JP2009070921A - Insulative resin sheet containing glass woven fabric, laminate sheet, multilayer printed wiring board, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulative resin sheet containing glass woven fabric which has low thermal expansivity, excellent thermal shock resistance and excellent fire retardancy, also has high inter-wall insulation reliability under high temperature and high humidity environments and can be formed in high density and numerous layers, and to provide a laminate sheet, a multilayer printed wiring board and a semiconductor device using the sheet. <P>SOLUTION: The insulative resin sheet containing glass woven fabric includes the glass woven fabric and an insulative resin composition, wherein the number of voids present in warp threads is 0.1 to 10 for 100,000 warp threads. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an insulating resin sheet containing a glass fiber woven fabric, a laminated board, a multilayer printed wiring board, and a semiconductor device.

  Insulating resin sheets with base materials used for the core material and build-up layer of multilayer printed wiring boards are impregnated with resin varnish made of epoxy resin, etc. on base materials such as glass cloth and glass nonwoven fabric, heat-dried, and semi-cured resin Method (see, for example, Patent Document 1), insulating resin layers on both sides of the base material, and a carrier film made of copper foil or PET film on the outside, and this is heated and pressurized to apply resin to the base material. (For example, refer to Patent Document 2), a resin varnish is applied to a carrier film, a substrate is disposed thereon, and then a resin varnish is applied again (for example, (See Patent Document 3).

  When the insulating resin layer with a base material is used as a core material of a multilayer printed wiring board, one or a plurality of insulating resin sheets with a base material are stacked, and a copper foil or the like is disposed on at least one surface. A copper-clad laminate is produced by heating and pressurizing. Further, an inner layer circuit board is manufactured by forming an inner layer circuit pattern by etching or the like on the copper clad laminate, and at least one surface of the inner layer circuit board is provided with one or a plurality of insulating resin sheets containing a base material and copper foil, etc. Are stacked and heated and pressed to produce a multilayer printed wiring board.

  A through-hole is formed in the copper-clad laminate by drilling or laser processing, an interlayer circuit is electrically connected by plating or conductive filler, and a circuit pattern is formed by etching or the like to produce an inner layer circuit board. .

  In addition, when the insulating resin sheet with a base material is used for a build-up layer of a multilayer printed wiring board, a carrier film made of an insulating resin sheet with a base material and a copper foil, a PET film, or the like on at least one surface of the inner layer circuit board After heating and pressurizing this, vias are formed by laser processing, circuit patterns are formed by the additive method and subtra method, etc., and interlayer connection is made electrically, so that a multilayer printed wiring board by the build-up method can be formed. Make it.

  With recent downsizing and thinning of electronic parts and electronic devices, multilayer printed wiring boards and the like used for these are required to be further downsized and thinned. In order to meet such demands, thinning of the insulating resin layer constituting the multilayer printed wiring board and reduction of the circuit width and the pitch between the circuits have been studied. In such a case, it has been difficult to reduce the warpage of the substrate, to satisfy the impact resistance, and to satisfy the insulation reliability.

JP 2004-216784 A JP 2002-46125 A JP 2004-82687 A

  The present invention has low thermal expansion and impact resistance that does not cause peeling and cracking of the conductor circuit layer by thermal shock tests such as a thermal cycle test, and has flame retardancy, and is also high in a high temperature and high humidity environment. An insulating resin sheet containing a glass fiber woven fabric having inter-wall insulation reliability and capable of high density and high multilayer molding, and a laminated board, multilayer printed wiring board, and semiconductor device using the same are provided.

Such an object is achieved by the present invention described in the following (1) to (12).
(1) In an insulating resin sheet containing a glass fiber woven fabric composed of a warp yarn and a weft yarn and an insulating resin composition, when the glass fiber woven fabric is arbitrarily cut in a direction perpendicular to the warp yarn An insulating resin sheet with a glass fiber woven fabric, wherein the number of voids present in the warp yarn is 0.1 to 10 per 100,000 warp yarns.
(2) The voids present in the warp yarn are substantially cylindrical, and the maximum diameter of each void is 0.01 μm or more and 1.2 μm or less, and the insulating resin containing a glass fiber woven fabric according to (1) Sheet.
(3) The insulating resin sheet with a glass fiber woven fabric according to (1) or (2), wherein the length of the voids present in the warp is 200 mm or less.
(4) The insulating resin sheet containing glass fiber woven fabric according to any one of (1) to (3), wherein the glass fiber constituting the glass fiber woven fabric has a linear expansion coefficient of 1 ppm / ° C. or higher and 10 ppm / ° C. or lower.
(5) The glass fiber woven fabric-containing insulation according to any one of (1) to (4), wherein the glass fiber woven fabric has a thickness of 10 μm to 100 μm and a mass of 10 g / m ^{2 to} 110 g / m ^2. Resin sheet.
(6) The glass substrate-containing insulating resin sheet according to any one of (1) to (5), wherein the glass softening point of the glass fiber woven fabric is 800 ° C. or higher and 1800 ° C. or lower.
(7) The glass fiber woven fabric contains at least 50% by weight to 75% by weight SiO ₂ , 5% by weight to 30% by weight Al ₂ O ₃ , and 20% by weight or less MgO in the glass. The insulating resin sheet containing a glass fiber woven fabric according to any one of (1) to (6).
(8) The glass fiber woven fabric includes the glass fiber woven fabric insulation according to any one of (1) to (7), wherein the glass contains at least 0.1 wt% to 2 wt% of TiO _2. Resin sheet.
(9) The insulating resin composition according to any one of (1) to (8), including at least one selected from the group consisting of a bisphenol-type epoxy resin, a novolac-type epoxy resin, and an arylalkylene-type epoxy resin. Insulating resin sheet with glass fiber woven fabric.
(10) One or more sheets of the insulating resin sheet with glass fiber woven fabric according to any one of (1) to (9) are laminated, and a copper foil is provided on at least one outer surface of the insulating resin sheet with glass fiber woven fabric. Is a laminated board formed by heating and pressing.
(11) A multilayer printed wiring board using the insulating resin sheet containing a glass fiber woven fabric according to any one of (1) to (9) and / or the laminated board according to (10).
(12) A semiconductor device comprising a semiconductor element mounted on the multilayer printed wiring board according to (11).

  The insulating resin sheet with glass fiber woven fabric of the present invention has low thermal expansion and impact resistance and high insulation reliability between walls even in high temperature and high humidity environments, enabling high density and high multilayer molding. A multilayer printed wiring board and a semiconductor device using the same can be manufactured.

  The insulating resin sheet with glass fiber woven fabric, laminated board, multilayer printed wiring board, and semiconductor device of the present invention will be described in detail below.

  The glass fiber woven fabric used for the insulating resin sheet containing the glass fiber woven fabric of the present invention has 0.1 voids per 100,000 warp yarns when the warp yarns are arbitrarily cut in the direction perpendicular to the warp yarns. The number is 10 or less. Thereby, when the said insulating resin sheet containing a glass fiber woven fabric is used for a multilayer printed wiring board or a semiconductor device, the fall of the insulation reliability between walls of a through hole or a via wall can be suppressed. The gap may be inspected for either the warp or weft of the glass fiber woven fabric. However, when checking the gap, the gap in the flow direction is easier to check than the direction perpendicular to the glass fiber. It is desirable to inspect the voids contained in the warp yarn. The number of voids is preferably 0.1 or more and 8 or less per 100,000 warp yarns, more preferably 0.1 or more and 5 or less, and further preferably 0.1 or more and 3 or less. Thereby, the said effect | action can be expressed effectively.

  Also, if the number of the voids exceeds the upper limit, the insulation reliability between the through holes or via walls is impaired, thereby making it possible to produce a multilayer printed wiring board or a semiconductor device without any practical problems. The number of through holes or vias that can be formed is limited. When the number of the voids is less than the lower limit, it is difficult to produce glass fibers practically and deteriorates the yield, so that the productivity is lowered.

  The number of voids in the glass fiber woven fabric can be confirmed by immersing the glass fiber woven fabric in a solvent close to the refractive index of glass and observing it with an optical microscope. An example of a solvent having a refractive index close to that of glass is benzyl alcohol.

  The voids present in the glass fiber woven fabric used in the insulating resin sheet with glass fiber woven fabric of the present invention are substantially columnar in the same direction as the glass fiber woven fabric, and the maximum diameter of each void is 0.01 μm or more. 1.2 μm or less. Thereby, when the said insulating resin sheet containing a glass fiber woven fabric is used for a multilayer printed wiring board or a semiconductor device, the fall of the insulation reliability between walls of a through hole or a via wall can be suppressed. When the maximum diameter of the void is within the above range, when the through hole or via is formed with carbon dioxide gas or UV laser, the glass fiber void near the through hole or via wall can be blocked by the heat of the laser. . The maximum diameter of the void is particularly preferably 0.01 μm or more and 1.0 μm or less, more preferably 0.01 μm or more and 0.8 μm or less, and further preferably 0.01 μm or more and 0.5 μm or less. Thereby, said effect | action can be expressed effectively.

  When the maximum diameter of the void is less than the lower limit, it is difficult to confirm the void even if the glass fiber woven fabric is immersed in the solvent and observed with an optical microscope. The inter-wall insulation reliability of through-holes or via walls is impaired, which limits the number of through-holes or vias that can be formed per unit area in order to produce multilayer printed wiring boards and semiconductor devices without practical problems. The

  The length in the warp direction of the voids present in the glass fiber woven fabric used in the insulating resin sheet with the glass fiber woven fabric of the present invention is 200 mm or less. Thereby, when the said insulating resin sheet containing a glass fiber woven fabric is used for a multilayer printed wiring board or a semiconductor device, the fall of the insulation reliability between walls of a through hole or a via wall can be suppressed. The gap may be either a warp or a weft of a glass fiber woven fabric, but is preferably the length in the warp direction for the convenience of checking the gap. The length of the gap in the glass fiber direction is preferably 150 mm or less, and more preferably 100 mm or less. Thereby, said effect | action can be expressed effectively.

  When the length in the warp direction of the gap exceeds the upper limit value, the insulation reliability between the walls of the through hole or via wall is impaired, and thereby to produce a multilayer printed wiring board or a semiconductor device without any practical problem, The number of through holes or vias that can be formed per unit area is limited.

  The linear expansion coefficient of the glass fiber of the present invention is 1 ppm / ° C. or more and 10 ppm / ° C. or less. Thereby, even when the thickness of the multilayer printed wiring board using the insulating resin sheet with the glass fiber woven fabric is 0.2 mm or less, it is possible to reduce warpage when a thermal history such as solder reflow after chip mounting is applied. The linear expansion coefficient is particularly preferably from 1 ppm / ° C. to 8 ppm / ° C., more preferably from 1 ppm / ° C. to 6 ppm / ° C., and further preferably from 2 ppm / ° C. to 4 ppm / ° C. Thereby, the said effect | action can be expressed effectively.

  When the linear expansion coefficient is less than the lower limit value, depending on the thickness of the multilayer printed wiring board, it becomes impossible to suppress the warpage of the substrate during press molding or solder reflow due to a mismatch of linear expansion with the conductor circuit. Sometimes. Also, if the above upper limit is exceeded, the conductor circuit layer may also be peeled off during thermal shock tests such as warping of the multilayer printed wiring board during press molding or solder reflow and thermal cycle tests due to mismatch of linear expansion with the conductor circuit. And the generation of cracks may not be suppressed.

  The linear expansion coefficient can be obtained, for example, by increasing the temperature from 0 ° C. to 280 ° C. using TMA at 5 ° C./min and measuring the linear expansion coefficient at 25 ° C.

The glass fiber woven fabric of the present invention has a thickness of 10 μm to 100 μm and a mass of 10 g / m ^{2 to} 110 g / m ² . Thereby, the thickness of the multilayer printed wiring board using the said glass fiber woven insulating resin sheet and a semiconductor device can be made thin, and a through-hole and via | veer of a narrow pitch can be formed.

  When the thickness and / or mass of the glass fiber woven fabric is less than the above, the handling property of the glass fiber woven fabric may deteriorate. When the upper limit is exceeded, the insulating resin sheet with the glass fiber woven fabric is used. It is difficult to reduce the thickness of multilayer printed wiring boards and semiconductor devices, and it may be difficult to form through holes and vias with carbon dioxide gas or UV lasers in insulating resin layers when manufacturing multilayer printed wiring boards. .

  It is preferable that the tensile strength of the glass fiber which comprises the said glass fiber woven fabric is 2.5 GPa or more and 5.0 GPa or less. Thereby, even if the thickness of the multilayer printed wiring board using the said insulating resin sheet containing a glass fiber woven fabric is 0.2 mm or less, mechanical strength can be raised. When the tensile strength is less than the lower limit value, it is difficult to obtain sufficient mechanical strength when the thickness of the multilayer printed wiring board is thin. Through-hole processability with a mechanical drill may deteriorate.

The softening point of the glass constituting the glass fiber woven fabric is preferably 800 ° C. or higher and 1800 ° C. or lower. Thereby, glass fiber with few generation | occurrence | production of the space | gap contained in a glass fiber woven fabric can be produced. The glass fiber having the softening point contains at least 50 wt% to 75 wt% SiO ₂ , 5 wt% to 30 wt% Al ₂ O ₃ , and 20 wt% MgO in the glass. It is preferable. In some cases, it is preferable to contain 0.1 wt% or more and 2 wt% or less of TiO ₂ .

  Thereby, the thermal expansion coefficient of a glass fiber woven fabric can be made small, and thereby the thermal expansion coefficient of the insulating resin sheet containing a glass fiber woven fabric can be made more effective. Moreover, since the tensile strength and elastic modulus of the glass fiber woven fabric are large, the multilayer printed wiring board using the insulating resin sheet containing the glass fiber woven fabric, the mechanical strength of the semiconductor device, and the semiconductor element are mounted on the multilayer printed wiring board. An effect can be obtained by reducing warpage when a thermal history is applied such as later solder reflow.

  The insulating resin composition used for the insulating resin sheet with a glass fiber woven fabric of the present invention contains an epoxy resin. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, and bisphenol Z type epoxy resin. Bisphenol type epoxy resin, phenol novolac type epoxy resin, novolac type epoxy resin such as cresol novolac epoxy resin, biphenyl type epoxy resin, arylalkylene type epoxy resin such as biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, Phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type Such as epoxy resins such as epoxy resins. Thereby, the crosslinking density of the hardened | cured material of the said insulating resin composition can be increased, and high flame retardance and heat resistance can be provided.

  Although content of the said epoxy resin is not specifically limited, It is preferable that it is 60 to 90 weight% of the whole insulating resin composition. More preferably, it is 65 to 85% by weight. Thereby, the said effect | action can be expressed effectively. If the content of the epoxy resin is less than the lower limit, the effect of improving the heat resistance may not be sufficient. Moreover, when the said upper limit is exceeded, hardened | cured material will become hard and drill workability and punching workability may fall at the time of multilayer printed wiring board manufacture. Here, when liquid bisphenol A type epoxy resin and bisphenol F type epoxy resin are used in combination, the impregnation property to the glass fiber woven fabric can be improved. Moreover, when solid bisphenol A type epoxy resin and bisphenol F type epoxy resin are used in combination, adhesion to copper foil can be improved.

  The epoxy resin used in the insulating resin composition of the present invention is not halogenated. Thereby, flame retardancy can be imparted substantially without using a halogen compound, and the occurrence of corrosive and toxic components due to halogen can be eliminated during thermal decomposition of the cured product.

  The insulating resin composition of the present invention preferably contains an inorganic filler. As a result, even when the thickness of the multilayer printed wiring board or semiconductor device using the glass fiber woven insulating resin sheet is thin, the mechanical strength is increased and the warp when a thermal history such as solder reflow after chip mounting is applied. Can be reduced more effectively, and the linear expansion coefficient can be reduced.

  Examples of the inorganic filler include silicates such as talc, calcined clay, unfired clay, mica and glass, oxides such as titanium oxide, alumina, silica and fused silica, calcium carbonate, magnesium carbonate, hydrotalcite and the like. Carbonates, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, zinc borate, barium metaborate, aluminum borate, boron Examples thereof include borates such as calcium oxide and sodium borate, nitrides such as aluminum nitride, boron nitride, silicon nitride, and carbon nitride, titanates such as strontium titanate and barium titanate. One of these can be used alone, or two or more can be used in combination.

  Among these, silica is particularly preferable, and fused silica (particularly spherical fused silica) is preferable in terms of excellent low thermal expansion. There are crushed and spherical shapes, but in order to reduce the melt viscosity of the insulating resin composition in order to ensure the impregnation of the glass fiber woven fabric, the use method according to the purpose such as using spherical silica is adopted. Is done.

  The average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 to 5.0 μm, particularly preferably 0.1 to 2.0 μm. If the particle size of the inorganic filler is less than the lower limit, the viscosity of the varnish increases, so that the impregnation property of the insulating resin composition into the glass fiber woven fabric may decrease. When the upper limit is exceeded, phenomena such as sedimentation of the inorganic filler may occur in the varnish. This average particle diameter can be measured, for example, by a particle size distribution meter (manufactured by HORIBA, LA-500).

  The inorganic filler is not particularly limited, but an inorganic filler having a monodispersed average particle diameter can be used, and an inorganic filler having a polydispersed average particle diameter can be used. Furthermore, one type or two or more types of inorganic fillers having an average particle size of monodispersed and / or polydispersed can be used in combination.

  Furthermore, spherical silica (especially spherical fused silica) having an average particle size of 5.0 μm or less is preferable, and spherical fused silica having an average particle size of 0.01 to 2.0 μm is particularly preferable. Thereby, the filling property of an inorganic filler can be improved.

  Although content of the said inorganic filler is not specifically limited, 20 to 80 weight% of the whole insulating resin composition is preferable, and 30 to 70 weight% is especially preferable. When the content is within the above range, particularly low thermal expansion and low water absorption can be achieved.

  The insulating resin composition is not particularly limited, but it is preferable to use a coupling agent. The coupling agent improves the wettability of the interface between the insulating resin and the inorganic filler, thereby uniformly fixing the insulating resin and the inorganic filler to the glass fiber woven fabric, Solder heat resistance after moisture absorption can be improved.

  As the coupling agent, any commonly used one can be used. Specifically, an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a titanate coupling agent, and a silicone oil type coupling. It is preferable to use one or more coupling agents selected from among the agents. Thereby, the wettability with the interface of an inorganic filler can be made high, and thereby heat resistance can be improved more.

  The addition amount of the coupling agent is not particularly limited because it depends on the specific surface area of the inorganic filler, but is preferably 0.05 to 3% by weight, particularly 0.1 to 2% with respect to 100 parts by weight of the inorganic filler. % By weight is preferred. If the content is less than the lower limit, the inorganic filler cannot be sufficiently coated, and thus the effect of improving the heat resistance may be reduced. If the content exceeds the upper limit, the reaction is affected, and the bending strength is reduced. There is a case.

  A curing accelerator may be used in the insulating resin composition as necessary. A well-known thing can be used as said hardening accelerator. For example, organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III), triethylamine, tributylamine, diazabicyclo [2,2 , 2] tertiary amines such as octane, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole Imidazoles such as 2-phenyl-4,5-dihydroxyimidazole, phenolic compounds such as phenol, bisphenol A, and nonylphenol, organic acids such as acetic acid, benzoic acid, salicylic acid, paratoluenesulfonic acid, and the like, or a mixture thereof. . As the curing accelerator, one kind including these derivatives can be used alone, or two or more kinds including these derivatives can be used in combination.

  Although content of the said hardening accelerator is not specifically limited, 0.05 to 5 weight% of the whole insulating resin composition is preferable, and 0.2 to 2 weight% is especially preferable. If the content is less than the lower limit, the effect of promoting curing may not appear, and if the content exceeds the upper limit, the storage stability of the insulating resin sheet with a glass fiber woven fabric may deteriorate.

  The insulating resin composition is composed of thermoplastic resin such as phenoxy resin, polyimide resin, polyamideimide resin, polyphenylene oxide resin, polyethersulfone resin, polyester resin, polyethylene resin, polystyrene resin, styrene-butadiene copolymer, styrene-isoprene copolymer. Polystyrene thermoplastic elastomers such as polymers, polyolefin thermoplastic elastomers, polyamide elastomers, thermoplastic elastomers such as polyester elastomers, and diene elastomers such as polybutadiene, epoxy modified polybutadiene, acrylic modified polybutadiene, methacryl modified polybutadiene, etc. You may do it. In addition, for the insulating resin composition, additives other than the above components such as pigments, dyes, antifoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, ion scavengers, etc., as necessary May be added.

Next, the insulating resin sheet with glass fiber woven fabric will be described.
The glass fiber woven fabric-containing insulating resin sheet of the present invention is obtained by impregnating a glass fiber woven fabric with the above-described insulating resin composition. Thereby, it is possible to obtain an insulating resin sheet containing a glass fiber woven fabric suitable for producing a multilayer printed wiring board having excellent properties such as dielectric properties, mechanical properties under high temperature and high humidity, and electrical connection reliability. .

  Examples of the method of impregnating the glass fiber woven fabric with the insulating resin composition include, for example, preparing a resin varnish using the insulating resin composition, immersing the glass fiber woven fabric in the resin varnish, applying with various coaters, spraying And the like. Among these, the method of immersing the glass fiber woven fabric in the resin varnish is preferable. Thereby, the impregnation property of the insulating resin composition with respect to the glass fiber woven fabric can be improved. In addition, when a glass fiber woven fabric is immersed in a resin varnish, a normal impregnation coating equipment can be used.

  The solvent used in the resin varnish desirably has good solubility in the resin component in the insulating resin composition, but a poor solvent may be used as long as it does not adversely affect the resin varnish. Examples of the solvent exhibiting good solubility include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve and carbitol.

  The nonvolatile content concentration in the resin varnish is not particularly limited, but is preferably 40 to 80% by weight, and particularly preferably 50 to 65% by weight. Thereby, the viscosity of a resin varnish can be made into a suitable level, and the impregnation property to a glass fiber woven fabric can further be improved. An insulating resin sheet with a glass fiber woven fabric can be obtained by impregnating the glass fiber woven fabric with the insulating resin composition and drying at a predetermined temperature, for example, 80 to 200 ° C.

Next, a laminated board is demonstrated.
The laminate of the present invention is formed by molding at least one insulating resin sheet containing glass fiber woven fabric. Thereby, the laminated board excellent in the dielectric property and the mechanical and electrical connection reliability in high temperature and high humidity can be obtained.
In the case of one insulating resin sheet containing glass fiber woven fabric, a metal foil or film is stacked on both upper and lower surfaces or one surface. Two or more insulating resin sheets with glass fiber woven fabric can be laminated. When two or more insulating resin sheets with glass fiber woven fabric are laminated, a metal foil or film is laminated on the outermost upper and lower surfaces or one side of the laminated insulating resin sheets with glass fiber woven fabric. Next, a laminated board can be obtained by heating and pressurizing what laminated | stacked the insulating resin sheet containing a glass fiber woven fabric, metal foil, etc. FIG. Although the temperature to heat is not specifically limited, 120-220 degreeC is preferable and especially 150-200 degreeC is preferable. Moreover, the pressure to pressurize is not particularly limited, but is preferably 2 to 5 MPa, and particularly preferably 2.5 to 4 MPa.

Examples of the metal constituting the metal foil include copper and copper alloys, aluminum and aluminum alloys, silver and silver alloys, gold and gold alloys, zinc and zinc alloys, nickel and nickel alloys, tin and tin. Alloy, iron, iron alloy and the like.
Examples of the film include polyethylene, polypropylene, polyethylene terephthalate, polyimide, and fluorine resin.

  Next, a multilayer printed wiring board will be described.

A multilayer printed wiring board can be manufactured using the said laminated board. The manufacturing method is not particularly limited, and there are a subtractive method, a semi-additive method, and the like, for example, using a laminated plate having copper foil on both sides, providing an opening at a predetermined position with a drill machine, and electroless plating As a result, conduction between both surfaces of the inner layer circuit board is achieved. Then, an inner layer circuit is formed by etching the copper foil.
The inner layer circuit portion can be suitably used after roughening treatment such as blackening treatment. The opening can be appropriately filled with a conductor paste or a resin paste.

  Next, the insulating resin sheet containing the glass fiber woven fabric of the present invention or the insulating resin sheet with a film is laminated so as to cover the inner layer circuit to form an insulating resin layer. The lamination method is not particularly limited, but a lamination method using a vacuum press, a normal pressure laminator, and a laminator that is heated and pressurized under vacuum is preferable, and a method using a laminator that is heated and pressurized under vacuum is more preferable. It is.

  Thereafter, the insulating resin layer is cured by heating. Although the temperature to harden | cure is not specifically limited, For example, it can be made to harden | cure in the range of 100 to 250 degreeC. Preferably it is made to harden | cure at 150 to 200 degreeC.

  Next, an opening was provided in the insulating resin layer using a carbonic acid laser device, and an outer layer circuit was formed on the surface of the insulating resin layer by electrolytic copper plating, so that conduction between the outer layer circuit and the inner layer circuit was achieved. The outer layer circuit is provided with a connection electrode portion for mounting a semiconductor element.

  After that, a solder resist is formed on the outermost layer, the connection electrode part is exposed so that a semiconductor element can be mounted by exposure / development, nickel gold plating treatment is performed, and it is cut into a predetermined size to obtain a multilayer printed wiring board. Can do.

  Next, the semiconductor device will be described.

  A semiconductor element having a solder bump is mounted on the multilayer printed wiring board obtained above, and the multilayer printed wiring board and the semiconductor element are connected via the solder bump. A liquid sealing resin is filled between the multilayer printed wiring board and the semiconductor element to form a semiconductor device. The solder bump is preferably made of an alloy made of tin, lead, silver, copper, bismuth or the like. The connection method between the semiconductor element and the multilayer printed wiring board is to align the connection electrode part on the substrate with the solder bump of the semiconductor element using a flip chip bonder, etc. The solder bumps are heated to the melting point or higher by using a heating device, and the multilayer printed wiring board and the solder bumps are connected by fusion bonding. In order to improve connection reliability, a metal layer having a relatively low melting point, such as solder paste, may be formed in advance on the connection electrode portion on the multilayer printed wiring board. Prior to this joining step, the connection reliability can be improved by applying a flux to the solder bumps and / or the surface layer of the connection electrode portion on the multilayer printed wiring board.

Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to this.
In addition, the glass fiber woven fabric used by this invention is as follows.
Glass fiber woven fabric (1)
Thickness 80μm, mass 95g / m ² , cross style 2319, manufactured by Nitto Boseki, glass type A
Glass fiber woven fabric (2)
Thickness 42μm, mass 48g / m ² , cross style 1078, manufactured by Nitto Boseki, glass type A
Glass fiber woven fabric (3)
Thickness 28μm, mass 30g / m ² , cross style 1035, made by Nittobo, glass type A
Glass fiber woven fabric (4)
Thickness 95 μm, mass 104 g / m ² , cross style 2116, manufactured by Nitto Boseki, glass type A
Glass fiber woven fabric (5)
Thickness 14μm, Mass 12g / m ² , Cross Style 1014, Nittobo, Glass Type B
Glass fiber woven fabric (6)
Thickness 95 μm, mass 104 g / m ² , cross style 2116, manufactured by Nitto Boseki, glass type B
Glass fiber woven fabric (7)
Thickness 95 μm, mass 104 g / m ² , cross style 2116, manufactured by Nitto Boseki, glass type A
Glass fiber woven fabric (8)
Thickness 95 μm, mass 104 g / m ² , cross style 2116, manufactured by Nitto Boseki, glass type B
Glass fiber woven fabric (9)
Thickness 90μm, mass 104g / m ² , cross style 2116, Nitto Boseki, glass type B
Glass type A
(Physical properties) Linear expansion coefficient: 2.8 ppm / ° C., Tensile strength: 4.6 GPa, Softening point: 970 ° C. (Chemical composition) SiO ₂ : 64 wt%, Al ₂ O ₃ : 25 wt%, MgO: 10 wt %, TiO ₂ : 1% by weight
Glass type B
(Physical properties) Linear expansion coefficient: 5.8 ppm / ° C., Tensile strength: 3.2 GPa, Softening point: 850 ° C. (Chemical composition) SiO ₂ : 54 wt%, Al ₂ O ₃ : 14 wt%, MgO: 3 wt %)

Example 1
(1) Adjustment of resin varnish Cresol novolak type epoxy resin (“Epiclon N-690”, epoxy equivalent 210, manufactured by Dainippon Ink & Chemicals, Inc.) 22 parts by weight, bisphenol A type epoxy resin (I) (“Epiclon 850”) , Epoxy equivalent 190, manufactured by Dainippon Ink & Chemicals, Inc.) 6.5 parts by weight, bisphenol A type epoxy resin (II) (“Epiclon 7050”, epoxy equivalent 1900, manufactured by Dainippon Ink & Chemicals, Inc.) 1.5 Parts by weight, 1 part by weight of a biphenyl dimethylene type epoxy resin (NC-3000, epoxy equivalent 275, manufactured by Nippon Kayaku Co., Ltd.), 1.5 parts by weight of dicyandiamide (manufactured by Sigma Aldrich Japan Co., Ltd.), 10-benzyl-9, 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxy Sid (manufactured by Sanko Co., Ltd.) 6.4 parts by weight, 2-methylimidazole (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 0.1 part by weight, epoxy silane type coupling agent (A-187, manufactured by GE Toshiba Silicone Co., Ltd.) 1 part by weight is dissolved in methyl ethyl ketone at room temperature, 60 parts by weight of an inorganic filler (spherical fused silica, SO-25R, average particle size 0.5 μm, manufactured by Admatechs Co., Ltd.) is added, and a high-speed agitator is used. The resin varnish was adjusted to a non-volatile content of 55% by stirring for 10 minutes.

(2) Manufacture of insulating resin sheet with glass fiber woven fabric

  The glass fiber woven fabric (1) was impregnated with the above resin varnish and dried in a heating furnace at 150 ° C. for 2 minutes to obtain an insulating resin sheet with a glass fiber woven fabric having a thickness of about 0.1 mm.

(3) Manufacture of laminated plate A predetermined number of the above-mentioned insulating resin sheets with glass fiber woven fabric are stacked, a copper foil having a thickness of 12 μm is stacked on both surfaces, and pressure-molded at a pressure of 4 MPa and a temperature of 200 ° C. for 2 hours. Thus, a laminate having copper foil on both sides was obtained.

(4) Manufacture of multilayer printed wiring board After forming a through hole in the above-mentioned laminated board, a predetermined circuit wiring is formed on the copper foil by the subtractive method, and after roughening the surface of the circuit wiring, both sides of the laminated board An insulating resin sheet with a film (APL-3601, resin thickness: 60 μm, manufactured by Sumitomo Bakelite Co., Ltd.) was laminated on the inner layer circuit using a vacuum laminator. Next, the film was peeled off and heated at a temperature of 170 ° C. for 60 minutes to semi-cure the insulating resin layer. In addition, the conditions for laminating the insulating resin sheet with a film were set to a temperature of 100 ° C., a pressure of 1 MPa, and 30 seconds.

  Next, a φ60 μm aperture (blind via hole) is formed on the insulating resin layer using a carbonic acid laser device, and immersed in a swelling solution (Swelling Dip Securigant P, manufactured by Atotech Japan) at 70 ° C. for 10 minutes. Further, after being immersed in an aqueous potassium permanganate solution (manufactured by Atotech Japan Co., Ltd., Concentrate Compact CP) at 80 ° C. for 20 minutes, it was neutralized and roughened. Next, after passing through degreasing, catalyst application, and activation steps, an electroless copper plating film was formed with a power supply layer of about 0.5 μm. Next, a 25 μm thick UV-sensitive dry film (AQ-2558 manufactured by Asahi Kasei Co., Ltd.) is bonded to the surface of the power supply layer with a hot roll laminator, and a chromium having a pattern with a minimum line width / line spacing of 20/20 μm is drawn. Using a vapor deposition mask (manufactured by Towa Process Co., Ltd.), the position was adjusted, exposure was performed with an exposure apparatus (UX-1100SM-AJN01 manufactured by USHIO INC.), And development was performed with a sodium carbonate aqueous solution to form a plating resist.

  Next, electrolytic copper plating (81-HL manufactured by Okuno Pharmaceutical Co., Ltd.) was performed at 3 A / dm 2 for 30 minutes using the power feeding layer as an electrode to form a copper wiring having a thickness of about 25 μm. Here, the plating resist was peeled off using a two-stage peeling machine. Each chemical solution is mainly composed of monoethanolamine solution (R-100 manufactured by Mitsubishi Gas Chemical Co., Ltd.) in the first stage alkaline aqueous solution layer, and potassium permanganate and sodium hydroxide as the main ingredients in the second stage oxidizing resin etchant. An aqueous solution of acidic amine (Mc. Dicer 9279, manufactured by Nihon McDermid Co., Ltd.) was used for neutralization.

  Next, the power feeding layer was immersed in an aqueous ammonium persulfate solution (AD-485 manufactured by Meltex Co., Ltd.) to remove it by etching and ensure insulation between the wirings. Next, the insulating resin layer was finally cured at a temperature of 200 ° C. for 60 minutes, and finally a solder resist (PSR4000 / AUS308 manufactured by Taiyo Ink Co., Ltd.) was formed on the circuit surface to obtain a multilayer printed wiring board.

(5) Manufacture of a semiconductor device A semiconductor element having a thickness of 0.75 mm and a size of 15 mm × 15 mm is bonded to a predetermined position on the above-described multilayer printed wiring board having a size of 50 mm × 50 mm using a flip chip bonder and a reflow furnace, A semiconductor device was obtained by filling a liquid sealing resin (CRP-4152S, manufactured by Sumitomo Bakelite Co., Ltd.) and curing the liquid sealing resin. The curing condition of the liquid sealing resin was a temperature of 150 ° C. and 120 minutes.

(Example 2)
Laminated plate in the same manner as in Example 1 except that the glass fiber woven fabric (2) was used instead of the glass fiber woven fabric (1) to obtain an insulating resin sheet with a glass fiber woven fabric having a thickness of about 0.06 mm. A multilayer printed wiring board and a semiconductor device were produced.

(Example 3)
Laminated plate in the same manner as in Example 1 except that the glass fiber woven fabric (3) was used instead of the glass fiber woven fabric (1) to obtain an insulating resin sheet with a glass fiber woven fabric having a thickness of about 0.05 mm. A multilayer printed wiring board and a semiconductor device were produced.

Example 4
Laminated plate in the same manner as in Example 1, except that the glass fiber woven fabric (4) was used instead of the glass fiber woven fabric (1) to obtain an insulating resin sheet with a glass fiber woven fabric having a thickness of about 0.12 mm. A multilayer printed wiring board and a semiconductor device were produced.

(Example 5)
Laminated plate in the same manner as in Example 1 except that the glass fiber woven fabric (5) was used instead of the glass fiber woven fabric (1) to obtain an insulating resin sheet with a glass fiber woven fabric having a thickness of about 0.03 mm. A multilayer printed wiring board and a semiconductor device were produced.

(Example 6)
Laminated plate in the same manner as in Example 1, except that the glass fiber woven fabric (6) was used instead of the glass fiber woven fabric (1) to obtain an insulating resin sheet with a glass fiber woven fabric having a thickness of about 0.12 mm. A multilayer printed wiring board and a semiconductor device were produced.

(Comparative Example 1)
A laminated board similar to Example 1, except that the glass fiber woven fabric (7) was used instead of the glass fiber woven fabric (1), and an insulating resin sheet with a glass fiber woven fabric having a thickness of about 0.12 mm was obtained. A multilayer printed wiring board and a semiconductor device were produced.

(Comparative Example 2)
44 parts by weight of cresol novolac type epoxy resin, 13 parts by weight of bisphenol A type epoxy resin (I), 3 parts by weight of bisphenol A type epoxy resin (II), 2 parts by weight of biphenyldimethylene type epoxy resin, 3 parts of dicyandiamide 1 part by weight of 10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 0.2 part by weight of 2-methylimidazole, 20 parts by weight of inorganic filler In the same manner as in Example 1, except that the glass fiber woven fabric (8) was used instead of the glass fiber woven fabric (1) to obtain an insulating resin sheet with a glass fiber woven fabric having a thickness of about 0.12 mm. A laminated board, a multilayer printed wiring board, and a semiconductor device were produced.

(Comparative Example 3)
Laminated plate in the same manner as in Example 1 except that the glass fiber woven fabric (9) was used instead of the glass fiber woven fabric (1) to obtain an insulating resin sheet with a glass fiber woven fabric having a thickness of about 0.12 mm. A multilayer printed wiring board and a semiconductor device were produced.

  The characteristics of the resin compositions, the insulating resin sheets with glass fiber woven fabric, the laminates, and the semiconductor devices obtained in the examples and comparative examples were evaluated. The results are shown in Table 1.

The evaluation method is as follows.

1. Number of voids A glass fiber woven fabric having a width of 1060 mm is cut out by 1000 mm in the flow direction of the fiber woven fabric, and this may be of any size, but it is cut into a size of 265 mm wide and 250 mm long and immersed in benzyl alcohol. The number of voids per 100,000 warp yarns of the glass fiber woven fabric was determined by counting the number of voids in the glass fiber woven fabric while observing with a microscope. Here, benzyl alcohol is used because the refractive index of benzyl alcohol is close to the refractive index of the glass fiber woven fabric, so that voids in the glass fiber woven fabric can be easily found.

2. Diameter of the void The diameter of the void was measured by polishing the cross section of the warp yarn of the glass fiber woven fabric in the portion including the void and observing the void with an electron microscope.

3. A glass fiber woven fabric with a gap length of 1060 mm is cut out 1000 mm in the flow direction of the fiber woven fabric, immersed in benzyl alcohol, and observed with a loupe, is there a gap of 200 mm or more in the warp direction of the glass fiber woven fabric? confirmed.
○: No gap of 200 mm or more ×: There is a gap of 200 mm or more

4). The linear expansion coefficient glass fiber woven fabric was cut into a weft direction of 4 mm and a warp direction of 20 mm, and the linear expansion coefficient at 25 ° C. was measured using TMA under a pulling condition of 5 ° C./min.

5). Thermal shock test The semiconductor device obtained above was treated in 500 cycles for 1 cycle at -55 ° C for 10 minutes, 125 ° C for 10 minutes and -55 ° C for 10 minutes in Fluorinert. confirmed.
○: No crack occurrence ×: Crack occurrence

6). Insulation reliability test between walls Obtained above is a 0.8 mm thick laminated plate having copper foil on both sides (a laminated plate produced by stacking eight insulating resin sheets with a glass fiber woven thickness of about 0.1 mm) ), Using a mechanical drill, open a through hole with a diameter of 0.4 mm and a distance between walls of 0.4 mm, and then form a plating and circuit wiring, and 500 h under the conditions of 85 ° C., 85% RH and applied voltage 50 V. The insulation resistance was measured at 100V. N = 10 samples were prepared for measurement.
○: N is 1.0 × 10 ⁷ Ω or more Δ: 1.0 × 10 ⁷ Ω or more is N ≧ 8
×: 1.0 <10 ⁷ Ω or more is N <8

7). In accordance with the flame retardant UL-94 standard, a 1 mm thick test piece was measured by the vertical method.

8). Moisture-absorbing solder heat test A test piece was prepared by cutting 50 mm × 50 mm from a 0.8 mm thick laminate having copper foil on both sides obtained above, and performing half-side etching according to JIS C 6481. After being treated with a pressure cooker at 121 ° C. for 2 hours, it was floated in a solder bath at 260 ° C. with the copper foil face down, and the presence or absence of appearance abnormality after 120 seconds was examined.
○: No abnormality ×: There is swelling

As is clear from Table 1, Examples 1 to 6 are glass fiber woven fabric-containing insulating resin sheets in which the number of voids existing in the warp yarn of the glass fiber woven fabric is small and the maximum diameter and length of the voids are short. And a laminated board, a multilayer printed wiring board, and a semiconductor device using the same.
Examples 1 to 6 all had good results in all evaluations, such as low thermal expansion, impact resistance, insulation reliability, flame retardancy.
On the other hand, in Comparative Example 1 and Comparative Example 3, the number of voids in the warp yarn of the glass fiber woven fabric was large, and the length of the voids was long.
In Comparative Example 2, the number of voids in the warp yarn of the glass fiber woven fabric is large, the diameter is long, and the addition amount of the inorganic filler is small. Therefore, in the inter-wall insulation reliability test, thermal shock test, and flame retardancy test The result was unfavorable. In addition, in the flame retardant test, since the test piece was completely burned, it was described as out of specification in Table 1.

  The insulating resin sheet with a glass fiber woven fabric of the present invention can be suitably used for a laminated board, a multilayer printed wiring board comprising the laminated board, and a semiconductor device, but also has a low thermal expansion property, impact resistance, high temperature, wall Since it is excellent in inter-insulation reliability, it can also be used for applications requiring high reliability among multilayer printed wiring boards that are required to be downsized and thinned.

Claims (12)

  In an insulating resin sheet containing a glass fiber woven fabric composed of a warp yarn and a weft yarn and an insulating resin composition, in the warp yarn when the glass fiber woven fabric is arbitrarily cut in a direction perpendicular to the warp yarn An insulating resin sheet containing a glass fiber woven fabric, wherein the number of voids present is from 0.1 to 10 per 100,000 warp yarns.   The insulating resin sheet with a glass fiber woven fabric according to claim 1, wherein the voids present in the warp yarn are substantially cylindrical, and the maximum diameter of each void is 0.01 µm or more and 1.2 µm or less.   The insulating resin sheet with a glass fiber woven fabric according to claim 1 or 2, wherein the length of the gap existing in the warp yarn in the warp yarn direction is 200 mm or less. The insulating resin sheet with glass fiber woven fabric according to any one of claims 1 to 3, wherein a linear expansion coefficient of the glass fiber constituting the glass fiber woven fabric is 1 ppm / ° C to 10 ppm / ° C. 5. The insulating resin sheet with glass fiber woven fabric according to claim 1, wherein the glass fiber woven fabric has a thickness of 10 μm to 100 μm and a mass of 10 g / m ^{2 to} 110 g / m ² . The insulating resin sheet with a glass substrate according to any one of claims 1 to 5, wherein the glass fiber woven fabric has a glass softening point of 800C or higher and 1800C or lower. The glass fiber woven fabric contains at least 50% by weight to 75% by weight SiO ₂ , 5% by weight to 30% by weight Al ₂ O ₃ , and 20% by weight or less MgO in the glass. The insulating resin sheet containing a glass fiber woven fabric according to any one of 1 to 6. The glass fiber woven fabric, at least, glass fiber woven fabric containing insulating resin sheet according to any one of claims 1 to 7 is intended to include 0.1 wt% or more than 2 wt% of TiO ₂ in the glass. The glass fiber woven fabric according to any one of claims 1 to 8, wherein the insulating resin composition includes at least one selected from the group consisting of a bisphenol type epoxy resin, a novolac type epoxy resin, and an arylalkylene type epoxy resin. Insulating resin sheet. One or more insulating resin sheets with glass fiber woven fabric according to any one of claims 1 to 9 are overlapped, and copper foil is disposed on at least one outer surface of the insulating resin sheet with glass fiber woven fabric and heated. A laminated board formed by pressure molding. A multilayer printed wiring board using the insulating resin sheet with glass fiber woven fabric according to any one of claims 1 to 9 and / or the laminate according to claim 10. A semiconductor device comprising a semiconductor element mounted on the multilayer printed wiring board according to claim 11.