CN103347938A

CN103347938A - Pre-preg, laminate board, printed wiring board, and semiconductor device

Info

Publication number: CN103347938A
Application number: CN2012800062793A
Authority: CN
Inventors: 大东范行
Original assignee: Sumitomo Bakelite Co Ltd
Current assignee: Sumitomo Bakelite Co Ltd
Priority date: 2011-01-24
Filing date: 2012-01-19
Publication date: 2013-10-09
Anticipated expiration: 2032-01-19
Also published as: TWI539869B; MY155995A; WO2012101991A1; JP2012167256A; KR20130102654A; TW201251534A; JP5234195B2; CN103347938B; KR101355777B1

Abstract

This pre-preg (40) is formed by impregnating a woven fiber constituted of strands with a resin composition. In this pre-preg, silica particles are present in the strands. This makes it possible to obtain a pre-preg having a superior ability for woven fiber to be impregnated with the resin composition. It is further possible to use this pre-preg and/or a metal-clad laminate board produced using this pre-preg to produce a printed wiring board and a semiconductor device.

Description

Prepreg, veneer sheet, printed circuit board (PCB) and semiconductor device

Technical field

The present invention relates to prepreg, veneer sheet, printed circuit board (PCB) and semiconductor device.

Background technology

In recent years, along with the requirement of multifunction of electronics etc., quickening such as integrated and high-density installationization of the high-density of electronic unit.Therefore, for the printed circuit board (PCB) of employed reply high-density installation wherein, require the miniaturization of wiring and the downsizing of through hole and via.

Through hole and via can use laser such as drilling machine, carbon dioxide laser to form, and particularly the punching of minor diameter can be used laser.In the perforation processing of utilizing laser to carry out, form insulation layer wall concavo-convex more big in hole, aperture, shape more are easy to generate deviation, and working accuracy reduces.

The insulation layer of printed circuit board (PCB) can form by 1 prepreg or the overlapping prepreg of multi-disc are carried out heating and pressurizing.Generally, prepreg can be made by the following method,, makes that to contain with the thermosetting resin in the base material impregnation solvent such as woven fiber glass be the varnish that the resin combination of main component forms that is, and it is heated makes its drying, makes thus.Utilizing laser processing to form in the insulation layer wall in hole, in base material part and resin combination part, utilize the meltbility of laser there are differences.Therefore, when the little and hole of the density of base material is thick, there are aperture, shape to be easy to generate the tendency of deviation.On the other hand, by using compact highdensity base material, can improve the perforation processing (patent documentation 1,2) that insulation layer utilizes laser.

In addition, for the densification that the parts of tackling on printed circuit board (PCB) are installed, require to reduce warpage that printed circuit board (PCB) causes because of thermal expansion to guarantee connection reliability.Semiconductor device (semiconductor package body) semiconductor element mounted thereon on printed circuit board (PCB) forms, and the coefficient of thermal expansion of semiconductor element is 3～6ppm/ ℃, and is littler with the coefficient of thermal expansion of printed circuit board (PCB) than general semiconductor package.Therefore, when semiconductor package body was applied thermal shocking, warpage took place because of the thermal expansion rate variance of semiconductor element and semiconductor packages body and function printed circuit board (PCB) in semiconductor packages cognition sometimes.At this moment, between semiconductor element and the semiconductor packages body and function printed circuit board (PCB), between semiconductor package body and the printed circuit board (PCB) installed, bad connection takes place sometimes.

Be used for insulation layer by the insulativity material that coefficient of thermal expansion is little, can reduce the warpage that printed circuit board (PCB) causes because of thermal expansion.To become the prepreg of insulativity material low linear expansionization in order making, as the resin combination for the manufacture of prepreg, can to use the highly-filled resin combination (patent documentation 3) that inorganic filling material is arranged.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2001-38836 communique

Patent documentation 2: TOHKEMY 2000-22302 communique

Patent documentation 3: TOHKEMY 2009-138075 communique

Summary of the invention

Yet when using highdensity base material to make prepreg, resin combination is poor to the impregnation of base material, especially contains the resin combination of a large amount of packing materials, does not enter the impregnation that is difficult to carry out resin combination between the fiber of base material because of packing material.In addition, in order to improve impregnation, when for example reducing the content etc. of packing material, be difficult to keep other various characteristics that prepreg has sometimes.

The present invention finishes in order to address the above problem, and the objective of the invention is to, and provides can keep various characteristics that prepreg has and compositions of thermosetting resin to the prepreg of the impregnation excellence of fiber weaving cloth.In addition, the objective of the invention is to, the metal-coated laminated board that uses this prepreg is provided and uses printed circuit board (PCB) and the semiconductor device that they obtain.

According to the present invention, a kind of prepreg can be provided, it is the prepreg that the fiber weaving cloth impregnation resin combination that is made of precursor (strand) is formed, and has silica dioxide granule in the aforementioned precursor.

According to the present invention, can provide and to keep various characteristics that prepreg has and compositions of thermosetting resin to the prepreg of the impregnation excellence of fiber weaving cloth.

In addition, according to the present invention, can use aforementioned prepreg and/or use the metal-coated laminated board made from aforementioned prepreg to make printed circuit board (PCB) and semiconductor device.

Description of drawings

Preferred implementation by the following stated and subsidiary the following drawings thereof can further clear and definite above-mentioned purposes, and other purpose, feature and advantage.

Fig. 1 is the sketch chart of an example of the manufacture method of expression metal-coated laminated board of the present invention.

Fig. 2 is the sketch chart of an other example of the manufacture method of expression metal-coated laminated board of the present invention.

Fig. 3 is the photo of the sectional view of the prepreg that obtains of embodiment 1.

Fig. 4 is the photo of the sectional view of the prepreg that obtains of comparative example 4.

Fig. 5 be metal-coated laminated board that embodiment 1 is obtained the whole facet etch of Copper Foil the photo on surface.

Fig. 6 be metal-coated laminated board that comparative example 6 is obtained the whole facet etch of Copper Foil the photo on surface.

Fig. 7 is the SEM photo of the enlarged view in observed space among Fig. 6.

Fig. 8 is the SEM photo of the enlarged view of the section in observed space among Fig. 7.

Fig. 9 is the SEM photo of sectional view of a part of precursor of the expression fiber weaving cloth that constitutes the prepreg that embodiment 1 obtains.

Figure 10 is the SEM photo of sectional view of a part of precursor of the expression fiber weaving cloth that constitutes the prepreg that embodiment 1 obtains.

Figure 11 is the SEM photo of sectional view of a part of precursor of the expression fiber weaving cloth that constitutes the prepreg that embodiment 1 obtains.

Figure 12 is the SEM photo of sectional view of a part of precursor of the expression fiber weaving cloth that constitutes the prepreg that embodiment 1 obtains.

Embodiment

Below, at length prepreg of the present invention, metal-coated laminated board, printed circuit board (PCB) and semiconductor device are described.

1. prepreg

Prepreg of the present invention is the prepreg that the fiber weaving cloth impregnation resin combination that is made of precursor is formed.In addition, there is silica dioxide granule in the precursor of formation fiber weaving cloth.Need to prove that precursor is the fibrous bundle that constitutes fiber weaving cloth.By precursor being woven so that it becomes braiding structure described later, form fiber weaving cloth.

The inventor finds, when existing silica dioxide granule to form prepreg, can keep the various characteristics that prepreg has in precursor, and can improve resin combination to the impregnation of fiber weaving cloth.Here, various characteristics refers to for example insulating reliability, the laser processing of prepreg or the low heat expansion property of prepreg etc. of printed circuit board (PCB) described later.

When resin combination is good to the impregnation of fiber weaving cloth, produce the space in the prepreg that can suppress to obtain.Thus, use in the printed circuit board (PCB) of this prepreg at insulation layer, can seek to improve insulating reliability.

In addition, even when using highdensity fiber weaving cloth, also can obtain higher impregnation.Therefore, use highdensity fiber weaving cloth, can form the prepreg of laser processing excellence.

And then, by improving resin combination to the impregnation of fiber weaving cloth, can fill packing material at the fiber weaving cloth inner height.Therefore, can seek the low-thermal-expansionization of prepreg.Thus, can suppress insulation layer uses the printed circuit board (PCB) of this prepreg to produce warpage.Thereby, can improve the connection reliability of semiconductor device.

Constitute the resin combination of prepreg for comprising compositions of thermosetting resin (following abbreviate as sometimes " resin combination " of thermosetting resin and packing material at least.）。

For the resin combination that constitutes prepreg, for example preferably contain the silica dioxide granule of median size 5～100nm with the ratio of 1～20 quality % of packing material.The inventor finds, even the prepreg that resin combination that highdensity fiber weaving cloth impregnation contains a large amount of packing materials is obtained, by making aforementioned packing material contain the silica dioxide granule of median size 5～100nm with the ratio of 1～20 quality %, the impregnation of resin combination is also good.Think this be because, the silica dioxide granule of aforementioned median size 5～100nm enters between the fiber of fiber weaving cloth, be in the precursor and make and expand between fiber, so the packing material beyond the silica dioxide granule of median size 5～100nm also can enter fiber weaving cloth.So, the silica dioxide granule of the nano-scale by using median size 5～100nm can obtain having in the precursor prepreg of silica dioxide granule as packing material.

In addition, the surface potential of the silica dioxide granule of median size 5～100nm is different with the surface potential of other packing material, so the silica dioxide granule of median size 5～100nm and aforementioned packing material attract because of interaction.Therefore, the silica dioxide granule of median size 5～100nm be present in aforementioned packing material around, the silica dioxide granule of median size 5～100nm has the effect of spacer.So, the silica dioxide granule of median size 5～100nm be present in aforementioned packing material around, work as spacer, thus, the power of being brought by Van der Waals force that attracts each other of aforementioned packing material is reduced, prevent cohesion.Thus, aforementioned packing material becomes more high dispersion state, can prevent mobile the reduction.

The silica dioxide granule of aforementioned median size 5～100nm preferably uses with the form that is dispersed in the slurry that forms in the organic solvent in advance.Thus, can improve the dispersiveness of packing material, the flowability that takes place in the time of can suppressing to use other packing material reduces.Think that it be the reasons are as follows.At first, the particle of the nano-scale that the silicon-dioxide of nano-scale is such condenses easily, often forms 2 aggregates etc. when being compounded in the resin combination, by using the particle of pulp-like, can prevent 2 times such cohesions, can prevent that the flowability that causes thus from reducing.In addition, for being used for packing material of the present invention, in order to prevent cohesion and to improve dispersiveness, preferably implement surface treatment in advance.

Need to prove that so-called highdensity fiber weaving cloth among the present invention refers to not only increase the filling density radical of yarn, and the fiber weaving cloth that has carried out in heterogeneity per 1 fiber height being opened fibrillation, thickness reduction etc. has been handled by flattening.The volume density of highdensity fiber weaving cloth for example is 1.05g/cm ³More than.Thus, impregnation resin combination between per 1 fiber can be further made, the highly-filled of packing material can be further sought.And then, owing to can fully guarantee amount of resin on the fiber weaving cloth, therefore, can maintain lamination Copper Foil on the prepreg and when making copper-clad laminate or the formability when making the surface smoothing of copper-clad laminate.

So, prepreg of the present invention is because resin combination is good to the impregnation of fiber weaving cloth, and therefore, the space of generation is few.In addition, therefore owing to contain a large amount of packing materials in the resin combination, be low heat expansion property, use the warpage of the printed circuit board (PCB) that prepreg of the present invention obtains little.Need to prove that the thermal expansivity of prepreg is the thermal expansivity of instigating under the state that prepreg solidified among the present invention.

In addition, prepreg of the present invention is by highly-filled packing material, excellent heat resistance and be high rigidity.And then the volume density that constitutes the fiber weaving cloth of prepreg of the present invention is preferably 1.05～1.30g/cm ³Be 1.05～1.30g/cm by using volume density ³Highdensity fiber weaving cloth like this, as the insulation layer of printed circuit board (PCB) the time, by laser processing, it is good and can suppress the outstanding hole of fiber to form the precision of aperture and shape.

In addition, generally, for use contains the prepreg that the resin combination of a large amount of packing materials obtains, because resin combination is to the impregnation deterioration of base material, therefore, base material is difficult to keep resin combination with uniform thickness, when this prepreg being used for insulation layer making printed circuit board (PCB), exists the surface smoothing of aforementioned dielectric layer poor,, the problem that be difficult to carry out fine wiring processing and so on poor with the adaptation of conductor layer.These problems may further worsen when making the prepreg slimming.On the other hand, for prepreg of the present invention, because resin combination is good to the impregnation of fiber weaving cloth, therefore, fiber weaving cloth can keep resin combination with uniform thickness, surface smoothing, good with the adaptation of conductor layer, and can tackle slimming.In addition, prepreg of the present invention becomes high heat resistance, high rigidity by the resin combination that use contains a large amount of packing materials.

At first, employed fiber weaving cloth among the present invention is described.

As employed fiber weaving cloth among the present invention, be not particularly limited, for example, can enumerate the fiber weaving cloth that is formed by synthon, steel fiber, carbon fiber, mineral fibre etc. such as glass fibre, aramid fiber (aramid), polyester, aromatic polyester, fluoro-resin.Wherein, owing to be low heat expansion property, high rigidity and excellent in dimensional stability, therefore, preferably the glass fibre that is formed by glass fibre is weaved cotton cloth.

Aforementioned glass fibre is not particularly limited, preferred contains SiO with the ratio of 50 quality %～100 quality % at least ₂, contain Al with the ratio of 0 quality %～30 quality % ₂O ₃, contain CaO with the ratio of 0 quality %～30 quality %, preferred especially use to be selected from by T glass (be also referred to as " S glass " sometimes.), at least a kind of glass in the group formed of D glass, E glass, NE glass, silica glass forms, wherein, more preferably T glass (S glass), silica glass, D glass are considered from low heat expansion property excellence, high strength aspect, more preferably T glass (S glass), silica glass.

Need to prove that in the present invention, T glass (S glass) is the glass that contains the composition of following material with following ratio: SiO ₂Be 62 quality %～65 quality %, Al ₂O ₃Be that 20 quality %～25 quality %, CaO is that 0 quality %～0.01 quality %, MgO is 10 quality %～15 quality %, B ₂O ₃Be 0 quality %～0.01 quality %, Na ₂O and K ₂O adds up to 0 quality %～1 quality %; D glass is the glass that contains the composition of following material with following ratio: SiO ₂Be 72 quality %～76 quality %, Al ₂O ₃Be that 0 quality %～5 quality %, CaO is that 0 quality %～1 quality %, MgO is 0 quality %～1 quality %, B ₂O ₃Be 20 quality %～25 quality %, Na ₂O and K ₂O adds up to 3 quality %～5 quality %; E glass is the glass that contains the composition of following material with following ratio: SiO ₂Be 52 quality %～56 quality %, Al ₂O ₃Be that 12 quality %～16 quality %, CaO is that 15 quality %～25 quality %, MgO is 0 quality %～6 quality %, B ₂O ₃Be 5 quality %～10 quality %, Na ₂O and K ₂O adds up to 0～0.8 quality %; NE glass is the glass that contains the composition of following material with following ratio: SiO ₂Be 52 quality %～56 quality %, Al ₂O ₃Be that 10 quality %～15 quality %, CaO is that 0 quality %～10 quality %, MgO is 0 quality %～5 quality %, B ₂O ₃Be 15 quality %～20 quality %, Na ₂O and K ₂O adds up to 0 quality %～1 quality %, TiO ₂Be 0.05 quality %～5 quality %, silica glass is that the ratio with 99.0 quality %～100 quality % contains SiO ₂The glass of composition.

Aforementioned glass fibre is not particularly limited, the tensile strength that preferably to make Young's modulus when tabular be 50～100GPa, make when tabular is that 25GPa is above, the tensile strength of the length direction when making fiber weaving cloth is more than the 30N/25mm, and the tensile strength that more preferably to make Young's modulus when tabular be 80～100GPa, make when tabular is that 35GPa is above, the tensile strength of the length direction when making fiber weaving cloth is more than the 45N/25mm.Thus, can obtain the prepreg of excellent in dimensional stability.Need to prove, aforementioned Young's modulus is the value of utilizing usually employed known three point bending test machine to measure according to JIS R1602, aforementioned tensile strength is to utilize the value of the tension type stretching test machine determination of employed known constant speed usually according to JIS R3420, and the tensile strength of aforementioned length direction is according to JISR3420 glass fibre to be made to weave cotton cloth and the value of utilization and the aforementioned same tension type stretching test machine determination of constant speed.

Need to prove that in the mensuration of the mensuration of aforementioned Young's modulus and aforementioned tensile strength, " tabular " refers to and will make the state of the sheet glass of thickness 0.5～1.0mm with the glass composition of glass fibre same composition.In addition, in the mensuration of the tensile strength of aforementioned length direction, " length direction " refers to organizine (vertical yarn) direction.

Aforementioned glass fibre is not particularly limited, and the thermal expansivity of the organizine direction of measuring according to JIS R3102 is preferably below 10ppm/ ℃, is preferably below 3ppm/ ℃ especially.Can reduce the warpage that printed circuit board (PCB) causes because of thermal expansion thus.

The thickness that aforementioned fibers is weaved cotton cloth is not particularly limited, and is preferably 10～200 μ m, more preferably 10～140 μ m, 20～90 μ m more preferably.Thus, resin combination becomes well to the impregnation of fiber weaving cloth, can also tackle slimming.

The volume density that aforementioned fibers is weaved cotton cloth is preferably 1.05～1.30g/cm ³, be preferably 1.10～1.25g/cm especially ³When volume density was lower than aforementioned lower value, the laser processing of insulation layer was poor, and when volume density surpassed aforementioned higher limit, resin combination was to the impregnation deterioration of fiber weaving cloth.Need to prove the thickness of the filling density radical by regulating organizine and tram, the fiber through opening fine flat processing, the volume density of regulating fiber weaving cloth.

Aforementioned fibers weaved cotton cloth to be not particularly limited, and Gas permeability is preferably 1～80cc/cm ²/ sec, be preferably 3～50cc/cm especially ²/ sec.When Gas permeability was lower than aforementioned lower value, resin combination was to the impregnation deterioration of fiber weaving cloth, and when Gas permeability surpassed aforementioned higher limit, the laser processing of insulation layer was poor.

Aforementioned fibers weaved cotton cloth to be not particularly limited, and mass area ratio is preferably 10～160g/m ², be preferably 15～130g/m especially ²When mass area ratio was lower than aforementioned lower value, the low heat expansion property of prepreg was poor, and when mass area ratio surpassed aforementioned higher limit, resin combination was to the impregnation deterioration of fiber weaving cloth, or the laser processing of insulation layer is poor.

In addition, employed fiber was not particularly limited during aforementioned fibers weaved cotton cloth, and flat ratio is preferably 1:2～1:50, is preferably 1:5～1:30 especially.Be in the aforementioned range by the flat ratio that makes employed fiber in the fiber weaving cloth, the impregnation wettability that resin combination is weaved cotton cloth to aforementioned fibers is more excellent, thereby can improve the insulating reliability between through hole, and improves the laser processing of insulation layer.Need to prove that flat ratio is the thickness with silk among the present invention: the value of the width means of silk.

In addition, the braiding structure that aforementioned fibers is weaved cotton cloth is not particularly limited, for example, can enumerate braiding structures such as plain weave, square flat sennit are knitted, satin weave, twill weave etc., wherein, consider from the excellent aspect of layer insulation reliability of laser processing, intensity, via, be preferably the plain weave structure.

Secondly, employed compositions of thermosetting resin among the present invention is described.

Employed compositions of thermosetting resin comprises thermosetting resin and packing material at least among the present invention.Ratio with 50～85 quality % of the solids component of aforementioned compositions of thermosetting resin contains aforementioned packing material.In addition, aforementioned compositions of thermosetting resin contains the silica dioxide granule of median size 5～100nm with the ratio of 1～20 quality % of aforementioned packing material.And then aforementioned compositions of thermosetting resin can also comprise solidifying agent, coupling agent etc. as required.

(packing material)

Aforementioned packing material contains the silica dioxide granule of median size 5～100nm with the ratio of 1～20 quality % of aforementioned packing material integral body.

As aforementioned silica dioxide granule, be not particularly limited, for example, can use the Combustion by VMC(Vaporized Metal) method, PVS(Physical Vapor Synthesis) silica dioxide granule made of combustion method such as method, the methods such as scorification, the precipitator method, gel method of flame fusion that broken silicon-dioxide carried out.Wherein, preferred especially VMC method.Aforementioned VMC method is the method for Si powder burn it after cooling off form silicon dioxide microparticle by dropping in the chemical flame that forms in oxygen-containing gas.In aforementioned VMC method, the particle diameter by the Si powder that regulate to drop into, input amount, flame temperature etc. can be regulated the particle diameter of the silica micro-particle that obtains.In addition, as aforementioned silica dioxide granule, can also use NSS-5N(Tokuyama Corporation to make), Sicastar43-00-501(Micromod Partikeltechnologie GmbH makes) etc. commercially available product.

For the silica dioxide granule of aforementioned median size 5～100nm, consider that from the impregnation aspect preferred especially especially median size is 10～75nm.Think, when the median size of silica dioxide granule is lower than 5nm, between the fiber of can not expansion fiber weaving cotton cloth, in addition, during greater than 100nm, can not enter between fiber sometimes.

The median size of aforementioned silica dioxide granule can be measured by for example laser diffraction and scattering method and dynamic light scattering method etc.Under the situation of the silica dioxide granule of aforementioned median size 5～100nm, in water, utilize ultrasonic wave to make particles dispersed, utilize dynamic light scattering formula particle size distribution device (HORIBA manufacturing, LB-550), with the size-grade distribution that the volume reference instrumentation is decided particle, (D50) is made as median size with its median particle diameter.

In addition, aforementioned silica dioxide granule is not particularly limited, is preferably hydrophobicity.Thus, can suppress the silica dioxide granule cohesion, silica dioxide granule is dispersed in the resin combination of the present invention well.In addition, because the affinity of thermosetting resin and silica dioxide granule improves, the adaptation on the surface of aforementioned hot thermosetting resin and aforementioned silica dioxide granule improves, and therefore, can obtain the insulation layer of physical strength excellence.

Be hydrophobic method as making silica dioxide granule, for example, can enumerate in advance and with the silicane and/or the alkyl silazane class that contain functional group silica dioxide granule be carried out surface-treated method etc.As the aforementioned silicane that contains functional group, can use known material, for example, can enumerate epoxy silane, aminosilane, vinyl silanes, acrylic acid or the like silane, hydrosulphonyl silane, isocynate silane, thioether silane, urea groups silane etc.As aforesaid alkyl silazane class, for example, can enumerate hexamethyldisilazane (HMDS), 1,3-divinyl-1,1,3,3-tetramethyl-disilazane, prestox three silazane, pregnancy basic ring three silazane etc.In addition, handle by silica dioxide granule being carried out aforementioned surfaces, also can bring into play and prevent the packing material cohesion, reach and improve dispersed effect.

Contain the silicane of functional group and/or the amount of alkyl silazane class in advance aforementioned silica dioxide granule being carried out surface-treated, be not particularly limited, with respect to aforementioned silica dioxide granule 100 weight parts, it is above and be below 5 weight parts to be preferably 0.01 weight part.More preferably 0.1 weight part is above and be below 3 weight parts.When the content of the silicane that contains functional group and/or alkyl silazane class surpassed aforementioned higher limit, insulation layer can crack when making printed circuit board (PCB) sometimes, and when being lower than aforementioned lower value, the bonding force of resinous principle and silica dioxide granule reduces sometimes.

For with the silicane and/or the alkyl silazane class that contain functional group aforementioned silica dioxide granule being carried out the surface-treated method in advance, be not particularly limited, be preferably wet type mode or dry type mode.Be preferably the wet type mode especially.The wet type mode is compared with the dry type mode, can handle the surface of aforementioned silica dioxide granule equably.

In addition, the aforementioned surfaces of carrying out more than 50% of preferred contrast table area is handled.

The silica dioxide granule that contains aforementioned median size 5～100nm with the ratio of 1～20 quality % of packing material integral body.When content was lower than aforementioned lower value, the effect that improves impregnation was insufficient, when content surpasses aforementioned higher limit, on the contrary, worried the insufficient formability of impregnation deterioration, prepreg.Need to prove that the content of the silica dioxide granule of aforementioned median size 5～100nm is 3～15 quality % of packing material integral body more preferably.

For employed packing material among the present invention, except the silica dioxide granule of aforementioned median size 5～100nm, be not particularly limited, for example can contain: talcum, calcined clay, silicate such as calcined clay, mica, glass not; Titanium oxide, aluminum oxide, median size are greater than the oxide compounds such as silica dioxide granule of 100nm; Carbonate such as calcium carbonate, magnesiumcarbonate, hydrotalcite; Aluminium hydroxide, boehmite (AlO(OH), be commonly referred to boehmite (that is Al, of " vacation " boehmite ₂O ₃XH ₂O, here, x=1～2)), metal hydroxides such as magnesium hydroxide, calcium hydroxide; Vitriol or sulphite such as barium sulfate, calcium sulfate, calcium sulfite; Borates such as zinc borate, barium metaborate, aluminum borate, lime borate, Sodium Tetraborate; Nitride such as aluminium nitride, boron nitride, silicon nitride, carbonitride; Inorganic filling materials such as titanate such as strontium titanate, barium titanate.For aforementioned inorganic filling material, can use wherein a kind separately, also two or more kinds may be used.Wherein, be preferably magnesium hydroxide, aluminium hydroxide, boehmite, median size greater than spherical silicon dioxide particle, talcum, fired talc, the aluminum oxide of 100nm, aspect low heat expansion property, impregnation, be preferably boehmite, median size especially greater than spherical silicon dioxide particle, the spherical alumina of 100nm.

As the inorganic filling material beyond the silica dioxide granule of aforementioned median size 5～100nm (below be sometimes referred to as " other inorganic filling material ".), be not particularly limited, can use the monodispersed inorganic filling material of median size, also can use the polydisperse inorganic filling material of median size.And then, also can also disperse and/or polydisperse inorganic filling material with median size more than a kind or 2 kinds is single.Median size is for referring to that the standard deviation of particle diameter is below 10% single the dispersion among the present invention, and polydispersion refers to that the standard deviation of particle diameter is more than 10%.

Median size to aforementioned other inorganic filling material is not particularly limited, and is preferably 0.1 μ m～5.0 μ m, is preferably 0.1 μ m～3.0 μ m especially.When the particle diameter of other inorganic filling material was lower than aforementioned lower value, because the viscosity of resin combination uprises, therefore, the operation during sometimes to the making prepreg brought influence.In addition, when surpassing aforementioned higher limit, occur in the resin combination phenomenons such as inorganic filling material precipitation sometimes.Need to prove that median size can use laser diffraction/diffuse transmission type particle size distribution device (common equipments such as SALD-7000 that Shimadzu Seisakusho Ltd. makes) to measure.

And then, process, reach fine rule at the narrow pitch in the processing of carrying out the path hole, hole and add man-hour, preferably aforementioned other inorganic filling material is carried out coarse grain and cut (coarse particle cut).Wherein, preferably carry out the above coarse grain of 45 μ m and cut, further preferably carry out the above coarse grain of 20 μ m and cut, especially preferably carry out the above coarse grain of 10 μ m and cut.Need to prove that " coarse grain is cut " refers to get rid of the coarse particles of the above size of described particle diameter.

In addition, for employed packing material among the present invention, preferably except aforementioned inorganic filling material, also contain organic filler materials such as rubber grain etc.As the preference of operable rubber grain among the present invention, can enumerate core-shell-type rubber grain, crosslink propylene nitrile divinyl rubber particle, cross-linked styrene divinyl rubber particle, acrylic rubber particle, organic silicon granule etc.

The core-shell-type rubber grain is the rubber grain with sandwich layer and shell, for example, can enumerate: outer field shell is by the rubber grain of 2 layers of structure that glassy polymers constitutes, the sandwich layer of internal layer is made of rubbery polymer; Or outer field shell by glassy polymers constitute, the middle layer is by rubber grain of the 3-tier architecture that rubbery polymer constitutes, sandwich layer is made of glassy polymers etc.The glassy polymers layer for example is made of Polymerization of Methyl thing etc., and the rubbery polymer layer is for example by butyl acrylate polymkeric substance formations such as (isoprene-isobutylene rubbers).As the concrete example of core-shell-type rubber grain, can enumerate: Sutafiroido AC3832, AC3816N(trade(brand)name, Ganz Chemical Co., Ltd. makes), METABLEN KW-4426(trade(brand)name, Mitsubishi Rayon Co., Ltd. makes).As the concrete example of crosslink propylene nitrile divinyl rubber (NBR) particle, can enumerate XER-91(median size 0.5 μ m, JSR Corporation and make) etc.

As the concrete example of cross-linked styrene divinyl rubber (SBR) particle, can enumerate XSK-500(median size 0.5 μ m, JSR Corporation and make) etc.As the concrete example of acrylic rubber particle, can enumerate: METABLEN W300A(median size 0.1 μ m), W450A(median size 0.2 μ m) (Mitsubishi Rayon Co., Ltd. make) etc.

For aforementioned organic silicon granule, so long as the caoutchouc elasticity particulate that is formed by organopolysiloxane gets final product, be not particularly limited, for example, can enumerate: the particulate that itself is formed by organo-silicone rubber (organopolysiloxane cross-linked elastomer), and the core shell structure particle that forms of the core that is formed by the organosilicon of the crosslinked main body of two dimension with the silicone covering of three-dimensional cross-linked type main body etc.As aforementioned organic silicon granule, can use: KMP-605, KMP-600, KMP-597, KCC of KMP-594(SHIN-ETSU HANTOTAI make), Trefil E-500, Trefil E-600(Dow Corning Toray Co., Ltd. makes) etc. commercially available product.

In packing material used in the present invention, be the silica dioxide granule packing material in addition of 5～100nm for median size, in order to prevent cohesion, to reach and improve dispersiveness, preferably implement surface treatment in advance.Surface treatment agent can use known silane coupling agent, for example, can enumerate: epoxy silane, aminosilane, vinyl silanes, acrylic acid or the like silane, hydrosulphonyl silane etc.In addition, preferred contrast table area carries out surface treatment more than 50%.

For the content of the packing material in the resin combination used in the present invention, in the solids component benchmark of resin combination integral body, be preferably 50～85 quality %, be preferably 65～75 quality % especially.When packing material content surpasses aforementioned higher limit, the mobile non-constant of resin combination, the operation when making prepreg is poor.When packing material content is lower than above-mentioned lower value, coefficient of thermal expansion height sometimes, the intensity of insulation layer is insufficient.

(thermosetting resin)

As the aforementioned hot thermosetting resin, be not particularly limited, can use Resins, epoxy, cyanate ester resin, bimaleimide resin, resol, benzoxazine colophony, vinyl benzyl ether resin, benzocyclobutane olefine resin etc., generally, other thermosetting resin of Resins, epoxy appropriate combination is used.

As aforementioned epoxy resins, be not particularly limited, be preferably in fact the not Resins, epoxy of halogen atom.Here, so-called " in fact not halogen atom " removes operation through halogen and still remains in the Resins, epoxy even refer to allow to come from the halogen of the halogen set member that uses in the building-up process of Resins, epoxy.Generally, do not contain in the preferred epoxy above 30ppm halogen atom.

As the aforementioned in fact Resins, epoxy of halogen atom not, for example can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol E-type Resins, epoxy, bisphenol-s epoxy resin, bisphenol Z type Resins, epoxy (4,4 '-hexylidene hexichol phenol-type epoxy resin, 4,4 '-cyclohexydiene bisphenol type epoxy resin), bis-phenol P type Resins, epoxy (4,4 '-(1,4)-and the phenylene di-isopropyl) the hexichol phenol-type epoxy resin, 4,4 '-(1,4)-and phenylene diisopropylidene) bisphenol type epoxy resin), bis-phenol M type Resins, epoxy (4,4 '-(1,3-phenylene di-isopropyl) hexichol phenol-type epoxy resin) bisphenol-type epoxy resin such as; Phenolic resin varnish type epoxy resins such as phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin; Biphenyl type epoxy resin, xylol type Resins, epoxy, phenol aralkyl-type epoxy resin, biphenyl aralkyl-type epoxy resin, biphenyl dimethylene type Resins, epoxy, tris-phenol phenolic resin varnish type epoxy resin, 1,1,2,2-(, four phenol) the Racemic glycidol ethers of ethane, 3 officials can or 4 officials can aryl alkylene type Resins, epoxy such as glycidyl amine, tetramethyl biphenyl type Resins, epoxy; Naphthalene type Resins, epoxy such as naphthalene framework modification Resins, epoxy, methoxynaphthalene modification cresols phenolic resin varnish type epoxy resin, methoxynaphthalene dimethylene type Resins, epoxy, naphthylidene ether type epoxy; Anthracene type Resins, epoxy, phenoxy group type Resins, epoxy, dicyclopentadiene-type epoxy resin, norbornene-type Resins, epoxy, diamantane type Resins, epoxy, fluorenes type Resins, epoxy, fire-retardantization Resins, epoxy that above-mentioned Resins, epoxy halogenation is obtained etc.

Both can use a kind of Resins, epoxy in these Resins, epoxy separately, also can and with Resins, epoxy more than 2 kinds with different weight-average molecular weight, can also and with the prepolymer of Resins, epoxy and Resins, epoxy more than a kind or 2 kinds.

In these Resins, epoxy, be preferably selected from especially by biphenyl dimethylene type Resins, epoxy, phenolic resin varnish type epoxy resin, naphthalene modification cresols phenolic resin varnish type epoxy resin, and the group formed of anthracene type Resins, epoxy at least a kind.By using these Resins, epoxy, can improve the veneer sheet that obtains and moisture absorption solder heat resistance and the flame retardant resistance of printed circuit board (PCB).

In addition, in these Resins, epoxy, the thermotolerance by using the naphthylidene ether type epoxy, can improve the veneer sheet that obtains and printed circuit board (PCB), low heat expansion property, and low thermal shrinkage behavior.

The naphthylidene ether type epoxy can use-case such as following general formula (1) expression.

[Chemical formula 1]

(in the formula, R ¹Expression hydrogen atom or methyl, R ²Represent alkyl, aralkyl, the naphthyl of hydrogen atom, carbonatoms 1～4 respectively independently or contain the naphthyl of glycidyl ether, o and m are respectively 0～2 integer, and among o or the m any is more than 1.）

Content to aforementioned epoxy resins is not particularly limited, and in the solids component benchmark of aforementioned resin integral body, is preferably 5～60 weight %.When content was lower than aforementioned lower value, the solidified nature of resin combination reduced sometimes, or used prepreg that this resin combination obtains or the wet fastness of printed circuit board (PCB) to reduce.In addition, when content surpassed aforementioned higher limit, the linear thermal expansion ratio of prepreg or printed circuit board (PCB) became big sometimes, or thermotolerance reduces.In the solids component benchmark of resin combination integral body, the content of aforementioned epoxy resins is preferably 10～50 weight % especially.

Weight-average molecular weight to aforementioned epoxy resins is not particularly limited, and is preferably 1.0 * 10 ²～2.0 * 10 ⁴When weight-average molecular weight was lower than aforementioned lower value, the surface of prepreg produced viscosity sometimes, when weight-average molecular weight surpasses aforementioned higher limit, and the solder heat resistance reduction of prepreg sometimes.By weight-average molecular weight is made as in the aforementioned range, can make the balance excellence of these characteristics.

In the present invention, the weight-average molecular weight of aforementioned epoxy resins can be measured with for example gel permeation chromatography (GPC), and is next specific with the weight molecular weight of polystyrene conversion.

Aforementioned resin is not particularly limited, by comprising cyanate ester resin, can improves flame retardant resistance, reduce thermal expansivity, and then, the electrical characteristic (low-k, low dielectric loss angle tangent) of prepreg etc. can be improved.

Aforementioned cyanate ester resin is not particularly limited, for example, can by with make the reaction of halogen cyan compound and phenol or aphthols and as required method such as heating carry out the pre-polymerization materialization and obtain.In addition, also can use the commercially available product of such operation preparation.

Kind as aforementioned cyanate ester resin is not particularly limited, and for example, can enumerate bisphenol type cyanate ester resins such as phenolic varnish type cyanate ester resin, bisphenol A cyanate ester resin, bisphenol E-type cyanate resin, tetramethyl-Bisphenol F type cyanate ester resin etc.

For aforementioned cyanate ester resin, preferred intramolecularly have more than 2 cyanate ester based (O-CN).For example, can enumerate: 2,2 '-two (the 4-cyanate radical closes phenyl) isopropylidene (2,2 '-bis(4-cyanatophenyl) isopropylidene), 1,1 '-two (the 4-cyanate radical closes phenyl) ethane, it is two that (the 4-cyanate radical closes-3, the 5-3,5-dimethylphenyl) methane, 1,3-two (the 4-cyanate radical closes phenyl-1-(1-methyl ethidine)) benzene, the dicyclopentadiene-type cyanate, phenol phenolic varnish type cyanate, two (the 4-cyanate radical closes phenyl) thioether, two (the 4-cyanate radical closes phenyl) ether, 1,1,1-three (the 4-cyanate radical closes phenyl) ethane, three (the 4-cyanate radical closes phenyl) phosphorous acid ester, two (the 4-cyanate radical closes phenyl) sulfone, 2, two (the 4-cyanate radical the closes phenyl) propane of 2-, 1,3-, 1,4-, 1,6-, 1,8-, 2,6-or 2,7-two cyanate radicals close naphthalene, 1,3,6-three cyanate radicals close naphthalene, 4,4-, two cyanate radicals close biphenyl, and by the phenol phenolic varnish type, the cyanate ester resin that the reaction of cresols phenolic varnish type polyatomic phenol and halogen cyan obtains, cyanate ester resin that reaction by the polynary aphthols of naphthols aralkyl-type and halogen cyan obtains etc.

Wherein, the flame retardant resistance of phenol phenolic varnish type cyanate ester resin, and low heat expansion property excellence, 2,2 '-two (the 4-cyanate radical closes phenyl) isopropylidene, and the cross-linking density control of dicyclopentadiene-type cyanate, and moisture-proof reliability excellence.Consider preferred especially phenol phenolic varnish type cyanate ester resin from the low heat expansion property aspect.In addition, also can be not particularly limited further also with other cyanate ester resin more than a kind or 2 kinds.

Aforementioned cyanate ester resin can use separately.In addition, also two or more kinds may be used the different cyanate ester resin of weight-average molecular weight, or and with aforementioned cyanate ester resin and its prepolymer.

Generally, aforementioned prepolymer is by utilizing reacting by heating etc. with the aforementioned cyanate ester resin material that obtains of trimerizing for example, is for the formability of regulating resin combination, flowability and the preferred material that uses.

Aforementioned prepolymer is not particularly limited, when using that for example the trimerization rate is the prepolymer of 20～50 weight %, can shows good formability, flowability.

Content to aforementioned cyanate ester resin is not particularly limited, and in the solids component benchmark of resin combination integral body, is preferably 5～60 weight %, more preferably 10～50 weight %.When the content of cyanate ester resin is in the aforementioned range time, can more effectively improve thermotolerance and the flame retardant resistance of prepreg.Aforementioned the thermal expansivity of prepreg increases sometimes, thermotolerance reduces down in limited time when the content of cyanate ester resin is lower than, and when the content of cyanate ester resin surpassed aforementioned higher limit, the intensity of prepreg reduced sometimes.

Weight-average molecular weight to aforementioned cyanate ester resin is not particularly limited, and is preferably 5.0 * 10 ²～4.5 * 10 ³, be preferably 6.0 * 10 especially ²～3.0 * 10 ³When weight-average molecular weight was lower than aforementioned lower value, the surface of prepreg produced viscosity sometimes, or physical strength reduces.In addition, when weight-average molecular weight surpassed aforementioned higher limit, the curing reaction of resin combination was accelerated sometimes, with the adaptation deterioration of conductor layer.

In the present invention, the weight-average molecular weight of aforementioned cyanate ester resin can be measured with for example gel permeation chromatography (GPC), and is next specific with the weight molecular weight of polystyrene conversion.

Aforementioned resin is not particularly limited, by comprising bimaleimide resin, can improves thermotolerance.

As aforementioned bimaleimide resin, be not particularly limited, can enumerate: N, N '-(4,4 '-ditan) bismaleimides, two (3-ethyl-5-methyl-4-maleimide phenyl) methane, 2, bimaleimide resins such as 2-two [4-(4-maleimide phenoxy group) phenyl] propane.Aforementioned bimaleimide resin also can be not particularly limited further also with other bimaleimide resin more than a kind or 2 kinds.In addition, aforementioned bimaleimide resin can use separately.In addition, also can and use the different bimaleimide resin of weight-average molecular weight, or also with aforementioned bimaleimide resin and its prepolymer.

Content to aforementioned bimaleimide resin is not particularly limited, and in the solids component benchmark of resin combination integral body, is preferably 1～35 weight %, is preferably 5～20 weight % especially.

(solidifying agent, curing catalyst)

Employed resin combination can and be used solidifying agent among the present invention.As solidifying agent, be not particularly limited, for example, when using Resins, epoxy as the aforementioned hot thermosetting resin, can use as the common employed phenol of curing agent for epoxy resin is solidifying agent, fatty amine, aromatic amine, Dyhard RU 100, dicarboxylic acid dihydrazide compound, acid anhydrides etc.

In addition, employed resin combination can add curing catalyst as required among the present invention.Aforementioned curing catalyst is not particularly limited, for example, can enumerates: organic metal salt, tertiary amines, imidazoles, organic acid, salt compound etc.As curing catalyst, both can use the derivative that comprises these materials at interior a kind separately, the derivative that also can comprise these materials is interior more than 2 kinds.

(coupling agent)

Aforementioned resin can also contain coupling agent.Coupling agent is compounding for the interface wet ability that improves thermosetting resin and packing material.Thus, resin and packing material are fixed on the fiber weaving cloth equably, can improve the solder heat resistance after the thermotolerance of prepreg, the especially moisture absorption.

Aforementioned coupling agent is not particularly limited, for example, can enumerates: epoxy silane coupling agent, cationic silane coupling agent, amino silicane coupling agent, titanic acid ester are coupling agent, silicone oil type coupling agent etc.Thus, the wettability with the interface of packing material can be improved, the thermotolerance of prepreg can be further improved thus.

Addition to aforementioned coupling agent is not particularly limited, and with respect to packing material 100 weight parts, is preferably 0.05～3 weight part, is preferably 0.1～2 weight part especially.When content is lower than aforementioned lower value, because improving stable on heating effect, reduces the packing material that can not fully be covered sometimes.In addition, when content surpasses aforementioned higher limit, sometimes reaction is brought influence, reductions such as flexural strength.

(other)

In addition, aforementioned resin can also be added mentioned components such as flame retardant, ion capturing agent such as defoamer, flow agent, UV light absorber, whipping agent, antioxidant, fire retardant, phosphorus system, phosphonitrile additive in addition as required.

Prepreg of the present invention can obtain by the following method, that is, make fiber weaving cloth remain on the varnish that contains above-mentioned compositions of thermosetting resin in the solvent, then, removes aforementioned solvents.Preparation method to aforementioned varnish is not particularly limited, preferable methods is that for example, preparation is dispersed with the slurry of thermosetting resin and packing material in solvent, in this slurry, add the composition of other resin combination, and then the adding aforementioned solvents is mixed its dissolving.Thus, can improve the dispersiveness of packing material, can make the silica dioxide granule of median size 5～100nm contained in the aforementioned packing material be easy to enter fiber weaving cloth, can improve resin combination to the impregnation of fiber weaving cloth.

Need to prove, contain compositions of thermosetting resin in the so-called solvent among the present invention, resin that refers to solubility contained in the aforementioned compositions of thermosetting resin etc. is dissolved in solvent, and insoluble packing material etc. are dispersed in the solvent.

As aforementioned solvents, be not particularly limited, be preferably the solvent that aforementioned resin is demonstrated good solubility, for example, can enumerate acetone, methyl ethyl ketone (MEK), pimelinketone (ANON), methyl iso-butyl ketone (MIBK) (MIBK), cyclopentanone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone etc.Need to prove, in not bringing dysgenic scope, also can use poor solvent.

The solids component of the resin combination that aforementioned varnish is comprised (remove from varnish solvent after composition) is not particularly limited, and is preferably 30～80 weight %, is preferably 40～70 weight % especially.Thus, can improve resin combination to the impregnation of fiber weaving cloth.In addition, the surface smoothing in the time of can suppressing to be coated with, thickness deviation etc.

For making the weave cotton cloth method of the aforementioned varnish of impregnation of aforementioned fibers, for example can enumerate: the method that impregnation of fibers is weaved cotton cloth in varnish; The method of utilizing various coating machines to be coated with; The method that sprays by injection; At base material coating varnish and make it dry and make resin flake, the mode that this resin flake is contacted with fiber weaving cloth with resin layer disposes and makes the method etc. of its crimping.In these methods, the preferred method that impregnation of fibers is weaved cotton cloth in varnish.Thus, can improve compositions of thermosetting resin to the impregnation of fiber weaving cloth.Need to prove, when impregnation of fibers is weaved cotton cloth in varnish, can use common impregnation coating apparatus.In addition, the solvent by making aforementioned varnish for example 90～180 ℃ dry 1～10 minute down, can obtain the prepreg of semicure.

Aforementioned prepreg is made of following layer: the resin layer that is formed by resin combination on the fiber weaving cloth layer that is formed by fiber weaving cloth, the two sides that is formed at this fiber weaving cloth layer.Thickness to the aforementioned fibers nonwoven fabric layer is not particularly limited, and is preferably 10～200 μ m, more preferably 10～140 μ m, 20～90 μ m more preferably.Thickness (the only thickness of one deck of single face) to the aforementioned resin layer is not particularly limited, and is preferably 0.5～20 μ m, is preferably 2～10 μ m especially.Thickness by making the fiber weaving cloth layer and the thickness of resin layer are in the aforementioned range, and is better with adaptation and the surface smoothing of conductor layer.

Integral thickness to aforementioned prepreg is not particularly limited, and is preferably 30～220 μ m, is preferably 40～165 μ m especially.Thus, the operability of prepreg is good, also can tackle slimming.

In aforementioned prepreg, constitute in the precursor of fiber weaving cloth, there is not the space with the length more than the 50 μ m in the direction of extending at the fiber that constitutes precursor.Thus, can improve the insulating reliability that insulation layer uses the printed circuit board (PCB) of prepreg.And then, in constituting the precursor of fiber weaving cloth, preferably the direction of extending at the fiber that constitutes precursor do not exist have more than the 20 μ m, the space of the length more than the 10 μ m especially.

In addition, in aforementioned prepreg, the diameter in the precursor of formation fiber weaving cloth is that the number density in the above space of 50 μ m is 50cm ^-1Below.At this moment also can improve the insulating reliability that insulation layer uses the printed circuit board (PCB) of prepreg.And then the number density that preferably constitutes diameter in the precursor of fiber weaving cloth and be the above space of 50 μ m is 20cm ^-1Below, 10cm especially ^-1Below.

Need to prove, by the median size of the silica dioxide granule that exists in the suitable adjusting precursor, volume density of fiber weaving cloth etc., can realize length, the number density in the space in the above-mentioned precursor.

2. veneer sheet

Next, veneer sheet is described.

Veneer sheet of the present invention is characterised in that it solidifies aforementioned prepreg of the present invention and obtains.In addition, veneer sheet of the present invention preferably, aforementioned prepreg of the present invention at least one the outside face be provided with conductor layer.

Aforementioned prepreg both can use 1, also can use 2 above laminations and the layered product that obtains.Arrange the veneer sheet that conductor layer forms (below be sometimes referred to as " metal-coated laminated board ".) situation under, can and carry out heating and pressurizing by laminated metal foil on above-mentioned prepreg and obtain.When using 1 prepreg, can descend two sides or single face overlapped metal paper tinsel thereon, when using the layered product that 2 above prepreg laminations are obtained, can be at outermost upper and lower surface or the single face overlapped metal paper tinsel of this layered product.Then, the overlapping body that overlapping prepreg and tinsel are formed carries out the heating and pressurizing moulding, can obtain metal-coated laminated board thus.

As the aforementioned metal paper tinsel, for example, can enumerate copper, copper series alloy, aluminium, aluminum series alloy, silver, silver and be alloy, gold, gold and be alloy, zinc, Zn based alloy, nickel, nickel system alloy, tin, tin is tinsels such as alloy, iron, iron-based alloy.In addition, also can form conductor layers such as aforesaid copper, copper series alloy by plating.

When making metal-coated laminated board, the temperature that heats is not particularly limited, be preferably 120～220 ℃, be preferably 150～200 ℃ especially.The pressure that pressurizes is not particularly limited, is preferably 0.5～5MPa, be preferably 1～3MPa especially.In addition, also can in high temperature groove etc., under 150～300 ℃ temperature, carry out after fixing as required.

In addition, as the another kind of method of making metal-coated laminated board of the present invention, can enumerate the manufacture method of metal-coated laminated board of the tinsel of use band resin layer shown in Figure 1.At first, prepare to be coated with in tinsel 11 with coating machine the tinsel 10 of the band resin layer of uniform resin layer 12.Then, in the both sides of fiber weaving cloth 20, the tinsel 10 of configuration band resin layer, 10 and make resin layer 12 be inboard (Fig. 1 (a)) heats in a vacuum under 60～130 ℃, the condition of pressurization 0.1～5MPa and makes its lamination impregnation.Thus, obtain (b) with prepreg 41(Fig. 1 of tinsel).Then, the prepreg 41 of being with tinsel is directly carried out the heating and pressurizing moulding, can obtain (c) of metal-coated laminated board 51(Fig. 1 thus).

And then, as the another kind of method of making metal-coated laminated board of the present invention, also can enumerate the manufacture method of metal-coated laminated board of the polymeric membrane thin slice of use band resin layer shown in Figure 2.At first, prepare to be coated with at polymeric membrane thin slice 31 with coating machine the polymeric membrane thin slice 30 of the band resin layer of uniform resin layer 32.Then, at the polymeric membrane thin slice 30 of the both sides of fiber weaving cloth 20 configuration band resin layer, 30 and make resin layer 32 be inboard (Fig. 2 (a)), in a vacuum, make its lamination impregnation under the condition of 60～130 ℃ of heating, pressurization 0.1～5MPa.Thus, can obtain (b) with prepreg 42(Fig. 2 of polymeric membrane thin slice).Then, the polymeric membrane thin slice 31 of the single face at least of the prepreg 42 of band polymeric membrane thin slice is peeled off back (in (c) of Fig. 2 for peeling off the two sides), (d) at the face configuration tinsel 11(Fig. 2 that has peeled off polymeric membrane thin slice 31), carry out the heating and pressurizing moulding.Thus, can obtain metal-coated laminated board 52(Fig. 2 (e)).And then, same with aforesaid prepreg when peeling off the polymeric membrane thin slice on two sides, also can lamination more than 2.When 2 above prepregs of lamination, outermost upper and lower surface or single face configuration tinsel or polymeric membrane thin slice at the prepreg of lamination carry out the heating and pressurizing moulding, can obtain metal-coated laminated board thus.Thickness and precision height, the thickness of the metal-coated laminated board that obtains by above-mentioned manufacture method are even, and the surface smoothing excellence.And owing to can obtain the little metal-coated laminated board of shaping and deformation, therefore, use the warpage of printed circuit board (PCB) that the metal-coated laminated board that obtains by this manufacture method makes and semiconductor device little, the warpage deviation is also little.And then can yield rate make printed circuit board (PCB) and semiconductor device well.

Condition as aforementioned heating and pressurizing moulding is not particularly limited temperature, is preferably 120～250 ℃, is preferably 150～220 ℃ especially.The aforementioned pressure that pressurizes is not particularly limited, is preferably 0.1～5MPa, be preferably 0.5～3MPa especially.And then also can in high temperature groove etc., under 150～300 ℃ temperature, carry out after fixing as required.

Metal-coated laminated board to Fig. 1～2 grades is not particularly limited, and for example, can use the device of the tinsel of making the band resin layer and the device of manufacturing metal-coated laminated board to make.

In the device of the tinsel of making aforementioned band resin layer, tinsel for example can be by using the tinsel of will rectangular sheet product making the roll form etc., also sending out supply thus continuously.By the feedway of resin, resinous varnish is supplied on the tinsel continuously with specified amount.Here, as resinous varnish, can use resin combination of the present invention dissolving, be dispersed in the solvent and the coating fluid that obtains.The glue spread of resinous varnish can be by comma roller and this comma roller the gap of support roll control.Be coated with the tinsel of resinous varnish of specified amount in the delivered inside of the hot-air drying device of lateral transfer type, in fact the dry organic solvent that contains in the resinous varnish etc. of removing can form the tinsel that curing reaction proceeds to the band resin layer in the way as required.The tinsel of band resin layer also can directly be reeled, but utilizes laminating roll, is being formed with the folded protective membrane that stresses of resin layer, the coiling lamination tinsel of band resin layer of this protective membrane, obtain the tinsel of the tape insulation resin layer of roll form.When using the manufacture method of Fig. 1～2 grades, compare with the manufacture method of in the past impregnation varnish, can control uniform amount of resin, thickness and precision excellence in the face, therefore, the warpage deviation of semiconductor device that is equipped with semiconductor element is little, and yield rate improves.

In addition, when obtaining metal-coated laminated board by above-mentioned manufacture method, need to consider that resin combination is to the impregnation of fiber weaving cloth.Packing material is by using the silica dioxide granule of median size 5～100nm, especially to the impregnation raising of fiber base material, therefore, when the heating and pressurizing moulding, the resin combination that can suppress in the metal-coated laminated board flows, and can suppress the inhomogeneous movement of molten resin, therefore, the striated inequality on metal-coated laminated board surface can be prevented, and uniform thickness can be formed.

3. printed circuit board (PCB)

Next, printed circuit board (PCB) of the present invention is described.

Printed circuit board (PCB) of the present invention is that above-mentioned prepreg and/or above-mentioned veneer sheet are formed for the internal layer circuit substrate.

Perhaps, printed circuit board (PCB) of the present invention is that the insulation layer that above-mentioned prepreg is used on the internal layer circuit is formed.

Need to prove that use at the internal layer circuit substrate under the situation of printed circuit board (PCB) of prepreg of the present invention or veneer sheet of the present invention, the layer that the prepreg in the internal layer circuit substrate solidify to form is insulation layer.

In the present invention, printed circuit board (PCB) is that the printed circuit board (PCB) that conductor layer such as tinsel forms the conductor circuit layer is set at insulation layer, can be single-clad board (laminate), two-face printing circuit card (two laminates), and multilayer printed circuit board (multi-ply wood) in any.Multilayer printed circuit board be utilize plated-through-hole method (plated through-hole), lamination method etc. overlapping printed circuit board (PCB) more than 3 layers, can and carry out the heating and pressurizing moulding by lapped insulation layer on the internal layer circuit substrate and obtain.As aforementioned internal layer circuit substrate, for example, can use the internal layer circuit substrate that obtains with veneer sheet of the present invention and/or prepreg of the present invention.As the internal layer circuit substrate that obtains with veneer sheet of the present invention, for example, can preferably use the internal layer circuit substrate that forms by following operation: do not having on the veneer sheet of the present invention of tinsel, utilize the conductor circuit of formation predetermined patterns such as semi-additive process, and this conductor circuit is partly carried out melanism handle; Form the conductor circuit of predetermined pattern in the tinsel of metal-coated laminated board of the present invention, and this conductor circuit is partly carried out melanism handle.

In addition, as the internal layer circuit substrate that obtains with prepreg of the present invention, can also use the internal layer circuit substrate that forms by following operation: electrical/electronic components such as mounting condenser, resistance, chip on the insulativity supporter that is formed by cured resin etc., lamination prepreg of the present invention thereon, and carry out heating and pressurizing and solidify, on the parts built-in substrate that obtains thus, utilize the conductor circuit of formation predetermined patterns such as semi-additive process, and this conductor circuit is partly carried out melanism handle.

And then, in the present invention, also can with use the veneer sheet of the invention described above and/or internal layer circuit substrate that prepreg of the present invention obtains or on the conductor circuit of known internal layer circuit substrate in the past further lamination prepreg of the present invention, carry out that heating and pressurizing is solidified and the circuit substrate that obtains is made as the internal layer circuit substrate.As the insulation layer on the aforementioned internal layer circuit, can use prepreg of the present invention.Need to prove, when using prepreg of the present invention as the insulation layer on the aforementioned internal layer circuit, the internal layer circuit substrate that aforementioned internal layer circuit substrate also can not be to use prepreg of the present invention or veneer sheet to obtain.

Below, as the typical example of printed circuit board (PCB) of the present invention, describe as internal layer circuit substrate, multilayer printed circuit board when using prepreg of the present invention as insulation layer using metal-coated laminated board of the present invention.

By forming the conductor circuit of predetermined pattern at the single face of aforementioned metal-coated laminated board or two sides, and this conductor circuit is partly carried out melanism handle, make the internal layer circuit substrate.Formation method to aforementioned conductor circuit is not particularly limited, and can utilize known method such as subraction, additive process, semi-additive process to carry out.In addition, on the internal layer circuit substrate, can utilize drilling machine processing, laser processing etc. to form through hole, by the electrical connection on realization two sides such as plating.Because aforementioned internal layer circuit substrate comprises metal-coated laminated board of the present invention, therefore, especially by laser processing, can form the through hole of the precision excellence of aperture, shape etc.Aforementioned laser can be used excimer laser, UV laser and carbon dioxide laser etc.

Then, overlapping aforementioned prepreg and carry out the heating and pressurizing moulding on this internal layer circuit substrate further is heating and curing, and forms insulation layer thus.Particularly, make aforementioned prepreg and aforementioned internal layer circuit substrate overlapping, carry out the heating under vacuum extrusion forming with vacuum pressure type laminating machine device etc., thereafter, with hot-air drying device etc. insulation layer is heating and curing.Here, the condition as carrying out the heating and pressurizing moulding is not particularly limited, and as an example wherein, can implement under the condition of 60～160 ℃ of temperature, pressure 0.2～3MPa.In addition, as making its condition that is heating and curing, be not particularly limited, as an example wherein, can under 140～240 ℃ of temperature, the condition of 30～120 minutes time, implement.

Then, to the insulation layer irradiating laser of lamination, form aperture portion (via).Aforementioned laser can be used the laser identical with employed laser during through hole forms.Because the aforementioned dielectric layer comprises prepreg of the present invention, therefore, by laser processing, can form the aperture portion of the precision excellence of aperture, shape etc.

For the gum residue after the laser radiation (stain) etc., the processing that preferably utilizes oxygenants such as permanganate, dichromate to wait to remove is namely carried out decontamination and is handled.If decontamination is handled insufficient and can not fully be guaranteed soil release characteristics, handle even then aperture portion is carried out metal deposition, also can worry because of the former of stain thereby can not fully guarantee the top conductor circuit layer and the energising of lower floor's conductor circuit layer.In addition, handle by carrying out decontamination, can therefore, handle when surface of insulating layer forms conductor layer the adaptation excellence of surface of insulating layer and conductor layer by Metal plating simultaneously with the surface coarsening of level and smooth insulation layer.Need to prove, also can before forming aperture portion by laser radiation, form conductor layer at surface of insulating layer.

Then, carry out the Metal plating processing in aperture portion and surface of insulating layer, form conductor layer.At the aforementioned dielectric laminar surface, further utilize aforesaid known method to wait to form conductor circuit.Need to prove, handle to form conductor layer by carrying out Metal plating in aperture portion, can seek the conducting of top conductor circuit layer and lower floor's conductor circuit layer.

Further the lamination insulation layer with aforementioned same formation conductor circuit, in multilayer printed circuit board, after forming conductor circuit, forms soldering-resistance layer at outermost layer.Formation method to soldering-resistance layer is not particularly limited, and for example, can form by the following method: the solder resist of overlapping (lamination) dry-film type, the method for utilizing exposure and developing and form; Or to the matter utilization exposure of having printed aqueous resist and the method for developing and forming.When the multilayer printed circuit board that will obtain is used for semiconductor device, the connection electrode part for being installed, semiconductor element is set.Can suitably be covered to connect with the metal tunicle of gold-plated, nickel plating and plating scolder etc. and use electrode part.

4. semiconductor device

Next, semiconductor device of the present invention is described.

On the aforementioned printed circuit board (PCB) that obtains, the semiconductor element with solder projection is installed, by solder projection, realization is connected with aforementioned printed circuit board (PCB).Then, between printed circuit board (PCB) and semiconductor element, fill sealing resin, form semiconductor device.The preferred solder projection is made of the alloy that comprises tin, lead, silver, copper, bismuth etc.

Method of attachment for semiconductor element and printed circuit board (PCB), after using flip-chip bonder etc. to carry out the position alignment of connection with the solder projection of electrode part and semiconductor element on the printed circuit board (PCB), with IR reflow device, hot plate, other heating unit solder projection is heated to more than the fusing point, printed circuit board (PCB) and solder projection fusion are engaged, connect thus.Need to prove that good in order to make connection reliability, the connection on printed circuit board (PCB) in advance forms the layer of the lower metal of fusing point such as soldering paste with electrode part.Before this engages operation, also can be coated with solder flux with the top layer of electrode part by the connection on solder projection and/or printed circuit board (PCB) and improve connection reliability.

Embodiment

Below, explain the present invention based on embodiment and comparative example, but the present invention is not limited thereto.

The fiber weaving cloth that uses in embodiment and the comparative example is woven the weaving cotton cloth of glass fibre plain weave with JIS R3413 regulation, is the following glass fibre A～L that weaves cotton cloth.

A: use the glass fiber yarn of T glass, E1101/0, the filling density radical of every 25mm of organizine and tram is 44.5,42, and the thickness of opening after the fine flat processing is 130 μ m, and mass area ratio is 155g/m ²

B: use the glass fiber yarn of E glass, DE1501/0, the filling density radical of every 25mm of organizine and tram is 46.5,44, and the thickness of opening after the fine flat processing is 95 μ m, and mass area ratio is 121g/m ²

C: use the glass fiber yarn of T glass, E2251/0, the filling density radical of every 25mm of organizine and tram is 65,64, and the thickness of opening after the fine flat processing is 95 μ m, and mass area ratio is 121g/m ²

D: use the glass fiber yarn of D glass, E2251/0, the filling density radical of every 25mm of organizine and tram is 65,64, and the thickness of opening after the fine flat processing is 95 μ m, and mass area ratio is 121g/m ²

E: use the glass fiber yarn of T glass, D4501/0, the filling density radical of every 25mm of organizine and tram is 59,59, and the thickness of opening after the fine flat processing is 46 μ m, and mass area ratio is 53g/m ²

F: use the glass fiber yarn of T glass, BC15001/0, the filling density radical of every 25mm of organizine and tram is 90,90, and the thickness of opening after the fine flat processing is 20 μ m, and mass area ratio is 24g/m ²

G: use the glass fiber yarn of T glass, C12001/0, the filling density radical of every 25mm of organizine and tram is 74,77, and the thickness of opening after the fine flat processing is 25 μ m, and mass area ratio is 31g/m ²

H: use the glass fiber yarn of T glass, E1101/0, the filling density radical of every 25mm of organizine and tram is 44.5,42, and the thickness of opening after the fine flat processing is 115 μ m, and mass area ratio is 155g/m ²

I: use the glass fiber yarn of T glass, E1101/0, the filling density radical of every 25mm of organizine and tram is 43,40, and the thickness of opening after the fine flat processing is 145 μ m, and mass area ratio is 150g/m ²

J: use the glass fiber yarn of T glass, E2251/0, the filling density radical of every 25mm of organizine and tram is 59,54, and the thickness of opening after the fine flat processing is 97 μ m, and mass area ratio is 100g/m ²

K: use the glass fiber yarn of T glass, D4501/0, the filling density radical of every 25mm of organizine and tram is 60,47, and the thickness of opening after the fine flat processing is 50 μ m, and mass area ratio is 48g/m ²

L: use the glass fiber yarn of T glass, C12001/0, the filling density radical of every 25mm of organizine and tram is 68,72, and the thickness of opening after the fine flat processing is 27 μ m, and mass area ratio is 25g/m ²

The varnish that uses in embodiment and the comparative example is to make by following varnish Production Example 1～7 to contain the varnish that blended resin composition is made in the solvent.

(varnish Production Example 1)

Make and contain blending epoxy (HP-5000 that DIC company makes) 6 weight parts in the methyl ethyl ketone, phenol phenolic varnish type cyanate ester resin (PT30 that LONZA company makes) 12 weight parts, phenol is solidifying agent (bright and MEH-7851-4L that the company that changes into makes) 6 weight parts, silica dioxide granule (the NSS-5N that Tokuyama Corporation makes, median size 70nm) 10 weight parts, spherical silicon dioxide (Admatechs Co., Ltd. the SO-31R of Zhi Zaoing, median size 1.0 μ m) 65 weight parts, epoxy silane (KBM-403E that chemical industrial company of SHIN-ETSU HANTOTAI makes) 1.0 weight parts, stir with high-speed stirring apparatus, obtain composition epoxy resin is counted 70 weight % with the solids component benchmark varnish.Need to prove that when containing packing material integral body contained in the resin combination of mixing in the varnish and be made as 100 quality %, contained silica dioxide granule is that 13 quality %, spherical silicon dioxide are 87 quality % in this packing material.

(varnish Production Example 2)

Make and contain mixing in the dimethyl formamide as biphenyl aralkyl-type epoxy resin (NC-3000 that Japanese chemical drug corporate system is made) 9 weight parts of Resins, epoxy, bimaleimide resin (KI Chemical Industry Co., Ltd. the 17 weight parts BMI-70 of Zhi Zaoing), 4,4 '-diaminodiphenyl-methane, 3 weight parts, silica dioxide granule (the NSS-5N that Tokuyama Corporation makes, median size 70nm) 10 weight parts, (BMB that lime company makes is closed in the river to boehmite, median size 0.5 μ m) 60 weight parts, epoxy silane (KBM-403E that chemical industrial company of SHIN-ETSU HANTOTAI makes) 1.0 weight parts.Then, stir with high-speed stirring apparatus, regulate so that nonvolatile component is the mode of 70 weight %, the preparation resinous varnish.Need to prove that when containing packing material integral body contained in the resin combination of mixing in the varnish and be made as 100 quality %, contained silica dioxide granule is that 14 quality %, boehmite are 86 quality % in this packing material.

(varnish Production Example 3)

Make to contain in the methyl ethyl ketone and mix biphenyl aralkyl-type epoxy resin (NC-3000FH that Japanese chemical drug corporate system is made) 20 weight parts, naphthalene type Resins, epoxy (HP4032D that DIC Corporation makes) 5 weight parts, cyanate ester resin (the derivative of the SN485 that Toto Kasei KK makes, naphthol type) 17 weight parts, bimaleimide resin (KI Chemical Industry Co., Ltd. the 7.5 weight parts BMI-70 of Zhi Zaoing), silica dioxide granule (the NSS-5N that Tokuyama Corporation makes, median size 70nm) 7 weight parts, spherical silicon dioxide (Admatechs Co., the SO-31R that Ltd. makes, median size 1.0 μ m) 35.5 weight parts, organic silicon granule (the KMP600 that Shin-Etsu Chemial Co., Ltd makes, median size 5 μ m) 7.5 weight parts, zinc octoate 0.01 weight part, epoxy silane (KBM-403E that chemical industrial company of SHIN-ETSU HANTOTAI makes) 0.5 weight part.Then, stir with high-speed stirring apparatus, regulate so that nonvolatile component is the mode of 70 weight %, the preparation resinous varnish.Need to prove, when containing packing material integral body contained in the resin combination of mixing in the varnish and be made as 100 quality %, contained silica dioxide granule is that 14 quality %, spherical silicon dioxide are that 71 quality %, organic silicon granule are 15 quality % in this packing material.

(varnish Production Example 4)

Make and contain mixing in the dimethyl formamide as biphenyl aralkyl-type epoxy resin (NC-3000 that Japanese chemical drug corporate system is made) 18.5 weight parts of Resins, epoxy, bimaleimide resin (KI Chemical Industry Co., Ltd. the 34.9 weight parts BMI-70 of Zhi Zaoing), 4,4 '-diaminodiphenyl-methane, 6.1 weight parts, silica dioxide granule (the NSS-5N that Tokuyama Corporation makes, median size 70nm) 5 weight parts, (BMB that lime company makes is closed in the river to boehmite, median size 0.5 μ m) 35 weight parts, epoxy silane (KBM-403E that chemical industrial company of SHIN-ETSU HANTOTAI makes) 0.5 weight part.Then, stir with high-speed stirring apparatus, regulate so that nonvolatile component is the mode of 70 weight %, the preparation resinous varnish.Need to prove that when containing packing material integral body contained in the resin combination of mixing in the varnish and be made as 100 quality %, contained silica dioxide granule is that 12.5 quality %, boehmite are 87.5 quality % in this packing material.

(varnish Production Example 5)

Make and contain mixing in the dimethyl formamide as biphenyl aralkyl-type epoxy resin (NC-3000 that Japanese chemical drug corporate system is made) 2.80 weight parts of Resins, epoxy, bimaleimide resin (KI Chemical Industry Co., Ltd. the 5.27 weight parts BMI-70 of Zhi Zaoing), 4,4 '-diaminodiphenyl-methane, 0.93 weight part, silica dioxide granule (the NSS-5N that Tokuyama Corporation makes, median size 70nm) 10 weight parts, (BMB that lime company makes is closed in the river to boehmite, median size 0.5 μ m) 80 weight parts, epoxy silane (KBM-403E that chemical industrial company of SHIN-ETSU HANTOTAI makes) 1.0 weight parts.Then, stir with high-speed stirring apparatus, regulate so that nonvolatile component is the mode of 70 weight %, the preparation resinous varnish.Need to prove that when containing packing material integral body contained in the resin combination of mixing in the varnish and be made as 100 quality %, contained silica dioxide granule is that 11 quality %, boehmite are 89 quality % in this packing material.

(varnish Production Example 6)

Make and contain blending epoxy (HP-5000 that DIC Corporation makes) 6 weight parts in the methyl ethyl ketone, phenol phenolic varnish type cyanate ester resin (PT30 that LONZA company makes) 12 weight parts, phenol is solidifying agent (bright and MEH-7851-4L that the company that changes into makes) 6 weight parts, silica dioxide granule (the NSS-5N that Tokuyama Corporation makes, median size 70nm) 30 weight parts, spherical silicon dioxide (Admatechs Co., Ltd. the SO-31R of Zhi Zaoing, median size 1.0 μ m) 45 weight parts, epoxy silane (KBM-403E that chemical industrial company of SHIN-ETSU HANTOTAI makes) 1.0 weight parts, stir with high-speed stirring apparatus, obtain composition epoxy resin is counted 70 weight % with the solids component benchmark varnish.Need to prove that when containing packing material integral body contained in the resin combination of mixing in the varnish and be made as 100 quality %, contained silica dioxide granule is that 40 quality %, spherical silicon dioxide are 60 quality % in this packing material.

(varnish Production Example 7)

Make and contain blending epoxy (NC-3000 that Japanese chemical drug corporate system is made) 6 weight parts in the methyl ethyl ketone, phenol phenolic varnish type cyanate ester resin (PT30 that LONZA company makes) 12 weight parts, phenol is solidifying agent (bright and MEH-7851-4L that the company that changes into makes) 6 weight parts, spherical silicon dioxide (Admatechs Co., Ltd. the SO-31R of Zhi Zaoing, median size 1.0 μ m) 75 weight parts, epoxy silane (KBM-403E that chemical industrial company of SHIN-ETSU HANTOTAI makes) 1.0 weight parts, stir with high-speed stirring apparatus, obtain composition epoxy resin is counted 70 weight % with the solids component benchmark varnish.Need to prove that when containing packing material integral body contained in the resin combination of mixing in the varnish and be made as 100 quality %, contained silica dioxide granule is that 0 quality %, spherical silicon dioxide are 100 quality % in this packing material.

The composition of employed resin combination in the varnish Production Example 1～7 is shown in table 1.Need to prove that the compounding amount of each composition is represented with weight part.

[table 1]

Use above-mentioned glass fibre to weave cotton cloth and above-mentioned varnish, make prepreg, metal-coated laminated board, printed circuit board (PCB) (internal layer circuit substrate), multilayer printed circuit board and semiconductor device.

＜embodiment 1＞

(1) making of prepreg

To be coated on by the varnish curtain coating that Production Example 1 obtains on the polyethylene terephthalate base material (hereinafter referred to as the PET base material) of thickness 38 μ m, under 140 ℃ of temperature, the condition of 10 minutes time, make the solvent evaporates drying, so that the thickness of resin layer is 30 μ m.With the base material of aforementioned band resin layer be configured in glass woven fabric A the two sides so that resin layer contact with glass woven fabric, under pressure 0.5MPa, 140 ℃, 1 minute condition of temperature, utilize vacuum pressure type laminating machine (MLVP-500 that Co., Ltd. Mingji Koito makes) to carry out heating and pressurizing, make the resin combination impregnation.Thus, must arrive the prepreg (resin layer (single face): 10 μ m, fiber weaving cloth layer: 130 μ m) that the two sides has the thickness 150 μ m of PET base material.

(2) making of metal-coated laminated board

The Copper Foil of 2 μ m of the two sides of aforementioned prepreg overlap zone carrier (mining company of Mitsui Metal Co., Ltd. makes, Micro Thin MT18Ex-2), the heating and pressurizing moulding is 2 hours under the condition of 220 ℃ of pressure 3MPa, temperature.Thus, obtain the metal-coated laminated board that two sides that prepreg solidifies the insulation layer of the thickness 150 μ m form has Copper Foil.

(3) the multilayer printed circuit board insulation layer making of prepreg

Make glass woven fabric (E glass woven fabric, E02Z, mass area ratio 17.5g/m that thickness 16 μ m, UNITIKA LTD. make ²) varnish that obtains of the aforementioned Production Example 1 of impregnation, with dry 2 minutes of 180 ℃ process furnace, obtain resin combination in the prepreg is counted about 78 weight % with the solids component benchmark prepreg (thickness 40 μ m).Need to prove that the volume density of aforementioned glass woven fabric is 1.09g/cm ³, Gas permeability is 41cc/cm ²/ sec, flat ratio (thickness: width) be 1:16.In addition, the glass fibre that aforementioned glass woven fabric is 93GPa by making Young's modulus when tabular, to make tensile strength when tabular be 48GPa, the tensile strength of the length direction when making fiber weaving cloth is 90N/25mm forms.

(4) manufacturing of printed circuit board (PCB) (internal layer circuit substrate)

Peel off foils from aforementioned metal-coated laminated board, with carbon dioxide laser (Mitsubishi Electric Corporation's manufacturing, ML605GTX3-5100U2), in the aperture Under the condition of the about 120 μ m of beam diameter, energy 7～9mJ, irradiation number (number of shots) 6, form

Communicating pores.Then, this metal-coated laminated board was flooded 5 minutes in 70 ℃ swelling solution (Atotech Japan K.K. manufacturing, Swelling Dip Securiganth P), and then in 80 ℃ potassium permanganate solution (Atotech Japan K.K. makes, Concentrate Compact CP), flooded 10 minutes, neutralize then and carry out roughening treatment.Then, realize the conducting between Copper Foil up and down by electroless plating (going up the manufacturing of village industrial, Thru-cup PEA process).

Then, on the surface of this chemical plating, utilize the hot-roll lamination machine to paste the UV-radiation-sensitive dry film of thickness 25 μ m (manufacturing of company of Asahi Chemical Industry, San Fort UFG-255).Then, aim at the position of describing the glass mask that minimum feature/spacing is the pattern of 20/20 μ m (TOPIK CO., LTD makes).Then, use this glass mask, after exposing with exposure apparatus (the little wild EV-0800 that device company makes that surveys), develop with aqueous sodium carbonate, form Etching mask.Then, be the power supply layer electrode with the chemical plating, with 3A/dm ²Carried out copper electroplating (81-HL that wild drugmaker difficult to understand makes) 25 minutes.Thus, form the pattern of the copper wiring of the about 20 μ m of thickness.Then, use stripping machine, utilize monoethanolamine solution (MITSUBISHI GAS CHEMCAL COMPANY, the R-100 that INC. makes), peel off aforementioned Etching mask.Then, utilize fast-etching (SAC-702M that weak former electric product company makes and the pure water solution of SAC-701R35) to remove as useless Copper Foil and chemical plating beyond the pattern form of giving the electricity layer, form the pattern of L/S=20/20 μ m.

Then, carry out the roughening treatment (MEC CO., LTD. manufacturing, MEC etch BOND CZ-8100) of conductor circuit.Handle by carrying out spraying under the condition of pressing 0.15MP in 35 ℃ of liquid temperature, injection, the asperitiesization that implement about roughness 3 μ m on the copper surface is carried out this roughening treatment.Then, carry out the surface treatment (MEC CO., LTD. manufacturing, MEC etch BOND CL-8300) of conductor circuit.In this surface treatment, under 25 ℃ of liquid temperature, 20 seconds condition of dipping time, flood, antirust processing is carried out on the copper surface.Make printed circuit board (PCB) (internal layer circuit substrate) thus.

(5) manufacturing of multilayer printed circuit board

Then, be the internal layer circuit substrate with the aforementioned printed circuit board (PCB) that obtains, at the Copper Foil (Mitsui Metal Co., Ltd. mining company manufacturing, Micro Thin MT18Ex-2) of the aforementioned multilayer printed circuit board insulation layer of its two sides overlay configuration with 2 μ m of prepreg and band carrier, carry out lamination with the lamination vacuum lamination apparatus, under 200 ℃ of temperature, pressure 3MPa, the condition of 120 minutes time, be heating and curing, obtain the laminated multi-layer body.Then, similarly carry out outer circuit with the manufacture method of aforementioned (4) printed circuit board (PCB) (internal layer circuit substrate) and form, last, form solder resist (TAIYO INK MFG at circuit surface, CO., LTD. manufacturing, PSR4000/AUS308), obtain multilayer printed circuit board.

For aforementioned multilayer printed circuit board, the connection that is equivalent to the solder projection arrangement of semiconductor element is implemented ENEPIG with electrode part handle.Give the operation of palladium catalyst, the processing of [6] electroless nickel plating, the processing of [7] electroless plating palladium, the processing of [8] electroless gold plating by [1] clean, [2] soft etch processes, [3] cleanup acid treatment, [4] pre-preg, [5] and carry out the ENEPIG processing.

(6) manufacturing of semiconductor device

Semiconductor device can obtain by the following method, namely, on the printed circuit board (PCB) of having implemented the ENEPIG processing, utilize the flip-chip bonder device, carry the semiconductor element (TEG chip, size 10mm * 10mm, thickness 0.1mm) with solder projection by adding thermo-compressed, then, with IR reflow stove the solder projection fusion is engaged, then, fill aqueous sealing resin (SUMITOMO BAKELITE CO., LTD. make, CRP-4152S), and aqueous sealing resin is solidified.Need to prove, aqueous sealing resin is solidified.Need to prove the solder projection that the eutectic that the solder projection use of aforesaid semiconductor element is made up of Sn/Pb forms.At last, turn to the size of 14mm * 14mm with the router monolithic, obtain semiconductor device.

＜embodiment 2～3, and comparative example 1～6＞

The varnish that fiber weaving cloth shown in the use table 4 and the Production Example by varnish obtain, the two sides that obtains the insulation layer of prepreg, thickness 150 μ m similarly to Example 1 has the metal-coated laminated board of Copper Foil, printed circuit board (PCB) (internal layer circuit substrate), multilayer printed circuit board and semiconductor device.

＜embodiment 4～6, and comparative example 7＞

When making prepreg, make the band resin layer base material resin layer thickness such as table 5 record, in addition, the varnish that fiber weaving cloth shown in the use table 5 and the Production Example by varnish obtain, operation similarly to Example 1, the two sides that obtains the insulation layer of prepreg, thickness 100 μ m has the metal-coated laminated board of Copper Foil, printed circuit board (PCB) (internal layer circuit substrate), multilayer printed circuit board and semiconductor device.

Need to prove, for the communicating pores formation of printed circuit board (PCB), use carbon dioxide laser (Mitsubishi Electric Corporation's manufacturing, ML605GTX3-5100U2), in the aperture The condition of the about 110 μ m of beam diameter, energy 7～9mJ, irradiation several 6 gets off to carry out, and forms the communicating pores of diameter 100 μ m.

＜embodiment 7,8 and comparative example 8＞

For embodiment 7 and comparative example 8, when making prepreg, make the band resin layer base material resin layer thickness such as table 6 record, in addition, the varnish that fiber weaving cloth shown in the use table 6 and the Production Example by varnish obtain, the two sides that obtains the insulation layer of prepreg, thickness 60 μ m similarly to Example 1 has the metal-coated laminated board of Copper Foil, printed circuit board (PCB) (internal layer circuit substrate), multilayer printed circuit board and semiconductor device.

For embodiment 8, when making prepreg, make the band resin layer base material resin layer thickness such as table 6 record, in addition, the varnish that fiber weaving cloth shown in the use table 6 and the Production Example by varnish obtain obtains prepreg (integral thickness 30 μ m) similarly to Example 1, the prepreg lamination of 2 these 30 μ m and the two sides of solidifying the insulation layer of the thickness 60 μ m that form is had metal-coated laminated board, internal layer circuit substrate, multilayer printed circuit board and the semiconductor device of Copper Foil.

Need to prove, for the communicating pores formation of printed circuit board (PCB), use carbon dioxide laser (Mitsubishi Electric Corporation's manufacturing, ML605GTX3-5100U2), in the aperture

The condition of the about 110 μ m of beam diameter, energy 6～8mJ, irradiation several 6 gets off to carry out, and forms the communicating pores of diameter 100 μ m.

＜embodiment 9, and comparative example 9＞

When making prepreg, make the band resin layer base material resin layer thickness such as table 7 record, in addition, the varnish that fiber weaving cloth shown in the use table 7 and the Production Example by varnish obtain, the two sides that obtains the insulation layer of prepreg, thickness 40 μ m similarly to Example 1 has the metal-coated laminated board of Copper Foil, printed circuit board (PCB) (internal layer circuit substrate), multilayer printed circuit board and semiconductor device.

Prepreg, metal-coated laminated board, printed circuit board (PCB) (internal layer circuit substrate) and semiconductor device for embodiment and comparative example obtain carry out following evaluation.Assessment item is illustrated with content.The evaluation result that obtains is shown in table 4～7.

Need to prove, because the measurement result of PKG warpage described later depends on the thickness of the insulation layer of metal-coated laminated board, therefore, be that the embodiment of 150 μ m and the evaluation result of comparative example are shown in table 4 with the thickness of the insulation layer of metal-coated laminated board, be that the embodiment of 100 μ m and the evaluation result of comparative example are shown in table 5 with the thickness of the insulation layer of metal-coated laminated board, being that the embodiment of 60 μ m and the evaluation result of comparative example are shown in table 6 with the thickness of the insulation layer of metal-coated laminated board, is that the embodiment of 40 μ m and the evaluation result of comparative example are shown in table 7 with the thickness of the insulation layer of metal-coated laminated board.

In addition, in table 4～7, packing material amount when the expression of packing material amount (quality %) in the resin combination is made as 100 quality % with resin combination integral body, each components in proportions when composition of packing material (quality) % represents that packing material integral body is made as 100 quality %.

＜evaluation method＞

(1) impregnation of resin combination

The prepreg that previous embodiment and comparative example are obtained utilizes the SEM(scanning electron microscope after solidifying 1 hour under 170 ℃ the temperature) observe section (for the scope of the 300mm of section portion of width), estimating fibrous inside has tight.On image, the point of the white particulate of fibre profile is regarded as the space.

Each symbol is as described below.

Zero: resin combination is impregnation well all, and fibrous inside does not have the situation in space

*: fibrous inside has the situation in space

(2) formability

Behind the whole facet etch of Copper Foil of the metal-coated laminated board that previous embodiment and comparative example are obtained, utilize the SEM(scanning electron microscope) scope of observing 500mm * 500mm, there is tight on the surface of estimating insulation layer (being positioned at the resin layer on the surface of fiber weaving cloth layer).On image, the point of white particulate be regarded as the space.

Each symbol is as described below.

Zero: do not have the space

*: the space is arranged

(3) moisture absorption solder heat resistance

The metal-coated laminated board that use obtains previous embodiment and comparative example cuts into the square and sample that obtains of 50mm * 50mm, based on JIS C-6481, half whole Copper Foil in addition of the single face of aforementioned sample are removed in etching, with pressure cooker testing machine (ESPEC CORP manufacturing) after handling 2 hours under 121 ℃, 2 the atmospheric conditions, dipping is 30 seconds in 260 ℃ solder bath, and the visual observations appearance change has no abnormal.

Each symbol is as described below.

Zero: do not have unusual situation

*: swelling is arranged, peel off

(4) coefficient of linear thermal expansion (CTE) (ppm/K)

For coefficient of linear thermal expansion (CTE), use the TMA(thermo-mechanical analysis) device (manufacturing of TA Instruments company, Q400), make the test film of 4mm * 20mm, under 30～300 ℃ of temperature ranges, 10 ℃/minute, the condition of load 5g, measure 50～100 ℃ CTE of the 2nd circulation.Need to prove that sample uses the sample after the Copper Foil etching of the metal-coated laminated board that each embodiment and comparative example are obtained is removed.

(5) laser processing

The printed circuit board (PCB) (internal layer circuit substrate) that uses previous embodiment and comparative example to obtain is measured the intersection overhang (cross protrusions) of the communicating pores after carbon dioxide laser is processed, the circularity in aperture.Mensuration for intersection overhang and circularity, use colored 3D laser microscope (KEYENCE CORPORATION makes, installs name VK-9710), directly over the hole of laser light incident side, observe, mensuration is from the outstanding length of wall surface of the hole, intersect the mensuration of overhang thus, directly over the hole of laser light incident side, observe, measure major diameter and the minor axis of hole top diameter, calculate major diameter ÷ minor axis, carry out the mensuration of circularity thus.Need to prove, the printed circuit board (PCB) (internal layer circuit substrate) that sample uses previous embodiment and comparative example to obtain, under the carbon dioxide laser condition shown in the following table 2, from directly over observe diameter 100 μ m the substrate of hole processing after just having finished, get the mean value of 10 communicating poress.

[table 2]

Each symbol is as described below.

Zero: the overhang of intersecting is 10 μ m with interior and circularity is situation more than 0.85

△: the overhang of intersecting is more than the 10 μ m or circularity is lower than 0.85 situation

*: the overhang of intersecting is more than the 10 μ m and circularity is lower than 0.85 situation

(6) insulating reliability of communicating pores

The printed circuit board (PCB) (internal layer circuit substrate) that uses previous embodiment and comparative example to obtain is estimated the insulating reliability between communicating pores.

Use 0.1mm part between the through-holes of printed circuit boards wall, estimate by METHOD FOR CONTINUOUS DETERMINATION under the condition that applies voltage 10V, 130 ℃ of temperature, humidity 85%.Need to prove, use height accelerated life test device (EHS-211(M that ESPEC CORP makes), AMI ion migration test macro) measure, becoming at insulating resistance value is lower than 10 ⁸The moment of Ω finishes.

Each symbol is as described below.

◎: above 200 hours.

Zero: be more than 100 hours and be below 200 hours.

△: be more than 50 hours and be lower than 100 hours.

*: be lower than 50 hours.

(7) PKG warpage

(14mm * 14mm) is arranged on variable temperatures 3-d laser measurement instrument (Hitachi Technologies and Services to the semiconductor device that embodiment and comparative example are obtained, Ltd. make, model LS220-MT100MT50) the sample chamber in and make the semiconductor element face for time, use the said determination machine, measure the warpage of semiconductor device under room temperature (25 ℃) and 260 ℃.For the mensuration of warpage, measure the displacement of short transverse, the maximum value of displacement difference is made as amount of warpage.Need to prove that measurement range is size 13mm * 13mm.

Each symbol is as described in the following table 3.Need to prove that the mensuration of PKG warpage depends on the thickness of the insulation layer of metal-coated laminated board, therefore, to the thickness of the insulation layer of each metal-coated laminated board, as shown in table 3ly judge.

[table 3]

[table 4]

[table 5]

[table 6]

[table 7]

As the typical example of the observations of the impregnation of aforementioned (1) resin combination, the photo of the sectional view of the prepreg that embodiment 1 is obtained is shown in Fig. 3, and the photo of the sectional view of the prepreg that comparative example 4 is obtained is shown in Fig. 4.

As shown in Figure 4, because the impregnation of the resin combination of comparative example 4 is poor, therefore, can be observed the space in the fiber weaving cloth.On the other hand, as shown in Figure 3, because the impregnation of the resin combination of embodiment 1 is good, therefore, there is not the space in the fiber weaving cloth.

In embodiment 1, can think to enter in the precursor by the silica dioxide granule that makes nano-scale the impregnation raising of resin combination.With respect to this, in comparative example 4, owing to do not contain the silica dioxide granule of nano-scale, therefore, can not seek the raising of the impregnation of resin combination.

Typical example as the formability observations of aforementioned (2) metal-coated laminated board, the whole facet etch of the Copper Foil of the metal-coated laminated board that embodiment 1 is obtained the photo on surface be shown in Fig. 5, the whole facet etch of the Copper Foil of the metal-coated laminated board that comparative example 6 is obtained the photo on surface be shown in Fig. 6, and then the SEM photo of the enlarged view of observed space among Fig. 6 (point of the white particulate on the image) is shown in Fig. 7, the SEM photo of the enlarged view of the section in observed space among Fig. 7 is shown in Fig. 8.By Fig. 6,7,8 as can be known, in comparative example 6, with the whole facet etch of metal-coated laminated board the surface can be observed the space.On the other hand, as shown in Figure 5, in embodiment 1, whole facet etch the surface do not have the space.

Fig. 9～12nd, the SEM photo of the sectional view of a part of precursor of the fiber weaving cloth of the prepreg that expression formation embodiment 1 obtains.Fig. 9 represents the section parallel with the bearing of trend of precursor.Figure 10～12 expressions the section vertical with the bearing of trend of precursor.

Shown in Fig. 9～12, as can be known, in the prepreg that embodiment 1 obtains, there is silica dioxide granule in the precursor.

In the embodiment 1～9 shown in table 4～7, can obtain good prepreg impregnation.In addition, for other various characteristics, also all can obtain good result as can be known.Think that this is owing to the making of carrying out prepreg under the condition that enters at silica dioxide granule in the precursor that constitutes fiber weaving cloth.

Need to prove, enter the factor in the precursor as the control silica dioxide granule, for example can enumerate: the median size of silica dioxide granule, the content of the silica dioxide granule in the packing material, the content of the packing material in the resin combination, the multiple factors such as volume density of fiber weaving cloth.

By table 4～7 as can be known, in embodiment 1～9, the resin combination that contains in the varnish contains the packing material of 50～85 quality % that account for this resin combination integral body, the silica dioxide granule that contains median size 5～100nm of 1～20 quality % in this packing material, and the volume density of fiber weaving cloth is 1.05～1.30g/cm ³At this moment, the evaluation result excellence of above-mentioned all assessment item.Namely, for the prepreg of present embodiment, resin combination is to the impregnation excellence of fiber weaving cloth as can be known, be low heat expansion property, laser processing excellence during as the insulation layer of printed circuit board (PCB), the aperture in the hole that forms by laser and the precision of shape are good, and can form and can suppress the outstanding hole of fiber.And then, for the prepreg of present embodiment, we can say because moisture absorption solder heat resistance excellence, be high heat resistance therefore because the formability excellence, so also excellence of surface smoothing, so with the adaptation excellence of conductor layer.In addition, because the PKG warpage of semiconductor device of the present invention is little, therefore, the prepreg of present embodiment is low heat expansion property as can be known, and is high rigidity.

Also can obtain good prepreg impregnation in the comparative example 1 and 6.

Yet in comparative example 1, CTE and package warpage can not obtain good result.Think this be owing to the content of packing material low thus only the resinous principle of resin combination enter and suppressed silica dioxide granule in the precursor and enter in the precursor.Thus, think, can not highly-filled packing material, the CTE of prepreg raises, and has produced the package warpage.

In addition, in comparative example 6, can not obtain good result.Think that this is owing to can not make the resin combination impregnation of q.s because volume density is low, suppressed also therefore that contained silica dioxide granule enters in the precursor in the resin combination.In addition, owing to become thicker fiber base material because the volume density of fiber weaving cloth is little, therefore, the thickness attenuation of the resin layer on the top layer of prepreg.Therefore, think that formability, moisture absorption solder heat resistance are poor, though CTE has well produced the PKG warpage.

In comparative example 4 and 7～9, for the impregnation of prepreg, can not obtain good result.In comparative example 4 and 7～9, do not contain the silica dioxide granule of nano-scale in the resin combination of formation prepreg.Therefore, think that silica dioxide granule does not enter in the precursor, can not seek the raising of the impregnation of resin combination.Thus, other various characteristics such as CTE and package warpage can not obtain good result.

In comparative example 7, because the volume density of fiber weaving cloth is little so laser processing is poor, because of the impregnation difference so the insulating reliability of communicating pores is poor.In addition, so the thickness attenuation of the resin layer of prepreg, formability, moisture absorption solder heat resistance are poor, have produced the PKG warpage because having used thicker fiber weaving cloth.

In comparative example 8 and 9, because the thickness of insulating layer of metal-coated laminated board is thinner, therefore, the insulating reliability excellence of formability, moisture absorption solder heat resistance, communicating pores.Yet because the volume density of fiber weaving cloth is little, so laser processing can not obtain good result.

Comparative example 2,3, and 5 in, for the impregnation of prepreg, can not obtain good result.In addition, for other various characteristics, can not obtain good result.In comparative example 2, think that the result has suppressed silica dioxide granule and entered in the precursor because therefore the too high levels of packing material, can not obtain the flowability of the silica dioxide granule in the resin combination.In comparative example 3, think that because the content height of the silica dioxide granule of nano-scale, therefore, cohesion has taken place the silica dioxide granule of nano-scale, the result has suppressed silica dioxide granule and has entered in the precursor.In comparative example 5, think because the volume density of fiber weaving cloth is big, therefore, suppressed silica dioxide granule and entered in the precursor.

In comparative example 5, because the volume density of fiber weaving cloth is excessive, therefore, the impregnation of resin combination is poor, and the moisture absorption solder heat resistance is poor, the insulating reliability inequality of laser processing and communicating pores.

In comparative example 6, because the volume density of fiber weaving cloth is little, therefore, the insulating reliability of laser processing and communicating pores is poor.And then, owing to become thicker fiber base material because the volume density of fiber weaving cloth is little, and therefore, the thickness attenuation of the resin layer on the top layer of prepreg.Therefore, formability, moisture absorption solder heat resistance are poor, have produced the PKG warpage.

The application has required based on the special right of priority of being willing to 2011-012166 number of the Japanese publication of submission on January 24th, 2011 its content all to be introduced among the application.

Claims

1. prepreg, it is the prepreg that the fiber weaving cloth impregnation resin combination that is made of precursor is formed, and has silica dioxide granule in the described precursor.

2. prepreg according to claim 1, wherein, in described precursor, there is not the space with the length more than the 50 μ m in the direction of extending at the fiber that constitutes described precursor.

3. prepreg according to claim 1 and 2, wherein, the diameter in the described precursor is that the number density in the above space of 50 μ m is 50cm ^-1Below.

4. according to each the described prepreg in the claim 1～3, wherein, the volume density of described fiber weaving cloth is 1.05～1.30g/cm ³

5. according to each the described prepreg in the claim 1～4, wherein, the median size that is present in the described silica dioxide granule in the described precursor is 5～100nm.

6. according to each the described prepreg in the claim 1～5, wherein, described resin combination comprises thermosetting resin and packing material at least,

Be that the ratio of 50～85 quality % contains described packing material with the solids component with respect to described resin combination.

7. prepreg according to claim 6, wherein, described packing material is being that the ratio of 1～20 quality % contains described silica dioxide granule with respect to described packing material.

8. according to each the described prepreg in the claim 1～7, its integral thickness is 30～220 μ m.

9. according to each the described prepreg in the claim 1～8, wherein, described precursor is made of glass fibre, and described glass fibre contains SiO with the ratio of 50～100 quality % at least ₂, contain Al with the ratio of 0～30 quality % ₂O ₃, contain CaO with the ratio of 0～30 quality %.

10. prepreg according to claim 9, wherein, described glass fibre uses at least a glass that is selected from the group of being made up of T glass, S glass, D glass, E glass, NE glass, silica glass to form.

11. according to claim 9 or 10 described prepregs, wherein, to make the Young's modulus when tabular be 50～100GPa to described glass fibre, the tensile strength made when tabular is that 25GPa is above, the tensile strength of the length direction when making fiber weaving cloth is more than the 30N/25mm.

12. according to each the described prepreg in the claim 9～11, wherein, the Gas permeability of described fiber weaving cloth is 1～80cc/cm ²/ sec.

13. according to each the described prepreg in the claim 1～12, wherein, utilize the silicane or the alkyl silazane class that contain functional group that described silica dioxide granule has been implemented surface treatment.

14. a veneer sheet, it obtains each the described prepreg curing in the claim 1～13.

15. veneer sheet according to claim 14, wherein, described prepreg at least one the outside face be provided with conductor layer.

16. a printed circuit board (PCB), it is each the described prepreg in the claim 1～13 or claim 14 or 15 described veneer sheets to be used for the internal layer circuit substrate form.

17. printed circuit board (PCB) according to claim 16, wherein, the described prepreg of each in the claim 1～13 is arranged on the described internal layer circuit substrate as insulation layer.

18. a semiconductor device, its semiconductor element mounted thereon on claim 16 or 17 described printed circuit board (PCB)s forms.