereafter, using the resin varnish of Example 1 and the base material subjected to the release treatment with the release agent B, an insulating sheet with a base material, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 1.

<Example 5>
A solution of release treatment agent B diluted with acetone is applied to one side of a polyethylene naphthalate film (made by Teijin DuPont Film, thickness 38 μm) as a substrate using a gravure coater so as to be 0.5 g / m ^2. Then, the substrate was dried for 1 minute with a drying apparatus at 90 ° C., and the substrate was peeled off.
15.0 parts by weight of epoxy resin A, 5.0 parts by weight of phenoxy resin, 14.9 parts by weight of cyanate resin, and 0.1 parts by weight of a curing accelerator were dissolved and dispersed in methyl ethyl ketone. Furthermore, 65.0 parts by weight of an inorganic filler was added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 50% by weight.
Using this resin varnish and the base material subjected to the release treatment with the release treatment agent B, an insulating sheet with a base material, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 1.

<Comparative Example 1>
Using the resin varnish of Example 1 and a base material (polyethylene terephthalate film, manufactured by Mitsubishi Chemical Polyester Film, thickness 38 μm) that has not been subjected to a release treatment, in the same manner as Example 1, an insulating sheet with a base material and a multilayer printed wiring A plate and a semiconductor device were obtained.

<Comparative example 2>
Using the resin varnish of Example 2 and a base material (polyethylene terephthalate film, manufactured by Mitsubishi Chemical Polyester Film, 38 μm in thickness) that has not been subjected to a release treatment, in the same manner as in Example 1, an insulating sheet with a base material and a multilayer printed wiring A plate and a semiconductor device were obtained.

<Comparative Example 3>
Using the resin varnish of Example 3 and a base material (polyethylene naphthalate film, made by Teijin DuPont Film, thickness 38 μm) that has not been subjected to a release treatment, the insulating sheet with the base material and the multilayer printed wiring are the same as in Example 1. A plate and a semiconductor device were obtained.

  The characteristics of the insulating sheets with base materials, multilayer printed wiring boards, and semiconductor devices obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated. The results are shown in Table 1.

The evaluation method is as follows.
(1) Peel strength of base material In the manufacturing process of the above multilayer printed wiring board, an insulating sheet with a base material is laminated on an inner layer circuit board, and the peeling strength when peeling the base material from the insulating layer is a precision universal testing machine ( Using an autograph AG-IS (manufactured by Shimadzu Corporation), in a 20 ° C. environment, part of the tip of a 1 cm wide base material is peeled off and gripped with a gripper, and the tensile direction is adhered to the sample surface (inner circuit board) It was measured by peeling 30 mm continuously at a speed of 5 mm / min in a direction perpendicular to the insulating layer and taking the average value.
(2) Resin transfer to substrate In the manufacturing process of the multilayer printed wiring board, after peeling the substrate, the surface of the substrate was observed with a microscope to confirm the presence or absence of resin transfer to the substrate.
Each code is as follows.
○: Resin transfer not observed ×: Transfer observed

(3) Appearance evaluation of insulating layer The insulating layer of the multilayer printed wiring board was observed with a microscope.
Each code is as follows.
○: Appearance is good ×: Defects such as cracks and defects are observed (4) Mounting reliability test The mounting reliability is 100 hours in an atmosphere at a temperature of 85 ° C. and a humidity of 85%. After leaving, 260 ° C. reflow was performed three times, and peeling of the back surface of the semiconductor element and chipping of the solder bumps were evaluated with an ultrasonic deep flaw inspection apparatus.
Each code is as follows.
◎: Good peeling, no bump defect ○: Virtually no problem Only minute peeling around the underfill, no bump defect △: Virtually unusable 10% or more peeling and bump defect ×: Unusable 80% peeling or more Bump defect

(5) Thermal shock test The above-mentioned semiconductor device is treated in 1000 cycles for 1 cycle at −55 ° C. for 10 minutes, 125 ° C. for 10 minutes, and −55 ° C. for 10 minutes in Fluorinert. It was observed visually.
Each code is as follows.
○: No crack occurrence ×: Crack occurrence

Examples 1-5 are the insulating sheet with a base material of this invention whose peeling strength of an insulating layer and a base material is 0.05 kN / m or less, a multilayer printed wiring board using this, and a semiconductor device.
In each of Examples 1 to 5, there was no resin transfer to the substrate, the appearance of the insulating layer was good, and a highly reliable semiconductor device could be manufactured.
In Comparative Examples 1 to 3, since the peel strength between the insulating layer and the base material exceeds 0.05 kN / m, there is a problem that the insulating sheet is cracked or resin transfer occurs to the base material. In (4) mounting reliability test and (5) thermal shock test, defects were observed.

<Example 6>
(1) Exfoliation treatment of base material A solution of exfoliation treatment agent A diluted with acetone is 0.5 g / m ^{2 on} one side of a polyethylene terephthalate film (Mitsubishi Chemical Polyester Film, thickness 38 μm) using a gravure coater. The substrate was coated and dried with a drying apparatus at 90 ° C. for 1 minute, and the substrate was peeled off.

(2) Preparation of resin varnish 35.0 parts by weight of epoxy resin A, 24.8 parts by weight of cyanate resin, and 0.2 parts by weight of a curing accelerator were dissolved and dispersed in methyl ethyl ketone. Further, 40.0 parts by weight of an inorganic filler was added and stirred for 10 minutes using a high-speed stirring device to prepare a resin varnish having a solid content of 50% by weight.

(3) Production of Insulating Sheet with Substrate The thickness of the insulating film after drying the resin varnish obtained above on the release-treated surface of the substrate surface-treated above using a comma coater device is 40 μm. Then, this was dried with a drying apparatus at 150 ° C. for 5 minutes to produce an insulating sheet with a substrate.

(4) Manufacture of multilayer printed wiring board On the front and back of the inner layer circuit board on which the predetermined inner layer circuit is formed on both sides, the insulating sheet surface of the insulating sheet with the base material obtained above is overlaid, Using a vacuum pressurizing laminator, vacuum heating and press molding was performed at a temperature of 100 ° C. and a pressure of 1 MPa for 1 minute. This was heated and cured at 170 ° C. for 60 minutes in a hot air dryer, and then the substrate was peeled from the insulating sheet to obtain a multilayer printed wiring board for evaluation.
In addition, the following were used as the inner layer circuit board.
Insulation layer: Halogen-free FR-4 material, thickness 0.4mm
Conductor layer: copper foil thickness 18 μm, L / S = 120/180 μm, clearance holes 1 mmφ, 3 mmφ, slit 2 mm

(5) Manufacture of package substrate An opening is provided in the insulating layer of the multilayer printed wiring board using a carbonic acid laser device, and an outer layer circuit is formed on the surface of the insulating layer by electrolytic copper plating, so that the outer layer circuit and the inner layer circuit are electrically connected. planned. Note that the outer layer circuit was provided with a connection electrode part for mounting a semiconductor element.
After that, a solder resist (PSR4000 / AUS308 manufactured by Taiyo Ink Co., Ltd.) is formed on the outermost layer, the connection electrode part is exposed so that a semiconductor element can be mounted by exposure and development, and nickel gold plating is performed, and the size is 50 mm × 50 mm. To obtain a package substrate.

(6) Manufacture of Semiconductor Device A semiconductor element (TEG chip, size 15 mm × 15 mm, thickness 0.8 mm) has a solder bump formed of an eutectic of Sn / Pb composition, and a circuit protective film formed of a positive photosensitive resin (Sumitomo). What was formed by Bakelite CRC-8300) was used. In assembling the semiconductor device, first, a flux material was uniformly applied to the solder bumps by a transfer method, and then mounted on the package substrate by thermocompression bonding using a flip chip bonder device. Next, after solder bumps were melt-bonded in an IR reflow furnace, a liquid sealing resin (manufactured by Sumitomo Bakelite Co., Ltd., CRP-4152S) was filled and the liquid sealing resin was cured to obtain a semiconductor device. The liquid sealing resin was cured at a temperature of 150 ° C. for 120 minutes.

<Example 7>
30.0 parts by weight of epoxy resin A, 20.0 parts by weight of epoxy resin B, 14.9 parts by weight of phenol curing agent and 0.1 part by weight of curing accelerator were dissolved and dispersed in methyl ethyl ketone. Furthermore, 35.0 parts by weight of an inorganic filler was added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 50% by weight.
Using this resin varnish, an insulating sheet with a substrate, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 6.

<Example 8>
Coating the solution of the release treatment agent A diluted with acetone on one side of a polyethylene naphthalate film (made by Teijin DuPont Film, thickness 38 μm) as a substrate, using a gravure coater, so as to be 0.5 g / m ^2. Then, the substrate was dried for 1 minute with a drying apparatus at 90 ° C., and the substrate was peeled off.
50.0 parts by weight of epoxy resin A, 10.0 parts by weight of phenoxy resin, 9.7 parts by weight of phenol curing agent and 0.3 part by weight of curing accelerator were dissolved and dispersed in methyl ethyl ketone. Further, 30.0 parts by weight of an inorganic filler was added and stirred for 10 minutes using a high-speed stirring device to prepare a resin varnish having a solid content of 50% by weight.
Using this resin varnish and the base material subjected to the release treatment with the release treatment agent A, an insulating sheet with a base material, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 6.

<Example 9>
The solution of the release treatment agent B diluted with acetone was applied to one side of a polyethylene terephthalate film (Mitsubishi Chemical Polyester Film, thickness 38 μm) to 0.5 g / m ² using a gravure coater, and 90 ° C. The substrate was dried for 1 minute using a drying apparatus, and the substrate was peeled off.
Thereafter, using the resin varnish of Example 6 and the base material subjected to the release treatment by the release treatment agent B, an insulating sheet with a base material, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 6.

<Example 10>
A solution of release treatment agent B diluted with acetone is applied to one side of a polyethylene naphthalate film (made by Teijin DuPont Film, thickness 38 μm) as a substrate using a gravure coater so as to be 0.5 g / m ^2. Then, the substrate was dried for 1 minute with a drying apparatus at 90 ° C., and the substrate was peeled off.
15.0 parts by weight of epoxy resin A, 10.0 parts by weight of phenoxy resin, 9.9 parts by weight of cyanate resin, and 0.1 parts by weight of a curing accelerator were dissolved and dispersed in methyl ethyl ketone. Furthermore, 65.0 parts by weight of an inorganic filler was added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 50% by weight.
Using this resin varnish and the base material subjected to the release treatment with the release treatment agent B, an insulating sheet with a base material, a multilayer printed wiring board, and a semiconductor device were obtained in the same manner as in Example 6.

<Comparative example 4>
Using the resin varnish of Example 6 and a non-peeled base material (polyethylene terephthalate film, manufactured by Mitsubishi Chemical Polyester Film, thickness 38 μm), in the same manner as in Example 6, an insulating sheet with a base material and a multilayer print A wiring board and a semiconductor device were obtained.

<Comparative Example 5>
Using the resin varnish of Example 7 and a base material (polyethylene terephthalate film, manufactured by Mitsubishi Chemical Polyester Film, thickness 38 μm) that has not been subjected to a release treatment, in the same manner as in Example 6, an insulating sheet with a base material and a multilayer print A wiring board and a semiconductor device were obtained.

<Comparative Example 6>
Using the resin varnish of Example 8 and a base material (polyethylene naphthalate film, made by Teijin DuPont Film, 38 μm in thickness) that has not been subjected to a release treatment, an insulating sheet with a base material and a multilayer print are obtained in the same manner as in Example 6. A wiring board and a semiconductor device were obtained.

  The characteristics of the insulating sheets with base materials, multilayer printed wiring boards, and semiconductor devices obtained in Examples 6 to 10 and Comparative Examples 4 to 6 were evaluated. The results are shown in Table 2.

The evaluation method is as follows.
(1) Peeling strength of base material In the manufacturing process of the multilayer printed wiring board, the insulating sheet with a base material is laminated on the inner layer circuit board, the insulating layer is cured, and then pulled when the base material is peeled off from the insulating layer. Using a precision universal testing machine (Autograph AG-IS, manufactured by Shimadzu Corporation) for peeling strength, in a 20 ° C environment, part of the 1 cm wide base material is peeled off and gripped with a gripper. The measurement was performed by stripping 30 mm continuously at a speed of 5 mm / min in a direction perpendicular to the surface (insulating layer bonded to the inner layer circuit board) and taking the average value.
(2) Flatness on circuit The unevenness | corrugation of the insulating layer surface of the said multilayer printed wiring board was measured with the surface roughness measuring apparatus.
Each code is as follows.
○: Step is less than 1 μm ×: Step is 1 μm or more Note that the step is a difference in height generated between a portion where the inner layer circuit is located under the insulating layer and a portion where the inner layer circuit is not located under the insulating layer.

(3) Adhesion of base material After peeling off the base material, the surface of the base material after peeling was observed with a microscope, and the presence or absence of the residual adhesion of the base material was confirmed.
Each code is as follows.
○: No sticking residue ×: No sticking residue (4) Reflow heat resistance test Using a package substrate before mounting the semiconductor element of the semiconductor device, passing it through a 260 ° C. reflow furnace, The presence or absence of swelling was confirmed visually. The package substrate was passed through a reflow furnace 10 times.
Each code is as follows.
◎: No swelling even after repeated 10 times ○: Bulging occurs at the 7th to 9th times △: Bulging occurs at the 4th to 6th times ×: Bulging occurs by the 3rd time

(5) Mounting reliability test For mounting reliability, the semiconductor device was left in an atmosphere of 85 ° C. and 85% humidity for 100 hours, and then reflowed at 260 ° C. three times. The back surface peeling and solder bump defects were evaluated.
Each code is as follows.
◎: Good peeling, no bump defect ○: Virtually no problem Only minute peeling around the underfill, no bump defect △: Virtually unusable 10% or more peeling and bump defect ×: Unusable 80% peeling or more Bump defect (6) Thermal shock test The above semiconductor device was subjected to 1000 cycles in Fluorinert at −55 ° C. for 10 minutes, 125 ° C. for 10 minutes, and −55 ° C. for 10 minutes, and cracks occurred in the test piece. It was confirmed visually.
Each code is as follows.
○: No crack occurrence ×: Crack occurrence

In Examples 6 to 10, the insulating sheet with a base material of the present invention having a peel strength of 0.2 kN / m or less when the base material is peeled from the insulating layer after the insulating layer is heat-cured, and a multilayer using the same A printed wiring board and a semiconductor device.
In each of Examples 6 to 10, the flatness on the circuit was good, there was no adhesion residue of the base material, the reflow heat resistance was excellent, and a highly reliable semiconductor device could be manufactured.
In Comparative Examples 4 to 6, after the insulating layer is heated and cured, the peeling strength when peeling the substrate from the insulating layer exceeds 0.2 kN / m, and thus there is a problem that the remaining adhesion of the substrate occurs. Swelling was observed in the reflow heat resistance test. Further, in the evaluation of the semiconductor device, defects were found in both (5) mounting reliability test and (6) thermal shock test.

  INDUSTRIAL APPLICABILITY According to the insulating sheet with a substrate of the present invention, it is possible to provide a printed wiring board excellent in handling at a low cost, meeting the demand for downsizing and thinning, and for semiconductor packages that require high density and fine wiring. A substrate can also be provided.

Claims (26)

An insulating sheet with a base material used for forming an insulating layer of a multilayer printed wiring board,
An insulating layer made of a resin composition is provided on a base material. The insulating layer is bonded to the surface to be bonded by heating and pressing, and the insulating layer is heated and cured. An insulating sheet with a base material, wherein a peeling strength for peeling the base material from the layer is 0.2 kN / m or less, and the insulating layer is used by being peeled from the base material after heat curing.   The insulating layer is bonded to the adherend surface by heating and pressing the adherend surface at 60 to 160 ° C. and 0.2 to 5 MPa for 0.5 to 15 minutes, and 140 to 240 The peeling strength which peels the said base material from the said insulating layer after heating and hardening the said insulating layer by heating at 30 degreeC for 30 to 120 minutes is 0.2 kN / m or less. An insulating sheet with a substrate as described in 1.   The insulating sheet with a base material according to claim 1 or 2, wherein the base material has been subjected to a release treatment with a release treatment agent.   The insulating sheet with base material according to claim 3, wherein the release treatment agent is a non-silicone release treatment agent.   The insulating sheet with a base material according to claim 3 or 4, wherein the release treatment agent contains a compound having a urethane bond.   The insulating sheet with a base material according to any one of claims 1 to 5, wherein the base material is a polyester resin film.   The insulating sheet with base material according to claim 6, wherein the polyester resin film is a polyethylene terephthalate film or a polyethylene naphthalate film.   The insulating sheet with a base material according to any one of claims 1 to 7, wherein the resin composition contains an epoxy resin.   The insulating sheet with a base material according to any one of claims 1 to 8, wherein the resin composition contains an inorganic filler.   The insulating sheet with a substrate according to any one of claims 1 to 9, wherein the resin composition contains an imidazole compound.   A multilayer printed wiring board obtained by superposing the insulating sheet with a base material according to any one of claims 1 to 10 on one side or both sides of an inner layer circuit board and heating and pressing.   A semiconductor device using the multilayer printed wiring board according to claim 11 as a package substrate. The insulating sheet with a base material according to any one of claims 1 to 10 and an inner layer circuit board are overlaid with the insulating layer of the insulating sheet with a base material on the inner layer circuit board side, Heating and pressing at a temperature lower than the curing temperature of the resin composition to produce a multilayer printed wiring board precursor; and
After the multilayer printed wiring board precursor is heated to a temperature equal to or higher than the curing temperature of the resin composition to cure the insulating layer, the base material is peeled off to produce a multilayer printed wiring board;
A method for producing a multilayer printed wiring board, comprising: An insulating sheet with a base material used for forming an insulating layer of a multilayer printed wiring board,
An insulating layer made of a resin composition is provided on a substrate, and when the insulating layer is heated and pressed at 60 to 160 ° C. and 0.2 to 5 MPa for 0.5 to 15 minutes on the adherend surface, 20 An insulating sheet with a base material, wherein a peel strength at which the base material is peeled from the insulating layer at 0 ° C. is 0.05 kN / m or less.   The insulating sheet with a base material according to claim 14, wherein the base material has been subjected to a release treatment with a release treatment agent.   The insulating sheet with base material according to claim 15, wherein the release treatment agent is a non-silicone release treatment agent.   The insulating sheet with a base material according to claim 15 or 16, wherein the release agent contains a compound having a urethane bond.   The insulating sheet with a base material according to any one of claims 14 to 17, wherein the base material is a polyester resin film.   The insulating sheet with a substrate according to claim 18, wherein the polyester resin film is a polyethylene terephthalate film or a polyethylene naphthalate film.   The insulating sheet with base material according to any one of claims 14 to 19, wherein the resin composition contains an epoxy resin.   The insulating sheet with a base material according to any one of claims 14 to 20, wherein the resin composition contains an inorganic filler.   The insulating sheet with a base material according to any one of claims 14 to 21, wherein the resin composition contains an imidazole compound.   23. The method according to claim 14, wherein the peel strength before curing the insulating layer is 0.05 kN / m or less and is used by being peeled off from the base material before curing the insulating layer. The insulating sheet with a base material according to any one of the above.   A multilayer printed wiring board obtained by superposing the insulating sheet with a base material according to any one of claims 14 to 23 on one side or both sides of an inner layer circuit board and heating and pressing.   A semiconductor device using the multilayer printed wiring board according to claim 24 as a package substrate. The insulating sheet with a base material according to any one of claims 14 to 23 and the inner layer circuit board are overlapped with the insulating layer of the insulating sheet with a base material facing the inner layer circuit board, Heating and pressing at a temperature lower than the curing temperature of the resin composition to produce a multilayer printed wiring board precursor; and
In the multilayer printed wiring board precursor, after the substrate is peeled from the insulating layer, the insulating layer is cured by heating above the curing temperature of the resin composition, and a multilayer printed wiring board is produced;
A method for producing a multilayer printed wiring board, comprising: