Classifications

• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/46—Manufacturing multilayer circuits
  • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
  • H01L24/93—Batch processes
  • H01L24/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
  • H01L24/96—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips the devices being encapsulated in a common layer, e.g. neo-wafer or pseudo-wafer, said common layer being separable into individual assemblies after connecting
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/12—Mountings, e.g. non-detachable insulating substrates
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/12—Mountings, e.g. non-detachable insulating substrates
  • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/12—Mountings, e.g. non-detachable insulating substrates
  • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
  • H01L23/145—Organic substrates, e.g. plastic
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/0011—Working of insulating substrates or insulating layers
  • H05K3/0055—After-treatment, e.g. cleaning or desmearing of holes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
  • H01L2224/93—Batch processes
  • H01L2224/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
  • H01L2224/96—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips the devices being encapsulated in a common layer, e.g. neo-wafer or pseudo-wafer, said common layer being separable into individual assemblies after connecting
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
  • H05K2201/0203—Fillers and particles
  • H05K2201/0206—Materials
  • H05K2201/0212—Resin particles
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
  • H05K2203/04—Soldering or other types of metallurgic bonding
  • H05K2203/049—Wire bonding

Definitions

• the present invention relates to a method for manufacturing a circuit board and a resin sheet used therefor.
• the rewiring layer is generally formed by applying a curable resin material on a substrate such as a wafer or panel substrate by spin coating and curing the material. After forming an insulating layer, a conductor layer is formed, and this is repeated to form a multilayer structure (see, for example, Patent Document 1).
• the insulating layer of the circuit board must have excellent dielectric properties to suppress transmission loss when operating in a high-frequency environment, and to suppress the occurrence of warping when forming a large-area insulating layer in the manufacture of WLP and PLP.
• Various properties are required, such as the ability to obtain, and such requirements are likely to become more severe in the future.
• the inventors attempted to use an insulating material in the form of a resin sheet in order to achieve high functionality of the insulating layer, such as good dielectric properties and low warpage, and to provide an insulating layer with good surface flatness.
• the present inventors have studied a technique for forming an insulating layer by laminating a resin composition layer on a base material such as a wafer and curing the resin sheet by using a resin sheet having a resin composition layer provided on a support.
• voids hereinafter also referred to as "interface voids”
• An object of the present invention is to provide a method for producing a circuit board that can suppress an increase in the surface potential of a support while suppressing the occurrence of interfacial voids even when a substrate having a large area is used, and a method for producing a circuit board.
• the present invention includes the following contents.
• the total specific surface area of the inorganic filler in the resin composition layer is 1.5 m 2 /g or more.
• (ii-2) The surface resistivity of the first surface of the support is 1.0 ⁇ 10 10 ⁇ /sq.
• the base material is (a) a semiconductor wafer having an electrode pad surface, (b) a plurality of semiconductor chips obtained by singulating the semiconductor wafer of (a) so that the electrode pad surfaces are exposed.
• step (X) The method of [1], wherein the substrate is a substrate with a release layer.
• step (X) The method according to any one of [1] to [3], wherein the main surface dimension (minimum dimension) of the substrate is 150 mm or more.
• step (X) After step (X), (1) curing the resin composition layer to form an insulating layer; (2) a step of drilling the insulating layer; (3) Desmearing the insulating layer, and (4) The method according to any one of [1] to [4], including one or more steps selected from the step of forming a conductor layer on the surface of the insulating layer. .
• step (6] The method according to any one of [1] to [5], wherein the resin composition layer contains a stress relaxation material.
• the surface resistivity of the second surface of the support is 1.0 ⁇ 10 10 ⁇ /sq.
• a method for manufacturing a circuit board which can suppress the increase in the surface potential of a support while suppressing the occurrence of interfacial voids even when using a substrate having a large area, and the method for producing the circuit board.
• a resin sheet can be provided.
• the method for manufacturing a circuit board of the present invention comprises: (X) bonding a resin sheet comprising a support having first and second surfaces and a resin composition layer provided on the second surface of the support to a substrate through the resin composition layer; comprising a step of laminating to a substrate, such as It is characterized by satisfying the following conditions (i), (ii-1) and (ii-2). (i) The atmospheric pressure is reduced at the same time or before the bonding of the resin composition layer and the substrate (ii-1) The total specific surface area of the inorganic filler in the resin composition layer is 1.5 m 2 /g or more. (in terms of non-volatile components) (ii-2) The surface resistivity of the first surface of the support is 1.0 ⁇ 10 10 ⁇ /sq. is below
• the insulating layer of the circuit board must have excellent dielectric properties to suppress transmission loss when operating in a high-frequency environment, and warping can occur when forming large-area insulating layers in the manufacture of WLP and PLP.
• Various properties are required, such as the ability to suppress , and such requirements are likely to become more severe in the future.
• the present inventors have attempted to use an insulating material in the form of a resin sheet in order to provide an insulating layer that highly satisfies the properties required for the insulating layer of a circuit board and has good surface flatness. In this respect, it has been confirmed that when the insulating material in the form of a resin sheet is applied to a substrate having a large surface area, interfacial voids may occur and the desired circuit board may not be manufactured.
• this interfacial void is an improvement in terms of equipment/process and the composition of the insulating material, that is, (a) reducing the atmospheric pressure at the same time or before the bonding of the resin composition layer and the substrate, and ( b) It can be suppressed by adjusting the size and content of the inorganic filler so that the total specific surface area of the inorganic filler in the resin composition layer is 1.5 m 2 /g or more (in terms of non-volatile components).
• the above techniques (a) and (b) are employed, a new problem arises in that the surface potential of the support increases to such an extent that the semiconductor chip may be damaged, especially when the area of the substrate is large. I found out that it happens. Further, the inventors have found that the problem of such an increase in surface potential tends to become conspicuous in compositions of resin composition layers intended for further reduction in dielectric loss tangent and warpage.
• the insulating material in the form of a resin sheet can be applied to a large substrate. Even if there is, it is possible to suppress the generation of interfacial voids and suppress the increase in the surface potential of the support.
• the manufacturing method of the present invention highly satisfies the properties required for the insulating layer of circuit boards, and significantly contributes to the realization of finer wiring. It is.
• the method for manufacturing a circuit board of the present invention comprises: (X) bonding a resin sheet comprising a support having first and second surfaces and a resin composition layer provided on the second surface of the support to a substrate through the resin composition layer; As such, the step of laminating to a substrate is included.
• the “base material” used in the step (X) is a circuit element having a predetermined function and electrically connected to the circuit element when the circuit board is manufactured by the Chip-1 st method.
• a semiconductor wafer having an electrode pad surface on which a plurality of electrode pads are formed may be used.
• Suitable semiconductor wafers include silicon (Si)-based wafers, but are not limited thereto.
• Nitride (GaN)-based, gallium tellurium (GaTe)-based, zinc selenide (ZnSe)-based, silicon carbide (SiC)-based wafers, and the like may also be used.
• the chip 1st construction method is a construction method in which a semiconductor chip is first provided and a rewiring layer is formed on the electrode pad surface (for example, JP-A-2002-289731, JP-A-2006-173345, etc.).
• a rewiring layer may be formed on the exposed electrode pad surface and the surrounding sealing resin layer (for example, JP-A-2012-15191, JP-A-2015-126123, etc.).
• the carrier substrate a known substrate used in manufacturing a package with a fan-out structure may be used, and the type thereof is not particularly limited, but examples thereof include a glass substrate, a metal substrate, a plastic substrate, and the like.
• the "base material" in step (X) may be a substrate formed by encapsulating the peripheries of individualized semiconductor chips with an encapsulating resin so that the electrode pad surfaces thereof are exposed.
• a substrate further provided with a stopper resin may be used.
• the circuit board manufacturing method of the present invention is widely applicable to the manufacture of circuit boards including the step of laminating a resin sheet on a base material, and the rewiring layer (insulating layer thereof) is formed as described above.
• the rewiring layer (insulating layer thereof) is formed as described above.
• the "base material" in step (X) is a plurality of semiconductor chips formed by singulating a semiconductor wafer and separating them from each other. A carrier substrate placed thereon may be used.
• the method of manufacturing a circuit board can be classified into a face-up type and a face-down type from the viewpoint of the chip mounting direction.
• the semiconductor chip may be arranged so that the electrode pad surface faces the carrier substrate.
• the step (X) may be performed in forming the protective layer. .
• the substrate comprises (a) a semiconductor wafer having an electrode pad surface, and (b) a plurality of semiconductor chips obtained by singulating the semiconductor wafer of (a) so that the electrode pad surfaces are exposed.
• (a) corresponds to the case of forming (the insulating layer of) a rewiring layer in manufacturing a package with a fan-in structure
• (c) and (f) correspond to a package with a fan-out structure
• (b) and (e) are for forming a sealing layer
• (d) and (g) are for forming a solder resist layer. applicable in each case.
• (b) to (d) correspond to the face-up construction method
• (e) to (g) apply the face-down construction method.
• the "base material" used in the step (X) may be a substrate with a release layer.
• the rewiring layer 1st method is a method in which a rewiring layer is provided first, and a semiconductor chip is provided on the rewiring layer in such a state that the electrode pad surface of the rewiring layer can be electrically connected to the rewiring layer (for example, , JP-A-2015-35551, JP-A-2015-170767, etc.).
• the rewiring layer 1st method the rewiring layer is exposed by peeling off the substrate with the peeling layer after providing the semiconductor chip on the rewiring layer.
• a rewiring layer 1st construction method is particularly suitable for manufacturing a package with a fan-out structure.
• the substrate with a release layer a known substrate used in manufacturing a circuit board by the rewiring layer 1st method may be used, and the type thereof is not particularly limited.
• a metal substrate, a plastic substrate with a release layer, and the like are included.
• the substrate is a substrate with a release layer.
• the dimensions of the base material are not particularly limited, and may be determined according to the intended package design. Regarding dimensions in the direction parallel to the main surface of the substrate (dimensions in the XY direction; also simply referred to as “main surface dimensions”), a circular or substantially circular substrate (hereinafter also simply referred to as “circular substrate”). ), the diameter can be, for example, 100 mm (4 inches) or greater, 125 mm (5 inches) or greater. According to the production method of the present invention, it is possible to use a substrate having a larger area while suppressing the occurrence of interfacial voids and an increase in the surface potential of the support.
• a circular substrate may have a diameter of 150 mm (6 inches) or greater, 200 mm (8 inches) or greater, 300 mm (12 inches) or greater, 450 mm (18 inches) or greater.
• the upper limit of the diameter of the circular substrate is not particularly limited, and can be, for example, 600 mm (24 inches) or less.
• the main surface dimension in the case of a rectangle, the dimension of the short side is, for example, 50 mm or more, 75 mm or more, or 100 mm or more. , 125 mm or more.
• the dimension of the main surface of the square substrate (the dimension of the short side in the case of a rectangle) may be 150 mm or more, 200 mm or more, 300 mm or more, or 450 mm or more.
• the upper limit of the principal surface dimension of the rectangular substrate is not particularly limited, and can be, for example, 1000 mm or less.
• the main surface dimension (minimum dimension) of the substrate is 150 mm or more.
• the "principal surface dimension (minimum dimension)" of the substrate means the diameter in the case of a circular substrate, and the dimension of the short side of the principal surface in the case of a rectangular substrate.
• the production method of the present invention it is possible to use a substrate having a large area while suppressing the occurrence of interfacial voids and an increase in the surface potential of the support.
• the area of the substrate (the projected area when viewed from the direction perpendicular to the main surface of the substrate) is 150 cm 2 or more, 200 cm 2 or more, 300 cm 2 or more, 500 cm 2 or more, 700 cm 2 or more, 1000 cm 2 or more, 1500 cm 2 or more. It can be 2 or more, and so on.
• the upper limit of the area of the substrate is not particularly limited, and may be, for example, 10000 cm 2 or less, 8000 cm 2 or less.
• step (X) a resin sheet (details will be described later) is laminated on the substrate so that the resin composition layer of the resin sheet is bonded to the substrate.
• the atmospheric pressure is reduced at the same time as or before the bonding of the resin composition layer and the substrate ("Condition (i)").
• the step (X) in combination with the condition (ii-1) described later for the resin sheet, by performing the step (X) so as to satisfy the condition (i), even when using a large-area base material, interface voids can be suppressed.
• Step (X) may be carried out using any lamination device as long as such condition (i) can be achieved.
• a lamination device sheet sticking device described in JP-A-2013-229515, JP-A-2006-310338, etc. may be used.
• the atmospheric pressure (atmospheric pressure in the chamber in which the resin sheet to be treated and the base material are stored) is preferably 200 hPa or less, The pressure is reduced to more preferably 150 hPa or less, more preferably 100 hPa or less, 80 hPa or less, 60 hPa or less, 50 hPa or less, 40 hPa or less, or 30 hPa or less.
• the atmospheric pressure may be reduced to achieve the atmospheric pressure at the same time that the resin composition layer and the substrate are joined, and the atmospheric pressure may be reduced to achieve the atmospheric pressure before the resin composition layer and the substrate are joined. You may join a resin composition layer and a base material.
• lamination of the resin sheet and the substrate is preferably carried out under heating conditions.
• the heating temperature for laminating the resin sheet on the substrate is preferably 60° C. or higher, more preferably 80° C. or higher or 90° C. or higher, and the upper limit of the heating temperature is preferably 150° C. or lower, more preferably 140° C. °C or less or 120 °C or less.
• the pressure (crimping pressure) during lamination of the resin sheet and the substrate is preferably 0.098 MPa or more, more preferably 0.29 MPa or more, and the upper limit of the crimping pressure is preferably 1 .77 MPa or less, more preferably 1.47 MPa or less.
• the time for laminating the resin sheet and the substrate is preferably 20 seconds or longer, more preferably 30 seconds or longer, and the upper limit of the pressing time is preferably 400 seconds or shorter. , more preferably 300 seconds or less.
• a member for crimping the resin sheet and the base material (hereinafter, also referred to as a "crimping member”) may be appropriately determined according to the configuration of the laminating apparatus. be done.
• the production method of the present invention includes, after the above step (X), (1) curing the resin composition layer to form an insulating layer; (2) a step of drilling the insulating layer; (3) a step of desmearing the insulating layer; and (4) a step of forming a conductor layer on the surface of the insulating layer.
• step (X) is a step of forming (the insulating layer of) the rewiring layer
• all the steps (1) to (4) may be performed after the step (X)
• the step (X) is If it is a step of forming a sealing layer or a solder resist layer, step (1) may be performed after step (X).
• step (1) the resin composition layer is cured to form an insulating layer.
• the conditions for curing the resin composition layer are not particularly limited, and conditions that are normally employed when forming an insulating layer of a circuit board may be used.
• the curing conditions for the resin composition layer vary depending on the type of the resin composition and the like. 180°C to 230°C.
• the curing time can be preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, even more preferably 15 minutes to 120 minutes.
• the resin composition layer may be preheated at a temperature lower than the curing temperature before curing the resin composition layer.
• the resin composition layer prior to curing the resin composition layer, at a temperature of 50 ° C. to 120 ° C., preferably 60 ° C. to 115 ° C., more preferably 70 ° C. to 110 ° C., the resin composition layer is preferably cured for 5 minutes or more. may be preheated for 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, even more preferably 15 minutes to 100 minutes. Preheating is advantageous because it facilitates the formation of an insulating layer with a low surface roughness after desmearing.
• step (2) the insulating layer is perforated.
• Step (2) may be carried out using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used for forming the insulating layer.
• the dimensions and shape of the holes may be appropriately determined according to the design of the circuit board.
• step (3) the insulating layer is desmeared.
• Desmear treatment is not particularly limited, and can be performed by various known methods.
• desmearing may be dry desmearing, wet desmearing, or a combination thereof.
• Examples of dry desmear treatment include desmear treatment using plasma.
• Desmear processing using plasma removes smears generated in via holes by processing an insulating layer using plasma generated by introducing a gas into a plasma generator.
• the plasma generation method is not particularly limited, and examples include microwave plasma that generates plasma using microwaves, high frequency plasma that uses high frequency waves, atmospheric pressure plasma that is generated under atmospheric pressure, and vacuum plasma that is generated under vacuum. , a vacuum plasma generated under vacuum is preferred.
• the plasma used in the desmear process is preferably RF plasma that is excited at a high frequency.
• the plasmatizing gas is not particularly limited as long as the smear in the via hole can be removed.
• a gas containing SF6 may be used.
• the plasmatized gas may include other gases such as Ar and O 2 in addition to SF 6 .
• a mixed gas containing SF 6 and at least one of Ar and O 2 is preferable as the plasmatizing gas from the viewpoint of easily realizing an insulating layer with a small surface roughness after desmear treatment.
• Gas mixtures containing O2 are more preferred.
• the mixing ratio (SF 6 /other gas: unit: sccm) is preferable from the viewpoint of easily realizing an insulating layer with a small surface roughness after desmear treatment. is 1/0.01 to 1/1, more preferably 1/0.05 to 1/1, more preferably 1/0.1 to 1/1.
• the time for desmear treatment using plasma is not particularly limited, but is preferably 30 seconds or longer, more preferably 60 seconds or longer, 90 seconds or longer, or 120 seconds or longer.
• the upper limit of the desmear treatment time is preferably 10 minutes or less, more preferably 5 minutes or less, from the viewpoint of easily realizing an insulating layer with a small surface roughness after the desmear treatment.
• Desmear treatment using plasma can be performed using a commercially available plasma desmear treatment device.
• suitable examples for manufacturing circuit boards include a plasma dry etching device manufactured by Oxford Instruments, a microwave plasma device manufactured by Nissin, and a normal pressure device manufactured by Sekisui Chemical Co., Ltd. Plasma etching equipment and the like can be mentioned.
• a dry sandblasting treatment that can polish the object to be treated by spraying an abrasive from a nozzle may also be used. Dry sandblasting can be carried out using commercially available dry sandblasting equipment. When a water-soluble abrasive is used as the abrasive, smears can be effectively removed by washing with water after dry sandblasting without the abrasive remaining inside the via hole.
• the desmear treatment is preferably a dry desmear treatment, and more preferably a desmear treatment using plasma, from the viewpoint of easily realizing an insulating layer with a small surface roughness regardless of the composition of the resin composition layer. Therefore, in one preferred embodiment, the insulating layer is dry desmeared, particularly preferably the insulating layer is plasma desmeared.
• Wet desmear treatment includes, for example, desmear treatment using an oxidizing agent solution.
• the desmear treatment is performed using the oxidant solution, it is preferable to perform the swelling treatment with the swelling liquid, the oxidation treatment with the oxidant solution, and the neutralization treatment with the neutralization solution in this order.
• the swelling liquid include "Swelling Dip Security P" and “Swelling Dip Security SBU” manufactured by Atotech Japan Co., Ltd. be able to.
• the swelling treatment is preferably carried out by immersing the substrate with via holes formed therein in a swelling liquid heated to 60° C. to 80° C. for 5 to 10 minutes.
• the oxidizing agent solution an aqueous alkaline permanganate solution is preferable.
• a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be mentioned.
• the oxidation treatment with the oxidizing agent solution is preferably performed by immersing the substrate after the swelling treatment in the oxidizing agent solution heated to 60° C. to 80° C. for 10 minutes to 30 minutes.
• Examples of commercially available alkaline permanganate aqueous solutions include "Concentrate Compact P", “Concentrate Compact CP", and "Dosing Solution Security P" manufactured by Atotech Japan Co., Ltd. be done.
• the neutralization treatment with the neutralizing solution is preferably carried out by immersing the substrate after the oxidation treatment in the neutralizing solution at 30° C. to 50° C. for 3 to 10 minutes.
• an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Security P” manufactured by Atotech Japan Co., Ltd. can be mentioned.
• a wet sandblasting treatment that can polish the object to be treated by spraying an abrasive and a dispersion medium from a nozzle may also be used.
• Wet sandblasting can be carried out using commercially available wet sandblasting equipment.
• the insulating layer is wet desmeared, and particularly preferably the insulating layer is desmeared using an oxidant solution.
• dry desmear treatment may be performed first, or wet desmear treatment may be performed first.
• the resin sheet support may be removed before step (4), may be removed between steps (X) and (1), or may be removed between steps (1) and (2). may be removed between steps (2) and (3), or may be removed after step (3).
• the support is preferably removed after the step (2), more preferably after the step (3), from the viewpoint of easily realizing an insulating layer with a small surface roughness after the desmear treatment.
• step (4) a conductor layer is formed on the surface of the insulating layer.
• the conductor layer may be formed by plating.
• a conductive layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. It is preferably formed by a method.
• a semi-additive method is shown below.
• a plating seed layer is formed on the surface of the insulating layer by electroless plating.
• the plating seed layer includes at least a conductive seed layer.
• the conductive seed layer is a layer that functions as an electrode in electroplating.
• the conductive material constituting the conductive seed layer is not particularly limited as long as it exhibits sufficient conductivity, but preferred examples include copper, palladium, gold, platinum, silver, aluminum, and alloys thereof.
• the plating seed layer may also include a diffusion barrier layer.
• the diffusion barrier layer is a layer that prevents the conductive material forming the conductive seed layer from diffusing into the insulating layer and causing dielectric breakdown.
• the material constituting the diffusion barrier layer is not particularly limited as long as it can suppress or prevent the diffusion of the conductor material constituting the conductive seed layer, but suitable examples include titanium, tungsten, tantalum, and alloys thereof. mentioned.
• the thickness of the plating seed layer is preferably 1000 nm (1 ⁇ m) or less, more preferably 800 nm or less, 600 nm or less, 500 nm or less, 400 nm or less, or 300 nm or less. Since the manufacturing method of the present invention can realize an insulating layer with good surface flatness, the thickness of the plating seed layer may be even thinner. For example, the thickness of the plating seed layer may be 250 nm or less, 200 nm or less, 150 nm or less, 140 nm or less, 120 nm or less, or 100 nm or less.
• the "thickness of the plating seed layer" in the present invention refers to the average thickness of the entire plating seed layer including not only the conductive seed layer but also the diffusion barrier layer.
• the thickness of the diffusion barrier layer is not particularly limited as long as it can suppress or prevent the diffusion of the conductive material constituting the conductive seed layer, but from the viewpoint of contributing to fine wiring. , preferably 20 nm or less, more preferably 15 nm or less, still more preferably 10 nm or less.
• the lower limit of the thickness of the diffusion barrier layer is not particularly limited, and may be, for example, 1 nm or more, 3 nm or more, or 5 nm or more.
• the remainder of the plating seed layer is preferably a conductive seed layer, and the thickness of the conductive seed layer is within the above preferred range in relation to the thickness of the diffusion barrier layer. You can decide to be
• the plating seed layer may be formed by dry plating or wet plating.
• dry plating include physical vapor deposition (PVD) methods such as sputtering, ion plating, and vacuum deposition, and chemical vapor deposition (CVD) methods such as thermal CVD and plasma CVD.
• PVD physical vapor deposition
• CVD chemical vapor deposition
• Wet plating includes electroless plating.
• the dry plating method is preferable from the viewpoint of forming a thin plating seed layer having a more uniform thickness, and the sputtering method is particularly preferable from the viewpoint of realizing fine wiring with excellent adhesion strength.
• the metal layer comprises one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal.
• the metal layer may be a single metal layer or an alloy layer.
• the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys).
• the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern (hereinafter also referred to as "conductor pattern”) can be formed.
• a conductor pattern having an L/S of preferably 5/5 ⁇ m or less, more preferably 4/4 ⁇ m or less, and even more preferably 3/3 ⁇ m or less or 2/2 ⁇ m or less can be formed.
• L/S of 1/1 ⁇ m can be preferably formed.
• such a conductor pattern with a small L/S can be formed with a thickness of preferably 3 ⁇ m or less, 2.5 ⁇ m or less, 2 ⁇ m or less, 1.5 ⁇ m or less, or 1 ⁇ m or less.
• the lower limit of the thickness of the conductor pattern can be, for example, 0.5 ⁇ m or more, 0.6 ⁇ m or more.
• a rewiring layer having a multilayer structure By repeating the rewiring formation process, a rewiring layer having a multilayer structure can be formed.
• a rewiring layer on the semiconductor chip side (generally, a rewiring layer formed first in the chip 1st construction method, and a rewiring layer formed last in the rewiring 1st construction method) is formed.
• the manufacturing method of the present invention is preferably applied, and the manufacturing method of the present invention may be applied to all of the multi-layered rewiring layers.
• circuit boards such as WLP and PLP can be realized using a large-area substrate while suppressing the occurrence of interface voids and an increase in the surface potential of the support.
• step (X) may be carried out by using a semiconductor wafer obtained from the above process so that the electrode pad surface of the semiconductor wafer and the resin composition layer are bonded to each other. Then, step (1), step (2), step (3), and step (4) are sequentially performed to form a rewiring layer on the electrode pad surface of the semiconductor wafer. By repeating these steps, it is possible to form a multi-layered rewiring layer. Then, board connection terminals such as bumps are formed on the surface of the rewiring layer opposite to the semiconductor wafer, and the wafer is singulated to manufacture a WLP having a fan-in structure.
• a semiconductor wafer on which a circuit element having a predetermined function and a plurality of electrode pads electrically connected to the circuit element are formed is singulated. Then, after each semiconductor chip is placed on a carrier substrate (glass substrate, metal substrate, plastic substrate, etc.) while being spaced apart from each other, resin sealing is performed so that the electrode pad surfaces of the separated semiconductor chips are exposed. A substrate whose periphery is sealed with a sealing resin is obtained. Using such a substrate as a "base material", the step (X) may be carried out so that the surface of the substrate on the side of the electrode pad and the resin composition layer are bonded.
• step (1), step (2), step (3), and step (4) are sequentially performed to form a rewiring layer on the electrode pad surface of the semiconductor chip and the surrounding sealing resin layer. can be done. By repeating these steps, it is possible to form a multi-layered rewiring layer. Then, board connection terminals such as bumps are formed on the surface of the rewiring layer opposite to the substrate, and the substrate is again separated into individual pieces, thereby manufacturing a WLP with a fan-out structure.
• the WLP and PLP with the fan-out structure obtained by the manufacturing method of the present invention together with the inherent feature of the fan-out structure that the rewiring layer can be formed in a large area, have dielectric properties and low warpage. It is advantageous because it is possible to form extremely fine and high-density wiring over a large area while providing an insulating layer that satisfies the properties and the like to a high degree. Therefore, in one embodiment, the circuit board manufactured by the manufacturing method of the present invention is a WLP or PLP, more preferably a fan-out structure WLP (FOWLP) or a fan-out structure PLP (FOPLP). .
• WLP or PLP more preferably a fan-out structure WLP (FOWLP) or a fan-out structure PLP (FOPLP).
• Manufacturing methods for circuit boards such as WLP and PLP have developed in a wide variety of ways from the viewpoint of chip mounting direction (Face-down type, Face-up type), including the above-mentioned chip 1st construction method and rewiring layer 1st construction method.
• INDUSTRIAL APPLICABILITY The present invention relates to a highly versatile technology that is widely applicable to the manufacture of circuit boards including a step of laminating a resin sheet on a substrate in the manufacturing process.
• the method for manufacturing a circuit board of the present invention can be applied not only to the formation of a rewiring layer but also to the formation of a sealing layer and a solder resist layer.
• the resin sheet used in the production method of the present invention (hereinafter also simply referred to as “the resin sheet of the present invention”) will be described.
• the resin sheet of the present invention includes a support having first and second surfaces and a resin composition layer provided on the second surface of the support, and satisfies the following conditions (ii-1) and (ii). -2) is satisfied.
• the total specific surface area of the inorganic filler in the resin composition layer is 1.5 m 2 /g or more (in terms of non-volatile components)
• the surface resistivity of the first surface of the support is 1.0 ⁇ 10 10 ⁇ /sq. is below
• the resin composition layer contains an inorganic filler so as to satisfy the above condition (ii-1).
• total specific surface area of the inorganic filler in the resin composition layer means the total surface area of the inorganic filler contained per 1 g of non-volatile components in the resin composition layer.
• the total specific surface area of the inorganic filler in the resin composition layer is the inorganic filler when the specific surface area of the inorganic filler is A [m 2 /g] and the non-volatile component in the resin composition layer is 100% by mass.
• the content of is B [% by mass]
• it can be calculated by the formula: (A ⁇ B) / 100.
• the specific surface area of all inorganic fillers contained in the resin composition layer is A
• the content of all inorganic fillers is B. do it.
• the total specific surface area of the inorganic filler in the resin composition layer is 1.5 m 2 /g or more, preferably 2.0 m 2 /g or more, more preferably 2.5 m 2 /g or more, and still more preferably 3.0 m 2 /g or more or 3.5 m 2 /g or more.
• the production method of the present invention which satisfies the condition (ii-1) in combination with the condition (i) and further satisfies the condition (ii-2), an increase in the surface potential of the support is suppressed, and The total specific surface area of the inorganic filler can be increased.
• the total specific surface area of the inorganic filler in the resin composition is 4.0 m 2 /g or more, 5.0 m 2 /g or more, 6.0 m 2 /g or more, 7.0 m 2 /g or more. It may be increased to 0 m 2 /g or more or 9.0 m 2 /g or more. Therefore, in one preferred embodiment, the total specific surface area of the inorganic fillers in the resin composition layer is 4.0 m 2 /g or more.
• the production method of the present invention which is capable of increasing the total specific surface area of the inorganic filler in the resin composition layer while suppressing it, significantly contributes to highly satisfying each function required for the insulating layer of the circuit board. be.
• the upper limit of the total specific surface area of the inorganic filler in the resin composition layer is preferably 25 m 2 /g or less, 20 m 2 /g or less, 18 m 2 /g or less, 16 m 2 /g or less, or 15 m 2 /g or less.
• inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide , barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate.
• silica is particularly suitable.
• examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica.
• spherical silica is preferable as silica.
• An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.
• Examples of commercially available inorganic fillers include “SP60-05” and “SP507-05” manufactured by Nippon Steel Chemical &Materials; “SC2500SQ”, “SO-C4" and “SO-C2” manufactured by Admatechs.
• the average particle diameter of the inorganic filler is preferably 3 ⁇ m or less, more preferably 2 ⁇ m or less, still more preferably 1 ⁇ m or less, 0.8 ⁇ m or less, 0.8 ⁇ m or less, from the viewpoint of easily realizing an insulating layer with a small surface roughness after desmear treatment. 6 ⁇ m or less, 0.5 ⁇ m or less, 0.4 ⁇ m or less, or 0.3 ⁇ m or less.
• the lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, and still more preferably 0.07 ⁇ m or more, 0.1 ⁇ m or more, or 0.2 ⁇ m or more. be.
• the average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement.
• a measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes.
• a measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and from the obtained particle size distribution The average particle diameter was calculated as the median diameter.
• the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.
• the specific surface area (A) of the inorganic filler is the preferred range of the above "total specific surface area of the inorganic filler in the resin composition layer" in relation to the content (B) of the inorganic filler in the resin composition. Although it is not particularly limited as long as it meets the 10 m 2 /g or more.
• the upper limit of the specific surface area is not particularly limited, but is preferably 100 m 2 /g or less, more preferably 80 m 2 /g or less, and still more preferably 60 m 2 /g or less or 50 m 2 /g or less.
• the specific surface area of the inorganic filler is determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area using the BET multipoint method. obtained by
• the inorganic filler is a non-hollow inorganic filler (preferably non-hollow silica) with a porosity of 0 vol%, or a hollow inorganic filler (preferably hollow silica) with a porosity of more than 0 vol%. may also include both.
• the inorganic filler may contain only solid inorganic fillers (preferably solid silica), may contain only hollow inorganic fillers (preferably hollow silica), or may contain only solid inorganic fillers (preferably solid silica). ) in combination with hollow inorganic fillers (preferably hollow silica).
• the inorganic filler contains a hollow inorganic filler, it is preferable because it facilitates realization of a resin composition that keeps the dielectric constant lower and provides a cured product exhibiting even better dielectric properties.
• the porosity of the hollow inorganic filler is preferably 10% by volume or more, more preferably 15% by volume or more, and still more preferably 20% by volume or more, and the upper limit is preferably 90% by volume or less, more preferably 85% by volume. vol% or less, more preferably 80 vol% or less, 75 vol% or less, 70 vol% or less, 65 vol% or less, 60 vol% or less, 55 vol% or less, or 50 vol% or less.
• the porosity P (% by volume) of the inorganic filler is the volume-based ratio of the total volume of one or more pores present inside the particle to the volume of the entire particle based on the outer surface of the particle (the number of pores total volume/particle volume), e.g., the measured actual density D M (g/cm 3 ) of the inorganic filler and the theoretical material density D T (g/cm 3 ) of the material forming the inorganic filler. /cm 3 ), it is calculated by the following formula (1).
• the actual density of the inorganic filler can be measured using, for example, a true density measuring device.
• a true density measuring device examples include ULTRAPYCNOMETER 1000 manufactured by QUANTACHROME. Nitrogen, for example, is used as the measuring gas.
• the inorganic filler is preferably surface-treated with an appropriate surface treatment agent.
• the surface treatment can enhance the moisture resistance and dispersibility of the inorganic filler.
• surface treatment agents include vinyl-based silane coupling agents, epoxy-based silane coupling agents, styryl-based silane coupling agents, (meth)acrylic-based silane coupling agents, amino-based silane coupling agents, and isocyanurate-based silanes.
• Silane coupling agents such as coupling agents, ureido-based silane coupling agents, mercapto-based silane coupling agents, isocyanate-based silane coupling agents, and acid anhydride-based silane coupling agents; methyltrimethoxysilane, phenyltrimethoxysilane, etc. non-silane coupling-alkoxysilane compounds; silazane compounds;
• the surface treatment agents may be used singly or in combination of two or more.
• Examples of commercially available surface treatment agents include "KBM403” (3-glycidoxypropyltrimethoxysilane), “KBM803” (3-mercaptopropyltrimethoxysilane), “KBE903” (3 -aminopropyltriethoxysilane), “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane), “SZ-31” (hexamethyldisilazane) and the like.
• KBM403 (3-glycidoxypropyltrimethoxysilane
• KBM803 (3-mercaptopropyltrimethoxysilane
• KBE903 (3 -aminopropyltriethoxysilane
• KBM573 N-phenyl-3-aminopropyltrimethoxysilane
• SZ-31 hexamethyldisilazane
• the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2 to 5% by mass of a surface treatment agent.
• the degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler.
• the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and more preferably 0.2 mg/m 2 from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable.
• it is preferably 1.0 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, and even more preferably 0.5 mg/m 2 or less.
• the amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.
• EMIA-320V manufactured by Horiba Ltd.
• the content (B) of the inorganic filler in the resin composition layer is within the preferred range of the above "total specific surface area of the inorganic filler in the resin composition layer" in relation to the specific surface area (A) of the inorganic filler.
• the nonvolatile component in the resin composition layer is 100% by mass, Preferably 30% by mass or more, more preferably 40% by mass or more, more preferably 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 66% by mass or more, 68% by mass % or more, 70 mass % or more, 72 mass % or more, 74 mass % or more, or 75 mass % or more.
• the upper limit of the content of the inorganic filler is preferably 90% by mass or less, more
• the resin composition layer contains a curable resin as the resin.
• the type of curable resin is not particularly limited as long as it cures to form an insulating layer.
• the curable resin is preferably one or more selected from the group consisting of thermosetting resins and radically polymerizable resins, since various properties such as insulation and heat resistance are good.
• thermosetting resins examples include epoxy resins, benzocyclobutene resins, epoxy acrylate resins, urethane acrylate resins, urethane resins, polyimide resins, melamine resins, and silicone resins.
• Thermosetting resins may be used singly or in combination of two or more.
• the curable resin preferably contains an epoxy resin from the viewpoint of satisfactorily satisfying the properties required for the insulating layer of the circuit board, such as good dielectric properties and low warpage.
• the type of epoxy resin is not particularly limited as long as it has one or more (preferably two or more) epoxy groups in one molecule.
• epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, and naphthol type epoxy resin.
• naphthalene type epoxy resin naphthylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene skeleton type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanediene Examples include methanol-type epoxy resins, trimethylol-type epoxy resins, and halogenated epoxy resins.
• Epoxy resins can be classified into liquid epoxy resins at a temperature of 20° C. (hereinafter referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20° C. (hereinafter referred to as “solid epoxy resins”).
• the resin composition layer may contain only a liquid epoxy resin as a curable resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. It's okay.
• the blending ratio liquid:solid is in the range of 20:1 to 1:20 (preferably 10:1 to 1:10, more preferably 3:1 to 1:3).
• the solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.
• Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolak type epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol phthalate A mijin-type epoxy resin and a phenolphthalein-type epoxy resin are preferred.
• solid epoxy resins include “HP4032H” (naphthalene-type epoxy resin) manufactured by DIC; “HP-4700” and “HP-4710” (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC; “N-690” (cresol novolac type epoxy resin) manufactured by DIC Corporation; “N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200”, “HP-7200HH”, “HP -7200H”, “HP-7200L” (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", “EXA-7311-G3", “EXA-7311-G4S”, "HP6000", “HP6000L” "(naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd.
• a liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.
• Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, hydrogenated bisphenol A type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol A novolak type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, and an epoxy resin having a butadiene structure are preferred.
• liquid epoxy resins include "HP4032", “HP4032D”, and “HP4032SS” (naphthalene type epoxy resins) manufactured by DIC; “828US”, “828EL”, “jER828EL”, and “825" manufactured by Mitsubishi Chemical Corporation; “, (Bisphenol A type epoxy resin); Mitsubishi Chemical Corporation “jER807”, “1750” (bisphenol F type epoxy resin); Mitsubishi Chemical Corporation “jER152” (phenol novolak type epoxy resin); Mitsubishi Chemical Corporation “630", “630LSD”, “604" (glycidylamine type epoxy resin); ADEKA “ED-523T” (glycirrol type epoxy resin); ADEKA “EP-3950L”, “EP-3980S ” (Glycidylamine type epoxy resin); ADEKA “EP-4088S” (dicyclopentadiene type epoxy resin); “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celoxide 2021P” manufactured by Daice
• JP-100 “JP-200” (epoxy resin having a butadiene structure); Nippon Steel Chemical & Materials Co., Ltd.
• ZX1658 “ZX1658GS” (1,4-glycidyl Cyclohexane type epoxy resin), "YX8000” (hydrogenated bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "KF-101” (epoxy-modified silicone resin) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
• ZX1658 “ZX1658GS” (1,4-glycidyl Cyclohexane type epoxy resin)
• YX8000 hydrogenated bisphenol A type epoxy resin
• KF-101 epoxy-modified silicone resin manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
• These may be used individually by 1 type, and may be used in combination of 2 or more types.
• the epoxy group equivalent of the epoxy resin is preferably 50 g/eq. ⁇ 2000 g/eq. , more preferably 60 g/eq. ⁇ 1000g/eq. , more preferably 80 g/eq. ⁇ 500 g/eq. is.
• the epoxy group equivalent is the mass of an epoxy resin containing one equivalent of epoxy groups, and can be measured according to JIS K7236.
• the weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500.
• the Mw of the epoxy resin can be measured as a polystyrene-equivalent value by the GPC method.
• the type of the radically polymerizable resin is not particularly limited as long as it has one or more (preferably two or more) radically polymerizable unsaturated groups in one molecule.
• the radically polymerizable resin for example, one selected from a maleimide group, a vinyl group, an allyl group, a styryl group, a vinylphenyl group, an acryloyl group, a methacryloyl group, a fumaroyl group, and a maleoyl group as a radically polymerizable unsaturated group. Resins having the above are mentioned.
• the curable resin is one or more selected from maleimide resin, (meth)acrylic resin and styryl resin, from the viewpoint of satisfactorily satisfying the properties required for the insulating layer of the circuit board, such as good dielectric properties and low warpage. is preferably included.
• maleimide resin As the maleimide resin, as long as it has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule, is not particularly limited.
• maleimide resins include (1) “BMI-3000J”, “BMI-5000”, “BMI-1400", “BMI-1500”, “BMI-1700”, and “BMI-689” (all of which are (2) Maleimide resin containing an aliphatic skeleton having 36 carbon atoms derived from dimer diamine, such as (manufactured by Molecules, Inc.); Maleimide resin (commercially available products include “MIR-5000-60T” (manufactured by Nippon Kayaku Co., Ltd.) and the like); (3) “MIR-3000-70MT” (manufactured by Nippon Kayaku Co., Ltd.), “BMI-4000” (manufactured by Daiwa Kasei
• the type of the (meth)acrylic resin is not particularly limited as long as it has one or more (preferably two or more) (meth)acryloyl groups in one molecule, and may be a monomer or an oligomer.
• the term "(meth)acryloyl group” is a generic term for acryloyl group and methacryloyl group.
• methacrylic resins in addition to (meth)acrylate monomers, for example, “A-DOG” (manufactured by Shin-Nakamura Chemical Co., Ltd.), “DCP-A” (manufactured by Kyoeisha Chemical Co., Ltd.), “NPDGA”, “FM-400”. , “R-687”, “THE-330”, “PET-30”, and “DPHA” (all manufactured by Nippon Kayaku Co., Ltd.).
• styryl resin is not particularly limited as long as it has one or more (preferably two or more) styryl groups or vinylphenyl groups in one molecule, and it may be a monomer or an oligomer.
• styryl resins include styrene monomers as well as styryl resins such as "OPE-2St”, “OPE-2St 1200", and “OPE-2St 2200” (all manufactured by Mitsubishi Gas Chemical Company).
• the resin composition layer may contain only a thermosetting resin as a curable resin, may contain only a radically polymerizable resin, or may contain a combination of a thermosetting resin and a radically polymerizable resin. good.
• the content of the curable resin in the resin composition layer is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 12% by mass when the resin component in the resin composition layer is 100% by mass. % or more, 14 mass % or more, or 15 mass % or more.
• the upper limit of the content is not particularly limited, and may be determined according to the properties required for the resin composition. and so on.
• the "resin component” refers to a non-volatile component that constitutes the resin composition layer, excluding the inorganic filler described below.
• the content of the epoxy resin is preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 55% by mass or more. 60% by mass or more, 65% by mass or more, or 70% by mass or more.
• the upper limit of the content of the epoxy resin in the curable resin is not particularly limited, and may be 100% by mass.
• the resin composition layer may contain a curing agent.
• a curing agent usually has a function of reacting with a curable resin to cure the resin composition.
• curing agents examples include active ester curing agents, phenol curing agents, naphthol curing agents, acid anhydride curing agents, cyanate ester curing agents, carbodiimide curing agents, and amine curing agents.
• the curing agent may be used singly or in combination of two or more.
• the curing agent is selected from the group consisting of an active ester curing agent, a phenolic curing agent, and a naphthol curing agent, from the viewpoint that a cured product (insulating layer) having excellent dielectric properties and conductor adhesion can be obtained. It preferably contains one or more kinds, and in particular, it preferably contains an active ester curing agent from the viewpoint that a cured product having excellent dielectric properties can be obtained. Therefore, in one embodiment, the curing agent includes one or more selected from the group consisting of an active ester curing agent, a phenolic curing agent, and a naphthol curing agent, more preferably an active ester curing agent.
• a compound having one or more active ester groups in one molecule can be used as the active ester curing agent.
• active ester curing agents include phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, and the like, and have two or more ester groups per molecule with high reaction activity.
• Preferred are compounds having The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound.
• an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. .
• carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
• phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like.
• dicyclopentadiene-type diphenol compound refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.
• the active ester curing agent examples include an active ester curing agent containing a dicyclopentadiene type diphenol structure, an active ester curing agent containing a naphthalene structure, an active ester curing agent containing an acetylated phenol novolac, Examples include active ester curing agents containing benzoylated phenol novolacs. Among them, an active ester curing agent containing a naphthalene structure and an active ester curing agent containing a dicyclopentadiene type diphenol structure are more preferable.
• "Dicyclopentadiene-type diphenol structure” represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.
• active ester compounds include "EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000L-65TM” and “HPC-8000-65T” as active ester compounds containing a dicyclopentadiene type diphenol structure.
• Examples thereof include “YLH1026”, “YLH1030” and “YLH1048” (manufactured by Mitsubishi Chemical Corporation), and “PC1300-02-65MA” (manufactured by Air Water) as an active ester compound containing a styryl group and a naphthalene structure.
• the phenol-based curing agent and naphthol-based curing agent preferably have a novolac structure.
• nitrogen-containing phenolic curing agents and nitrogen-containing naphthol curing agents are preferred, and triazine skeleton-containing phenolic curing agents and triazine skeleton-containing naphthol curing agents are more preferred.
• phenol-based curing agents and naphthol-based curing agents include, for example, “MEH-7700”, “MEH-7810”, “MEH-7851” and “MEH-8000H” manufactured by Meiwa Kasei; Nippon Kayaku Co., Ltd. "NHN”, “CBN”, “GPH” manufactured by Nippon Steel Chemical & Materials Co., Ltd.
• acid anhydride-based curing agents include curing agents having one or more acid anhydride groups in one molecule.
• Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid.
• cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate, oligo(3-methylene-1,5-phenylenecyanate), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4 '-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethyl Bifunctional cyanate resins such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether; polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc.; prepolymers obtained by partially triazinizing these cyanate
• cyanate ester curing agents include “PT30” and “PT60” (phenol novolac type polyfunctional cyanate ester resins), “ULL-950S” (polyfunctional cyanate ester resins) and “BA230” manufactured by Lonza Japan. , “BA230S75” (a prepolymer in which part or all of bisphenol A dicyanate is triazined to form a trimer), and the like.
• carbodiimide-based curing agents include Nisshinbo Chemical Co., Ltd. Carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216 g/eq.), V-05 (carbodiimide group equivalent: 262 g/eq.), V- 07 (carbodiimide group equivalent: 200 g/eq.); V-09 (carbodiimide group equivalent: 200 g/eq.); Rhein Chemie Stabaxol (registered trademark) P (carbodiimide group equivalent: 302 g/eq.).
• Amine-based curing agents include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. mentioned. Specific examples of amine-based curing agents include 4,4′-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 3,3′.
• the content of the curing agent in the resin composition is preferably 5% by mass when the resin component in the resin composition is 100% by mass. Above, more preferably 10% by mass or more, still more preferably 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more.
• the upper limit of the content is not particularly limited, and may be determined according to the properties required for the resin composition.
• the curing agent preferably contains an active ester curing agent from the viewpoint of providing a cured product with excellent dielectric properties.
• the content of the active ester-based curing agent in the curing agent is determined from the viewpoint of obtaining a cured product exhibiting outstanding dielectric properties.
• the component is 100% by mass, it is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, 75% by mass or more, or 80% by mass or more.
• the upper limit of the content of the active ester curing agent in the curing agent is not particularly limited, and may be 100% by mass, but may be, for example, 95% by mass or less, or 90% by mass or less.
• the mass ratio of the active ester-based curing agent to the curable resin exhibits outstanding dielectric properties. From the viewpoint, it is preferably 0.5 or more, more preferably 0.6 or more, and still more preferably 0.7 or more or 0.8 or more.
• the upper limit of the mass ratio (active ester curing agent/curable resin) may be, for example, 2 or less, 1.8 or less, 1.6 or less, or 1.5 or less.
• the resin composition layer contains an inorganic filler, a curable resin and a curing agent, and satisfies the above condition (ii-1).
• the resin composition layer may further contain one or more selected from the group consisting of a stress relaxation agent and a curing accelerator within a range that satisfies the above condition (ii-1) and does not impair the effects of the present invention.
• the resin composition layer may further contain a stress relaxation material.
• a stress relaxation material By including the stress relaxation material, it is possible to suppress warpage even when forming an insulating layer on a large-area base material.
• the stress relaxation material one selected from a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule.
• a resin having the above structure is preferable, and one or more structures selected from a polybutadiene structure, a poly(meth)acrylate structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure. It is more preferable that the resin has "(Meth)acrylate” is a term that includes both methacrylate and acrylate. These structures may be contained in the main chain or may be contained in the side chain.
• the stress relaxation material preferably has a high molecular weight from the viewpoint of suppressing warpage.
• the number average molecular weight (Mn) of the stress relaxation material is preferably 1,000 or more, more preferably 1,500 or more, still more preferably 2,000 or more, 2,500 or more, 3,000 or more, 4,000 or more, or 5,000 or more.
• the upper limit of Mn is preferably 1,000,000 or less, more preferably 900,000 or less, 800,000 or less, or 700,000 or less.
• the number average molecular weight (Mn) can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.
• the stress relaxation material is preferably one or more selected from resins having a glass transition temperature (Tg) of 25°C or less and resins that are liquid at 25°C.
• Tg glass transition temperature
• the resin corresponds to “a resin having a Tg of 25° C. or less”.
• the Tg is preferably 20°C or lower, more preferably 15°C or lower.
• the lower limit of Tg is not particularly limited, it can usually be -50°C or higher.
• the resin that is liquid at 25° C. is preferably liquid at 20° C. or lower, more preferably 15° C. or lower.
• the stress relaxation material preferably has a functional group capable of reacting with the curable resin or the like.
• the functional group capable of reacting with a curable resin or the like also includes a functional group that appears upon heating.
• the functional group capable of reacting with a curable resin or the like is one or more selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group.
• the functional group is preferably a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, or a urethane group, and more preferably a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, or an epoxy group.
• the number average molecular weight (Mn) is preferably 5,000 or more.
• the stress relaxation material contains a resin containing a polybutadiene structure (hereinafter also referred to as "polybutadiene resin"). Part or all of the polybutadiene structure may be hydrogenated.
• polybutadiene resins include "Ricon 130MA8", “Ricon 130MA13", “Ricon 130MA20”, “Ricon 131MA5", “Ricon 131MA10", “Ricon 131MA17”, “Ricon 131MA20” and “Ricon 184MA6” (acid anhydride group-containing polybutadiene), Nippon Soda's “JP-100", “JP-200” (epoxidized polybutadiene), "GQ-1000” (hydroxyl group, carboxyl group-introduced polybutadiene), "G- 1000", “G-2000”, “G-3000” (both hydroxyl-terminated polybutadiene), “GI-1000", “GI-2000”, “GI-3000” (both hydroxyl-terminated polybutadiene), manufactured by Daicel Corporation "PB3600”, “PB4700” (polybutadiene skeleton epoxy resin), "Epofriend A1005", "Epofriend A1005"
• Polybutadiene resins also include linear polymers made from hydroxyl group-terminated polybutadiene, diisocyanate compounds and tetrabasic acid anhydride (polymers described in JP-A-2006-37083 and WO 2008/153208), phenolic Examples include hydroxyl group-containing butadiene.
• the butadiene structure content of the polymer is preferably 50% by mass or more, more preferably 60% to 95% by mass. Details of the polymer can be referred to JP-A-2006-37083 and WO-A-2008/153208, the contents of which are incorporated herein.
• the stress relaxation material contains a resin containing a poly(meth)acrylate structure (hereinafter also referred to as "poly(meth)acrylic resin”).
• poly(meth)acrylic resins include Teisan Resin “SG-70L”, “SG-708-6", “WS-023”, “SG-700AS” and “SG-280TEA” manufactured by Nagase ChemteX Corporation.
• the stress relaxation material contains a resin containing a polycarbonate structure (hereinafter also referred to as "polycarbonate resin”).
• polycarbonate resins include “T6002" and “T6001” (polycarbonate diols) manufactured by Asahi Kasei Chemicals, and “C-1090", “C-2090” and “C-3090” (polycarbonate diols) manufactured by Kuraray Co., Ltd. etc.
• Linear polyimides made from hydroxyl-terminated polycarbonates, diisocyanate compounds and tetrabasic acid anhydrides can also be used.
• the carbonate structure content of the polyimide resin is preferably 50 mass % or more, more preferably 60 mass % to 95 mass %. Details of the polyimide resin can be referred to in International Publication No. 2016/129541, the contents of which are incorporated herein.
• the stress relaxation material contains a resin containing a polysiloxane structure (hereinafter also referred to as "polysiloxane resin").
• polysiloxane resin include, for example, “SMP-2006”, “SMP-2003PGMEA”, and “SMP-5005PGMEA” manufactured by Shin-Etsu Silicone Co., Ltd., amine group-terminated polysiloxane and tetrabasic acid anhydride.
• polyimide International Publication No. 2010/053185, JP-A-2002-12667, JP-A-2000-319386, etc.
• the stress relaxation material includes a resin containing a polyalkylene structure and a polyalkyleneoxy structure (hereinafter also referred to as “polyalkylene resin” and “polyalkyleneoxy resin”, respectively).
• polyalkylene resin a resin containing a polyalkylene structure and a polyalkyleneoxy structure
• polyalkylene resin a resin containing a polyalkylene structure and a polyalkyleneoxy structure
• the stress relaxation material contains a resin containing a polyisoprene structure (hereinafter also referred to as "polyisoprene resin”).
• polyisoprene resin a resin containing a polyisoprene structure
• Specific examples of the polyisoprene resin include “KL-610" and “KL613” manufactured by Kuraray Co., Ltd.
• the stress relaxation material contains a resin containing a polyisobutylene structure (hereinafter also referred to as "polyisobutylene resin").
• polyisobutylene resin a resin containing a polyisobutylene structure
• Specific examples of the polyisobutylene resin include “SIBSTAR-073T” (styrene-isobutylene-styrene triblock copolymer) and “SIBSTAR-042D” (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation. .
• the stress relief material includes an organic filler.
• the organic filler a wide range of organic fillers containing a rubber component can be used.
• the rubber component contained in the organic filler include silicone elastomers such as polydimethylsiloxane; polybutadiene, polyisoprene, polychlorobutadiene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer Polymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, ethylene-propylene-butene terpolymer Olefin thermoplastic elastomers such as polymers; acrylic thermoplastic elastomers such as
• the rubber component may be mixed with silicone rubber such as polyorganosiloxane rubber.
• the rubber component contained in the rubber particles has a Tg of, for example, 0° C. or lower, preferably ⁇ 10° C. or lower, more preferably ⁇ 20° C. or lower, and even more preferably ⁇ 30° C. or lower.
• the organic filler is a core-shell type consisting of a core particle containing the above-mentioned rubber component and a shell part obtained by graft-copolymerizing a monomer component copolymerizable with the rubber component contained in the core particle. rubber particles.
• core-shell type does not necessarily refer only to particles in which the core particle and the shell part are clearly distinguishable, and includes particles in which the boundary between the core particle and the shell part is unclear. It does not have to be completely covered with
• organic fillers containing rubber components include “CHT” manufactured by Cheil Industries; “B602” manufactured by UMGABS; “Paraloid EXL-2602” and “Paraloid EXL-2603” manufactured by Kureha Chemical Industry ”, “Paraloid EXL-2655”, “Paraloid EXL-2311”, “Paraloid-EXL2313”, “Paraloid EXL-2315”, “Paraloid KM-330”, “Paraloid KM-336P”, “Paraloid KCZ-201”, Mitsubishi Rayon's “Metabrene C-223A”, “Metabrene E-901", “Metabrene S-2001”, “Metabrene W-450A”, “Metabrene SRK-200”, Kaneka's "Kane Ace M-511", “Kane Ace M-600”, “Kane Ace M-400", “Kane Ace M-580", “Kane Ace MR-01”, “Staphyroid AC3355”,
• the content of the stress relaxation material in the resin composition layer is 100% by mass of the resin component in the resin composition from the viewpoint of realizing an insulating material capable of suppressing warpage. , preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and even more preferably 4% by mass or more or 5% by mass or more.
• the content of the stress relaxation material in the resin composition layer is increased, warping can be suppressed, while condition (ii-1) is satisfied in combination with condition (i) described above, and interfacial voids are prevented from occurring.
• the inventors of the present invention have found that, in a method of manufacturing a circuit board intended to suppress the increase, the surface potential of the support tends to increase significantly to the extent that the semiconductor chip may be damaged.
• the production method of the present invention which satisfies the condition (ii-1) in combination with the condition (i) and further satisfies the condition (ii-2), the increase in the surface potential of the support is suppressed.
• the content of the stress relaxation material can be increased.
• the content of the stress relaxation material in the resin composition layer is 6% by mass or more, 8% by mass or more, 10% by mass or more, 12% by mass or more when the resin component in the resin composition is 100% by mass. , 14% by mass or more, and may be increased to 15% by mass or more.
• the upper limit of the content is preferably 40% by mass or less, more preferably 35% by mass or less or 30% by mass or less.
• the content of the stress relaxation material in the resin composition layer is also preferably 0 as the mass ratio of the stress relaxation material to the total of the curable resin and the curing agent, that is, the stress relaxation material/[curable resin + curing agent]. 0.05 or more, more preferably 0.06 or more, 0.08 or more, or 0.1 or more.
• the upper limit of the mass ratio is preferably 3 or less, more preferably 2 or less, 1.8 or less, 1.6 or less, or 1.5 or less.
• the resin composition layer may further contain a curing accelerator.
• a curing accelerator By including a curing accelerator, the curing time and curing temperature can be adjusted efficiently.
• curing accelerators examples include organic phosphine compounds such as “TPP”, “TPP-K”, “TPP-S”, and “TPTP-S” (manufactured by Hokko Chemical Industry Co., Ltd.); , “Cl1Z”, “Cl1Z-CN”, “Cl1Z-CNS”, “Cl1Z-A”, “2MZ-OK”, “2MA-OK”, “2PHZ” (manufactured by Shikoku Kasei Co., Ltd.) and other imidazole compounds; Amine adduct compounds such as Novacure (manufactured by Asahi Chemical Industry Co., Ltd.) and Fujicure (manufactured by Fuji Chemical Industry Co., Ltd.); 1,8-diazabicyclo[5,4,0]undecene-7,4-dimethylaminopyridine, benzyldimethylamine, 2, Amine compounds such as 4,6-tris(dimethylaminomethyl)phenol and 4-dimethylamin
• the content of the curing accelerator in the resin composition may be determined according to the properties required of the resin composition. When it is 100% by mass, it is preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less. .05% by mass or more, and so on.
• the resin composition layer may further contain other additives.
• additives include radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; phenoxy resins, polyvinyl acetal resins, polysulfone resins, polyethersulfone resins, and polyphenylene ether resins.
• Thermoplastic resins such as , polyether ether ketone resins, and polyester resins; Organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide , Colorants such as carbon black; Polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; Leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; Thickeners such as bentone and montmorillonite; , antifoaming agents such as acrylic antifoaming agents, fluorine antifoaming agents, and vinyl resin antifoaming agents; UV absorbers such as benzotriazole UV absorbers; adhesion improvers such as urea silane; triazole adhesiveness Adhesion-imparting agents such as adhesion-imparting agents, tetrazole-based adhesion
• stabilizers such as borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, and carboxylic anhydride stabilizers.
• the content of such additives may be determined according to the properties required for the resin composition layer.
• the thickness of the resin composition layer may be determined according to the intended design of the circuit board, but is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, 35 ⁇ m or less, 30 ⁇ m or less, 25 ⁇ m or less. or less or 20 ⁇ m or less.
• the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 1 ⁇ m or more, 2 ⁇ m or more, 3 ⁇ m or more, 5 ⁇ m or more, and the like.
• the melt viscosity of the resin composition layer at 100° C. is preferably 50,000 poise or less, more preferably 45,000 poise or less, still more preferably 40,000 poise or less, and 35 ,000 poise or less, or 30,000 poise or less.
• the resin composition layer preferably contains a stress relaxation material.
• the condition (ii-1) when the melt viscosity of the resin composition layer in the lamination temperature range decreases, such as when increasing the content of the stress relaxation material in the resin composition layer, the condition (ii-).
• the condition (ii-1) when the melt viscosity of the resin composition layer in the lamination temperature range decreases, such as when increasing the content of the stress relaxation material in the resin composition layer, the condition (ii-).
• the production method of the present invention that satisfies the condition (ii-1) in combination with the condition (i) and further satisfies the condition (ii-2), the content of the stress relaxation material is increased, etc.
• the melt viscosity of the resin composition layer at 100° C. is 25,000 poise or less, 20,000 poise or less, 18,000 poise or less, 16,000 poise or less, 15,000 poise or less, 14,000 poise or less, 12,000 poise or less, It may be 10,000 poise or less.
• the melt viscosity of the resin composition layer at 100° C. is preferably 1,000 poise or more, 1,500 poise or more, or 2,000 poise or more from the viewpoint of further suppressing the occurrence of interfacial voids.
• the melt viscosity of the resin composition layer at 100° C. can be measured according to the method described in the section ⁇ Measurement of Melt Viscosity> below.
• the support has first and second surfaces, and the surface resistivity of the first surface is 1.0 ⁇ 10 10 ⁇ /sq. It is characterized by the following (“Condition (ii-2)” above).
• the first surface of the support refers to the exposed surface that does not bond to the resin composition layer
• the second surface of the support refers to the surface that bonds to the resin composition layer
• a resin sheet having a resin composition layer that satisfies the condition (ii-1) is used to perform the step (X) so as to satisfy the condition (i), thereby using a large-area substrate. It has been found that the occurrence of interfacial voids can be suppressed even in this case.
• the inventors have found that, especially when the area of the base material is large, a new problem arises in that the surface potential of the support increases to such an extent that the semiconductor chip may be damaged. Moreover, as described above, the problem of such an increase in surface potential tends to become more pronounced in the composition of the resin composition layer intended for further reduction in dielectric loss tangent and warpage.
• the present inventors have found that by satisfying the condition (ii-2) in combination with the conditions (i) and (ii-1), it is possible to apply the insulating material in the form of a resin sheet to a large-area substrate. However, it is possible to suppress the occurrence of interfacial voids and to suppress an increase in the surface potential of the support.
• the surface resistivity of the first surface of the support is 1.0 ⁇ 10 10 ⁇ /sq. or less, preferably 1.0 ⁇ 10 9 ⁇ /sq. 1.0 ⁇ 10 8 ⁇ /sq. below, more preferably 1.0 ⁇ 10 8 ⁇ /sq. Below, more preferably 5.0 ⁇ 10 7 ⁇ /sq. Below, 1.0 ⁇ 10 7 ⁇ /sq. Below, 5.0 ⁇ 10 6 ⁇ /sq. Below, 1.0 ⁇ 10 6 ⁇ /sq. below or 5.0 ⁇ 10 5 ⁇ /sq. It is below.
• the lower limit of the surface resistivity is not particularly limited, it is usually 1.0 ⁇ 10 1 ⁇ /sq.
• the surface resistivity of the surface of the support can be measured according to the method described in ⁇ Measurement of Surface Resistivity> below.
• the surface resistivity of the second surface of the support is not particularly limited, and is, for example, 1.0 ⁇ 10 15 ⁇ /sq. Below, 1.0 ⁇ 10 14 ⁇ /sq. Below, 5.0 ⁇ 10 13 ⁇ /sq. 1.0 ⁇ 10 12 ⁇ /sq., preferably 1.0 ⁇ 10 12 ⁇ /sq. Below, more preferably 1.0 ⁇ 10 11 ⁇ /sq. Below, more preferably 1.0 ⁇ 10 10 ⁇ /sq. Below, 1.0 ⁇ 10 9 ⁇ /sq. Below, 1.0 ⁇ 10 8 ⁇ /sq. below or 5.0 ⁇ 10 7 ⁇ /sq. It is below.
• the lower limit of the surface resistivity is not particularly limited, it is usually 1.0 ⁇ 10 1 ⁇ /sq. Above, 5.0 ⁇ 10 1 ⁇ /sq. Above, 1.0 ⁇ 10 2 ⁇ /sq. and so on.
• the material and configuration of the support are not particularly limited as long as the above condition (ii-2) is satisfied.
• Examples of the support include thermoplastic resin films, metal foils, and release papers, with thermoplastic resin films being preferred.
• thermoplastic resin film When a thermoplastic resin film is used as the support, examples of the thermoplastic resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA). , cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable.
• the support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface ("second surface") that joins the resin composition layer.
• a support with a release layer having a release layer on the second surface may also be used.
• the release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. .
• the support is characterized in that the surface resistivity of its first surface is within the desired range (condition (ii-2)).
• the support is preferably subjected to antistatic treatment.
• antistatic treatment include (a) providing an antistatic layer containing an antistatic agent on the first surface side (and optionally the second surface side) of the support; For example, an antistatic agent is added to the material constituting the support.
• antistatic agent for example, one or more conventionally known agents selected from conductive polymers, conductive fine particles, ionic compounds, and quaternary ammonium salt compounds may be used.
• conductive polymers include polythiophene-based conductive polymers, polyaniline-based conductive polymers, and polypyrrole-based conductive polymers.
• polythiophene-based conductive polymers examples include polythiophene, poly( 3-alkylthiophene), poly(3-thiophene- ⁇ -ethanesulfonic acid), a mixture of polyalkylenedioxythiophene and polystyrene sulfonate (PSS) (including doped ones), etc.;
• Polymers include, for example, polyaniline, polymethylaniline, and polymethoxyaniline;
• polypyrrole-based conductive polymers include, for example, polypyrrole, poly3-methylpyrrole, poly3-octylpyrrole, and the like.
• conductive fine particles include conductive inorganic fine particles such as tin oxide, antimony-doped tin oxide (ATO), indium oxide-tin oxide (ITO), zinc oxide and antimony pentoxide; fine particles obtained by coating the surface of organic fine particles with a conductive compound; and conductive fine particles such as carbon fine particles.
• conductive inorganic fine particles such as tin oxide, antimony-doped tin oxide (ATO), indium oxide-tin oxide (ITO), zinc oxide and antimony pentoxide
• fine particles obtained by coating the surface of organic fine particles with a conductive compound and conductive fine particles such as carbon fine particles.
• Suitable examples of the ionic compound include nitrogen-containing onium salts, sulfur-containing onium salts, phosphorus-containing onium salts, alkali metal salts, and alkaline earth metal salts.
• quaternary ammonium salt compounds include pyrrolidium rings, quaternized alkylamines, copolymers thereof with acrylic acid or methacrylic acid, quaternized N-alkylaminoacrylamides, and vinylbenzyltrimethyl. ammonium salts, 2-hydroxy-3-methacryloxypropyltrimethylammonium salts and the like.
• the antistatic layer When an antistatic layer is provided on the first surface side (and optionally the second surface side) of the support as an antistatic treatment of the support, the antistatic layer contains an antistatic agent and a binder component. It is preferred to include The binder component is not particularly limited as long as it can disperse the antistatic agent and form a film.
• a curable resin such as a polyester resin, a urethane resin, or an acrylic resin may be used.
• the content of the antistatic agent in the antistatic layer is not particularly limited as long as the desired surface resistivity can be achieved, and may be determined as appropriate.
• the content of the antistatic agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, or 0.1% by mass or more when the entire antistatic layer is 100% by mass.
• the upper limit is preferably 50% by mass or less, more preferably 30% by mass or less.
• the support is a support with an antistatic layer having an antistatic layer bonded to the first surface of the support.
• All of the above embodiments (1) to (4) are embodiments using a support with an antistatic layer having an antistatic layer bonded to its first surface.
• the antistatic layer is also provided on the second surface side of the support, the surface resistivity of the second surface of the support can also be reduced. It is possible.
• the antistatic agent may be added to the release layer to provide a release layer exhibiting antistatic properties.
• the release layer also serves as an antistatic layer.
• the antistatic treatment of the support also includes adding the above antistatic agent to the material constituting the support to form a support exhibiting antistatic properties.
• a support is a thermoplastic resin film
• a thermoplastic resin film exhibiting antistatic properties can be formed by adding an antistatic agent to the thermoplastic resin and forming it into a film.
• the thickness of the support is not particularly limited, but is preferably in the range of 5 ⁇ m to 75 ⁇ m, more preferably in the range of 10 ⁇ m to 60 ⁇ m.
• the thickness of the entire support including the thickness of the antistatic layer and release layer is preferably within the above range.
• a resin varnish is prepared by dissolving a resin composition in an organic solvent, and this resin varnish is applied to the second surface side of the support using a die coater or the like, and then dried. It can be produced by forming a resin composition layer by pressing.
• organic solvents examples include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; cellosolve and butyl carbitol; carbitols; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone.
• An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
• Drying may be carried out by known methods such as heating and blowing hot air.
• the drying conditions are not particularly limited, but the resin composition layer is dried so that the amount of residual solvent is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes
• the resin composition layer can be formed.
• the resin sheet of the present invention includes a support having first and second surfaces and a resin composition layer provided on the second surface of the support, and the following conditions (ii- 1) and (ii-2) are satisfied.
• the total specific surface area of the inorganic filler in the resin composition layer is 1.5 m 2 /g or more (in terms of non-volatile components)
• the surface resistivity of the first surface of the support is 1.0 ⁇ 10 10 ⁇ /sq. is below
• Such a resin sheet of the present invention is produced by the method for producing a circuit board of the present invention, that is, a step of laminating a resin sheet containing a resin composition layer on a base material so that the resin composition layer is bonded to the base material. with the following condition (i): (i) It can be suitably used in a method of manufacturing a circuit board in which the atmospheric pressure is reduced at the same time or before the bonding of the resin composition layer and the base material.
• the resin sheet of the present invention highly satisfies the properties required for the insulating layer of circuit boards, and contributes significantly to the realization of finer wiring. It is.
• melt viscosity The melt viscosities of the resin composition layers of the resin sheets prepared in Examples and Comparative Examples were measured using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM Co., Ltd.). Using a parallel plate with a diameter of 18 mm, 1 g of a sample resin composition sampled from the resin composition layer was heated from a starting temperature of 60° C. to 200° C. at a heating rate of 5° C./min. The dynamic viscoelastic modulus was measured under the measurement conditions of 5°C, frequency of 1 Hz, and strain of 1 deg, and the melt viscosity (poise) at 100°C was measured.
• the surface potential (kV) of the support of the obtained laminate was measured using a surface potential meter (“FMX-004” manufactured by Simco Japan Co., Ltd.). Then, the surface potential was evaluated according to the following criteria.
• Warp evaluation criteria ⁇ : The amount of warp is 0 mm or more and 2 mm or less ⁇ : The amount of warp is greater than 2 mm
• the layer structure of the support used in Examples and Comparative Examples is as follows. In the following, the right side of the support (PET film) is the "first surface” side, and the left side is the "second surface” side.
• Support 1 PET film/antistatic layer (first surface surface resistivity 1.0 ⁇ 10 5 ⁇ /sq., second surface surface resistivity >1.0 ⁇ 10 13 ⁇ /sq., thickness about 38 ⁇ m)
• Support 2 release layer/PET film/antistatic layer (first surface surface resistivity 1.0 ⁇ 10 5 ⁇ /sq., second surface surface resistivity >1.0 ⁇ 10 13 ⁇ / sq., thickness about 38 ⁇ m)
• Support 3 release layer/antistatic layer/PET film/antistatic layer (surface resistivity of first surface 1.0 ⁇ 10 5 ⁇ /sq., surface resistivity of second surface 1.0 ⁇ 10 7 ⁇ /sq., thickness about 38 ⁇ m)
• Support 4 release layer/PET film (first surface surface resistivity>1.0 ⁇ 10 13 ⁇ /sq., second surface surface resistivity>1.0 ⁇ 10 13 ⁇ /sq. , thickness about 38 ⁇ m)
• the resulting dry powder was heated to 600° C. at a rate of 1° C./min with an air flow (3 L/min) using a high-speed heating electric furnace (“SK-2535E” manufactured by Motoyama Co., Ltd.). C. for 2 hours to remove organic components and obtain hollow silica precursor particles.
• 0.5 g of this hollow silica precursor particle is transferred to an alumina crucible and fired in the air at 1000 ° C. for 72 hours using the electric furnace to obtain hollow silica particles A (average particle size 1.6 ⁇ m, BET specific surface area 12 m 2 /g and a porosity of 50% by volume).
• Hollow silica particles B were synthesized according to the description in Japanese Patent No. 5940188. Specifically, hollow silica particles B were synthesized by the following procedure.
• silica-based particle precursor particles (1) Using 300 g of water glass aqueous solution (SiO 2 /Na 2 O molar ratio 3.2, SiO 2 concentration 24% by weight), one of the two-fluid nozzles is supplied with a flow rate of 0.12 kg / hr, and the other nozzle is supplied with air at 31800 L / Hot air at an inlet temperature of 400° C. was sprayed at a flow rate of hr (empty/liquid volume ratio: 31,800) to obtain silica-based particle precursor particles (1). At this time, the outlet temperature was 150°C. Then, 50 g of silica-based particle precursor particles (1) were immersed in 500 g of an aqueous sulfuric acid solution having a concentration of 10% by weight and stirred for 2 hours. Then, it was dried and heat-treated in a dryer at 90° C. for 12 hours to obtain hollow silica particles.
• aqueous sulfuric acid solution having a concentration of 10% by weight and stirred for 2 hours
• the resulting hollow silica particles were heated to 600°C at a rate of 1°C/min with an air flow (3L/min) using a high-speed heating electric furnace (“SK-2535E” manufactured by Motoyama Co., Ltd.), After firing at 600 ° C. for 2 hours, 0.5 g of the hollow silica particles are transferred to an alumina crucible and fired in the air at 1000 ° C. for 72 hours using the electric furnace to obtain hollow silica particles B (average particle size 2 0 ⁇ m, a BET specific surface area of 3.8 m 2 /g, and a porosity of 20% by volume).
• SK-2535E manufactured by Motoyama Co., Ltd.
• the temperature of the obtained solution was raised to 60° C., and 8 g of isophorone diisocyanate (“IPDI” manufactured by Evonik Degussa Japan, isocyanate group equivalent: 113 g/eq.) was added while stirring, and the reaction was carried out for about 3 hours. Thus, a first reaction solution was obtained.
• IPDI isophorone diisocyanate
• a solution (50% by mass of non-volatile components) containing, as a non-volatile component, the stress relaxation material A (phenolic hydroxyl group-containing polybutadiene resin) having a reactive functional group was obtained as a filtrate.
• the stress relaxation material A had a number average molecular weight of 5,900 and a glass transition temperature of -7°C.
• Paraloid EXL2655 2 parts, inorganic filler (Spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., surface-treated with an amine-based silane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.5 ⁇ m, specific surface area 5.8 m 2 /g )) 76 parts, phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK and cyclohexanone with a nonvolatile content of 30% by mass) 3 parts, phenolic curing agent (manufactured by DIC “KA-1160”, phenolic Hydroxy group equivalent 117 g / eq.) 3 parts, active ester curing agent (manufactured by DIC "HPC-8000-65T", active group equivalent 223 g / eq., solid content 65 mass% toluene solution) 11 parts, curing accelerator 0.05 parts of (4
• Example 2 Preparation of resin sheet 2
• a resin sheet 2 was produced in the same manner as in Example 1 except that the support 2 was used instead of the support 1 .
• the total specific surface area of the inorganic filler in the resin composition layer was 4.4 m 2 /g.
• Example 3 Preparation of resin sheet 3
• a resin sheet 3 was produced in the same manner as in Example 1 except that the support 3 was used instead of the support 1 .
• the total specific surface area of the inorganic filler in the resin composition layer was 4.4 m 2 /g.
• JP-100 epoxidized polybutadiene resin
• stress relaxation material A 3 parts
• inorganic filler amine-based silane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM573") surface-treated 76 parts of spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 ⁇ m, specific surface area 5.8 m 2 /g)
• phenolic curing agent (“KA-1160” manufactured by DIC, phenolic Hydroxy group equivalent 117 g / eq.) 2 parts
• active ester curing agent manufactured by DIC "HPC-8000-65T", active group equivalent 223 g / eq., solid content 65 mass% toluene solution
• Example 7 Preparation of resin sheet 7]
• resin composition (i) Spherical silica surface-treated with an inorganic filler (amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("SO-C2" manufactured by Admatechs, average The same as Example 5, except that the amount of the particle size of 0.5 ⁇ m and the specific surface area of 5.8 m 2 /g)) was changed from 76 parts to 66 parts, and (ii) 10 parts of the hollow silica particles A were used. Then, a varnish of the resin composition was prepared.
• amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)
• SO-C2 amine-based silane coupling agent manufactured by Admatechs
• Example 8 Preparation of resin sheet 8]
• resin composition (i) Spherical silica surface-treated with an inorganic filler (amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("SO-C2" manufactured by Admatechs, average The same as Example 5, except that the amount of the particle size of 0.5 ⁇ m and the specific surface area of 5.8 m 2 /g)) was changed from 76 parts to 66 parts, and (ii) 10 parts of the hollow silica particles B were used. Then, a varnish of the resin composition was prepared.
• amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)
• SO-C2 amine-based silane coupling agent manufactured by Admatechs
• Example 2 Fabrication of resin sheet
• a support 4 was used instead of the support 1, and the prepared resin composition varnish was applied to the second surface of the support 4. , to prepare a resin sheet C2.
• the total specific surface area of the inorganic filler in the resin composition layer was 9.8 m 2 /g.
• Table 1 shows the results of Examples 1 to 8 and Comparative Examples 1 and 2.
• Comparative Example 1 In Comparative Example 1, after the resin composition layer and the base material were bonded, the pressure in the chamber in which the resin sheet to be treated and the base material were stored was reduced.).
• the insulating material in the form of a resin sheet is applied to a large-area substrate. It was also confirmed that the occurrence of interfacial voids can be suppressed and the increase in the surface potential of the support can be suppressed (Examples 1 to 8).

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