KR101355777B1 - Prepreg, laminate, printed wiring board, and semiconductor device - Google Patents

Abstract

The prepreg which concerns on this invention is the prepreg 40 formed by impregnating a resin composition in the fiber woven fabric comprised by strand. In the prepreg according to the present invention, silica particles are present in the strand. Thereby, the prepreg excellent in the impregnation of the resin composition with respect to a fiber woven fabric can be obtained. Moreover, a printed wiring board and a semiconductor device can be manufactured using the said prepreg and / or the laminated board with metal manufactured using the said prepreg.

Description

Prepregs, laminates, printed wiring boards and semiconductor devices {PREPREG, LAMINATE, PRINTED WIRING BOARD, AND SEMICONDUCTOR DEVICE}

The present invention relates to prepregs, laminates, printed wiring boards and semiconductor devices.

Background Art In recent years, with the demand for higher functionality of electronic devices, higher density integration and higher density mounting of electronic components have been advanced. For this reason, the printed wiring boards corresponding to the high density mounting used for these are required to miniaturize the circuit wiring and to reduce the through holes and via holes.

Through-holes and via holes are formed using a drill or a laser such as a carbon dioxide laser. In particular, lasers are used to drill small diameter holes. In the punching process by a laser, the larger the unevenness | corrugation of the insulating-layer wall surface which forms a hole, the more easily a hole diameter and a shape become distorted, and the precision of a process will fall.

The insulating layer of a printed wiring board can be formed by heat-pressing what laminated | stacked one or multiple sheets of prepreg. The prepreg is generally produced by impregnating a varnish formed by containing a resin composition containing a thermosetting resin in a solvent in a substrate such as glass cloth and heating and drying it. There exists a difference in meltability by a laser in a base material part and a resin composition part among the insulating-layer wall surfaces which form a hole by laser processing. For this reason, the density of a base material is small, and there exists a tendency for a hole diameter and a shape to be disturbed easily when a snow is genital. On the other hand, by using the high-density base material with an eye blocked, the punching workability by the laser of an insulating layer can be improved (patent document 1, 2).

Moreover, in order to cope with the high density of component mounting on a printed wiring board, the curvature by thermal expansion of a printed wiring board is reduced, and securing connection reliability is calculated | required. A semiconductor device (semiconductor package) is formed by mounting a semiconductor element on a printed wiring board, but the semiconductor element has a thermal expansion rate of 3 to 6 ppm / 占 폚, which is smaller than that of a general printed circuit board for semiconductor packages. For this reason, when a thermal shock is applied to a semiconductor package, curvature may generate | occur | produce in a semiconductor package by the difference in the thermal expansion rate of a semiconductor element and the printed wiring board for semiconductor packages. In this case, a connection failure may occur between a semiconductor element and the printed wiring board for semiconductor packages, or between the semiconductor package and the printed wiring board mounted.

By using the insulating material with a small thermal expansion coefficient for an insulating layer, the curvature by the thermal expansion of a printed wiring board can be made small. In order to low-expansion the prepreg used as an insulating material, what filled the inorganic filler with high filling as a resin composition used for manufacture of a prepreg is used (patent document 3).

Japanese Patent Laid-Open No. 2001-38836 Japanese Patent Application Laid-Open No. 2000-22302 Japanese Patent Laid-Open No. 2009-138075

However, prepreg fabrication using a high density substrate is poor in impregnation of the resin composition with respect to the substrate, and particularly in resin compositions containing a large amount of filler, impregnation of the resin composition is difficult because the filler cannot enter through the fibers of the substrate. Become. In addition, in order to improve the impregnation, for example, when the content of the filler is reduced, it may be difficult to maintain various other properties of the prepreg.

This invention is made | formed in order to solve the said problem, The objective of this invention is providing the prepreg excellent in the impregnation of the thermosetting resin composition with respect to a fiber woven fabric, maintaining the various characteristic which a prepreg has. Moreover, the objective of this invention is providing the laminated board with a metal using the said prepreg, the printed wiring board obtained using these, and a semiconductor device.

According to the present invention, there is provided a prepreg obtained by impregnating a fiber composition composed of strands with a resin composition, wherein a prepreg having silica particles in the strands is provided.

According to the present invention, it is possible to provide a prepreg excellent in impregnation of the thermosetting resin composition with respect to a fiber woven fabric while maintaining various properties of the prepreg.

Moreover, according to this invention, a printed wiring board and a semiconductor device can be manufactured using the said prepreg and / or the laminated board with metal manufactured using the said prepreg.

The foregoing and other objects, features, and advantages will become more apparent from the preferred embodiments described below and the accompanying drawings attached thereto.
BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the manufacturing method of the laminated plate with a metal of this invention.
It is a schematic diagram which shows another example of the manufacturing method of the laminated plate with a metal of this invention.
3 is a photograph of a cross-sectional view of a prepreg obtained in Example 1. FIG.
4 is a photograph of a cross-sectional view of a prepreg obtained in Comparative Example 4. FIG.
It is a photograph of the surface which etched the copper foil of the laminated sheet with a metal obtained in Example 1 in the whole surface.
It is a photograph of the surface which etched the copper foil of the laminated plate with metal obtained by the comparative example 6 in full surface.
FIG. 7 is an SEM photograph of an enlarged view of the voids observed in FIG. 6.
FIG. 8 is an SEM photograph of an enlarged view of a cross section of the void observed in FIG. 7. FIG.
9 is a SEM photograph of a cross-sectional view showing a part of the strands forming the fiber woven fabric of the prepreg obtained in Example 1. FIG.
10 is a SEM photograph of a cross-sectional view showing a part of the strands constituting the fiber woven fabric of the prepreg obtained in Example 1. FIG.
11 is a SEM photograph of a cross-sectional view showing a part of the strands constituting the fiber woven fabric of the prepreg obtained in Example 1. FIG.
12 is a SEM photograph of a cross-sectional view showing a portion of the strand constituting the fiber woven fabric of the prepreg obtained in Example 1. FIG.

EMBODIMENT OF THE INVENTION Below, the prepreg of this invention, the laminated board with a metal, a printed wiring board, and a semiconductor device are demonstrated in detail.

1. Prepreg

The prepreg of this invention is a prepreg formed by impregnating a resin composition in the fiber woven fabric comprised by strand. Moreover, silica particle exists in the strand which comprises a fiber woven fabric. In addition, a strand is a bundle of the fiber which comprises a fiber woven fabric. A fiber woven fabric is formed by weaving a strand so that it may become the textile structure mentioned later.

The present inventors found that when the prepreg is formed so that silica particles are present in the strand, the impregnability of the resin composition to the fiber woven fabric can be improved while maintaining various properties of the prepreg. Here, various characteristics are the insulation reliability of the printed wiring board mentioned later, the laser workability of a prepreg, the low thermal expansion property of a prepreg, etc., for example.

When the impregnation property of the resin composition with respect to a fiber woven fabric is favorable, it can suppress that a void generate | occur | produces in the obtained prepreg. Thereby, insulation reliability can be improved in the printed wiring board which used the said prepreg for the insulating layer.

Moreover, high impregnation property can be obtained also when a high-density fiber woven fabric is used. For this reason, the prepreg excellent in laser workability can be formed using a high density fiber woven fabric.

Moreover, it becomes possible to high-fill a filler in a fiber woven fabric by improving the impregnation property of the resin composition with respect to a fiber woven fabric. For this reason, the low thermal expansion of a prepreg can be aimed at. Thereby, it can suppress that a curvature generate | occur | produces in the printed wiring board which used the said prepreg for the insulating layer. Therefore, it becomes possible to improve the connection reliability in a semiconductor device.

The resin composition constituting the prepreg is a thermosetting resin composition (hereinafter, simply referred to as a "resin composition") containing at least a thermosetting resin and a filler.

It is preferable that the resin composition which comprises a prepreg contains the silica particle of 5-100 nm of average particle diameters, for example in the ratio of 1-20 mass% of a filler. MEANS TO SOLVE THE PROBLEM Even if it is the prepreg obtained by impregnating the resin composition containing a large amount of filler in a high-density fiber woven fabric, this filler contains the silica particle of an average particle diameter of 5-100 nm in the ratio of 1-20 mass% of a resin composition. It was found that the impregnation became good. This is because the silica particles having an average particle diameter of 5 to 100 nm are entangled between fibers of the fiber woven fabric, i.e., the strands, and the fibers are widened, so that fillers other than the silica particles having an average particle diameter of 5 to 100 nm can be squeezed into the fiber fabric. I think. Thus, the prepreg which has a silica particle in a strand can be obtained by using the silica particle of the nanosize of an average particle diameter of 5-100 nm as a filler.

Moreover, due to the difference between the surface potential of the silica particles having an average particle diameter of 5 to 100 nm and the surface potential of the other fillers, the silica particles having an average particle diameter of 5 to 100 nm and the filler can be attracted by interaction. For this reason, silica particles having an average particle diameter of 5 to 100 nm are present around the filler, and silica particles having an average particle diameter of 5 to 100 nm have a spacer effect. As described above, silica particles having an average particle diameter of 5 to 100 nm are present around the filler to act as spacers, thereby reducing the pulling force due to van der Waals force of the filler and preventing aggregation. Thereby, the said filler becomes a high dispersion state and can prevent the fall of fluidity | liquidity.

It is preferable to use the said silica particle of average particle diameter 5-100 nm as a slurry previously disperse | distributed to the organic solvent. Thereby, the dispersibility of a filler can be improved and the fall of the fluidity which arises when using other filler can be suppressed. This reason is considered as follows. First, nano-sized particles such as nano-sized silica tend to aggregate and often form secondary aggregates when blended into a resin composition, but such secondary aggregation can be prevented by using a slurry. This can prevent the fluidity from being lowered. Moreover, it is preferable that the filler used for this invention is surface-treated beforehand in order to improve aggregation prevention and dispersibility.

In addition, in the present invention, the high-density fiber woven fabric means a fiber woven fabric which is treated not only to increase the number of yarns, but also to uniformly open one fiber and reduce the thickness by flattening. do. High-density fiber woven fabrics have a bulk density of at least 1.05 g / cm ³ , for example. Thereby, since the resin composition can be impregnated further by one fiber, the high filling of a filler can further be aimed at. Furthermore, since the amount of resin on a fiber woven fabric can be sufficiently secured, the moldability at the time of laminating | stacking copper foil on a prepreg to make a copper clad laminated board, or the smoothing of the surface of a copper clad laminated board can be maintained.

As described above, the prepreg of the present invention is less likely to generate voids because the impregnation of the resin composition to the fiber woven fabric is good. Moreover, since a large amount of filler is contained in a resin composition, the printed wiring board obtained by using the prepreg of this invention with low thermal expansion is small in curvature. In addition, in this invention, thermal expansion property of a prepreg means the thermal expansion property in the state which hardened the prepreg.

Moreover, the prepreg of this invention is excellent in heat resistance and high rigidity by high filling a filler. Moreover, it is preferable that the bulk density of the fiber woven fabric which comprises the prepreg of this invention is 1.05-1.30 g / cm <^3> . By using a high-density fiber woven fabric with a bulk density of 1.05 to 1.30 g / cm ³ , the hole diameter and shape accuracy by laser processing are good when used as an insulating layer of a printed wiring board, Can be formed.

Moreover, in general, the prepreg obtained by using the resin composition containing a large amount of filler deteriorates the impregnation of the resin composition with respect to a base material, and it is difficult for a base material to hold a resin composition at a uniform thickness, and the said prepreg When creating a printed wiring board for use in an insulating layer, there is a problem that the insulating layer is inferior in surface smoothness and adhesion to a conductor layer, and thus fine wiring processing is difficult. This tends to get worse when the prepreg is thinned. On the other hand, since the prepreg of the present invention has good impregnation of the resin composition with respect to the fiber woven fabric, the fiber woven fabric can maintain the resin composition at a uniform thickness, and the surface smoothness and adhesion with the conductor layer are good, It is possible. Moreover, the prepreg of this invention becomes high heat resistance and high rigidity by using the resin composition containing a large amount of filler.

First, the fiber woven fabric used for this invention is demonstrated.

Although it does not specifically limit as a fiber woven fabric used for this invention, For example, the fiber woven fabric which consists of synthetic fiber, such as glass fiber, aramid, polyester, aromatic polyester, fluororesin, metal fiber, carbon fiber, mineral fiber, etc. Can be mentioned. Among these, the glass fiber woven fabric which consists of glass fiber is preferable because it is low thermal expansion property, high rigidity, and is excellent in dimensional stability.

The glass fiber is not particularly limited, but preferably contains at least SiO ₂ of 50 mass% to 100 mass%, Al ₂ O ₃ 0% by mass to 30% by weight, CaO in a proportion of from 0% by mass to 30% by weight Especially, it is preferable to use at least 1 sort (s) of glass chosen from the group which consists of T glass (it may be called "S glass"), D glass, E glass, NE glass, and quartz glass, Among these, , T glass (S glass), quartz glass, and D glass are more preferable, and T glass (S glass) and quartz glass are more preferable at the point which is excellent in low thermal expansion property and is high strength.

Further, in the present invention, T glass (S glass) is, SiO ₂ of 62 mass% to 65 mass%, Al ₂ O ₃ to 20 mass% to 25 mass%, CaO 0 wt.% To 0.01 mass%, the MgO 10 % by mass to 15% by weight, B ₂ O ₃ 0% by mass to 0.01% by mass, the glass of the composition Altogether the Na ₂ O and K ₂ O contained in an amount of 0% by mass to 1% by weight, D glass column, 72% by mass to 76% by mass of SiO ₂ , 0% by mass to 5% by mass of Al ₂ O ₃ , 0% by mass to 1% by mass of CaO, 0% to 1% by mass of MgO, and B ₂ O ₃ to 20 mass% to 25 mass%, Na ₂ O and a glass of the following composition containing K ₂ O in a ratio of rolled 3% by mass to 5% by weight, E glass is 52% by mass to 56% by weight of SiO _2, Al ₂ O ₃ 12% by mass to 16% by weight, CaO 15% by mass to 25% by weight, 0% by mass to 6% by weight MgO, B ₂ O ₃ 5% by mass to 10% by weight, Na ₂ O and K ₂ Altogether the O and the glass of the following composition containing a proportion of 0 to 0.8% by weight, NE glass is, SiO ₂ of 52 mass% to 56 mass%, Al ₂ O ₃ to 10 mass% to 15 mass%, CaO 0 wt % To 10 %, The MgO 0% by mass to 5% by weight, B ₂ O ₃ to 15 mass% to 20 mass%, Na ₂ O and 1-5 K ₂ O a rolled 0% by mass to 1% by weight, 0.05% by weight of TiO ₂ the glass of the following composition containing a ratio of mass%, a silica glass is a glass of the following composition containing SiO ₂ in a proportion of 99.0% by mass to 100% by weight.

Although the said glass fiber is not specifically limited, The tensile strength of the Young's modulus at the time of plate shape is 50-100 GPa, the tensile strength at the time of plate shape is 25 GPa or more, and the tensile strength of the long direction when the fiber woven fabric is 30 N / 25mm. It is preferable that it is more than the above, More preferably, the Young's modulus at the time of plate shape is 80-100 GPa, The tensile strength at the time of plate shape is 35 GPa or more, and the tensile strength of the long direction when it is made into a fiber woven fabric is 45 N / 25 mm or more. Thereby, the prepreg excellent in dimensional stability can be obtained. In addition, the Young's modulus is a value measured by a known three-point bending tester generally used in accordance with JIS R1602, and the tensile strength is measured by a known constant speed extension type tensile tester generally used in accordance with JIS R3420. The tensile strength of the said long direction is a value measured by the constant speed elongation type tensile tester as mentioned above based on JISR3420, and using glass fiber as a woven fabric.

In addition, in the measurement of the said Young's modulus and the measurement of the said tensile strength, "plate shape" means the state which made the glass composition of the composition similar to glass fiber into the glass plate of thickness 0.5-1.0 mm. Moreover, about the measurement of the tensile strength of the said long direction, a "long direction" means the diagonal (warp) direction.

Although the said glass fiber is not specifically limited, It is preferable that the thermal expansion coefficient of the warp direction measured according to JIS R3102 is 10 ppm / degrees C or less, and it is especially preferable that it is 3 ppm / degrees C or less. Thereby, the curvature by the thermal expansion of a printed wiring board can be made small.

Although the thickness of the said fiber woven fabric is not specifically limited, It is preferable that it is 10-200 micrometers, More preferably, it is 10-140 micrometers, More preferably, it is 20-90 micrometers. Thereby, the impregnation of the resin composition with respect to a fiber woven fabric becomes favorable, and it becomes possible to respond to thickness reduction.

It is preferable that the bulk density of the said fiber woven fabric is 1.05-1.30g / cm <^3> , and it is especially preferable that it is 1.10-1.25g / cm <^3> . If the bulk density is less than the lower limit, the laser workability of the insulating layer is inferior. If the bulk density is exceeded, the impregnation of the resin composition with respect to the fiber woven fabric is deteriorated. In addition, adjustment of the bulk density of a fiber woven fabric is performed by adjusting the number of in which a warp and a horizontal thread are infiltrated, and the thickness of the fiber which it opened and flattened.

The fibrous web is not particularly limited, but it is particularly preferred air permeability is from 1 to preferably a 80cc / cm ² / sec, and ^{3 ~ 50cc / cm 2 / sec} . If air permeability is less than the said lower limit, the impregnation property of the resin composition with respect to a fiber woven fabric will worsen, and if it exceeds the said upper limit, the laser workability of an insulating layer will be inferior.

The fibrous web is not particularly limited, but it is particularly preferred basis weight of 10 ~ 160g / m ² is preferable, and the 15 ~ 130g / m ^2. When the basis weight is less than the lower limit, the low thermal expansion property of the prepreg is inferior. When the basis weight is exceeded, the impregnability of the resin composition to the fiber woven fabric is deteriorated or the laser workability of the insulating layer is inferior.

Moreover, although the fiber used for the said fiber woven fabric is not specifically limited, It is preferable that flatness is 1: 2-1: 50, It is especially preferable that it is 1: 5-1: 30. By carrying out the flatness of the fiber used for a fiber woven fabric in the said range, since the impregnation and wettability of the resin composition with respect to the said fiber woven fabric are more excellent, the insulation reliability between through-holes can be improved and the laser workability of an insulating layer can be improved. . In addition, in this invention, a flat rate is a value represented by thickness of a thread: width of a thread.

Moreover, although the textile structure of the said fiber woven fabric is not specifically limited, For example, textile structures, such as a plain weave, aza weave, a runner weave, a twill weave, etc. are mentioned, Among these, laser workability, strength, and a hole hole are mentioned. A plain weave structure is preferable at the point which is excellent in interlayer insulation reliability.

Next, the thermosetting resin composition used for this invention is demonstrated.

The thermosetting resin composition used for this invention contains at least a thermosetting resin and a filler. The said filler is contained in the ratio of 50-85 mass% of solid content of the said thermosetting resin composition. Moreover, the said thermosetting resin composition contains the silica particle of average particle diameter 5-100 nm in the ratio of 1-20 mass% of the said filler. Moreover, the said thermosetting resin composition may further contain a hardening | curing agent, a coupling agent, etc. as needed.

(filling)

The filler contains silica particles having an average particle diameter of 5 to 100 nm in a proportion of 1 to 20% by mass of the whole filler.

Although it does not specifically limit as said silica particle, For example, by the combustion method, such as the VMC (Vaporized Metal Combustion) method, PVS (Physical Vapor Synthesis) method, the melting method of flame-melting crushed silica, the sedimentation method, the gel method, etc. What was manufactured can be used. Among these, VMC method is especially preferable. The VMC method is a method of forming silica fine particles by adding silicon powder into a chemical salt formed in an oxygen-containing gas and burning it, followed by cooling. In the said VMC method, the particle diameter of the silica fine particle obtained can be adjusted by adjusting the particle diameter, injection amount, flame temperature, etc. of the silicon powder to introduce | pour. Moreover, as said silica particle, commercial items, such as NSS-5N (made by Tokuyama Corporation) and Sicastar43-00-501 (made by Micromod), can also be used.

It is especially preferable that the said average particle diameters 5-100 nm silica particle is an average particle diameter 10-75 nm especially from an impregnation point. When the average particle diameter of a silica particle is less than 5 nm, it is thought that it may not spread between the fibers of a fiber woven fabric, and when larger than 100 nm, it may not be able to squeeze into between fibers.

The average particle diameter of the said silica particle can be measured by a laser diffraction scattering method, a dynamic light scattering method, etc., for example. In the case of the silica particles having an average particle diameter of 5 to 100 nm, the particles are dispersed by ultrasonic waves in water and the particle size distribution of the particles is measured on a volume basis by a dynamic light scattering particle size distribution measuring apparatus (manufactured by HORIBA, LB-550). Let median diameter (D50) be an average particle diameter.

Moreover, the said silica particle is not specifically limited, It is preferable that it is hydrophobic. Thereby, aggregation of a silica particle can be suppressed and a silica particle can be disperse | distributed favorably in the resin composition of this invention. Moreover, since the affinity of a thermosetting resin and a silica particle improves, and the adhesiveness of the surface of the said thermosetting resin and a said silica particle improves, the insulating layer excellent in mechanical strength can be obtained.

As a method of making a silica particle hydrophobic, the method of surface-treating a silica particle with functional group containing silanes and / or alkylsilazane beforehand, etc. are mentioned, for example. As the functional group-containing silanes, known ones can be used, and examples thereof include epoxy silane, amino silane, vinyl silane, acrylic silane, mercapto silane, isocyanate silane, sulfide silane and ureide silane. Examples of the alkylsilazanes include hexamethyldisilazane (HMDS), 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octamethyltrisilazane, and hexamethylcyclotri Silazane and the like. Moreover, the said surface treatment is given to a silica particle, and also the effect of preventing aggregation of a filler and dispersibility is exhibited.

Although the quantity of the functional group containing silanes and / or alkylsilazanes which surface-treat on the said silica particle beforehand is not specifically limited, It is preferable that they are 0.01 weight part or more and 5 weight part or less with respect to 100 weight part of said silica particles. More preferably, 0.1 weight part or more and 3 weight part or less are preferable. When content of functional group containing silane and / or alkyl silazane exceeds the said upper limit, a crack may enter into an insulating layer at the time of manufacture of a printed wiring board, and if it is less than the said lower limit, the bonding force of a resin component and a silica particle may fall.

Although the method of surface-treating the said silica particle with functional group containing silanes and / or alkylsilazane beforehand is not specifically limited, A wet system or a dry system is preferable. Especially preferably, a wet system is preferable. When the wet method is compared with the dry method, the surface of the silica particles can be treated uniformly.

Moreover, it is preferable to perform the said surface treatment in 50% or more of a specific surface area.

The said silica particle of the average particle diameter of 5-100 nm is contained in the ratio of 1-20 mass% of the whole filler. If content is less than the said lower limit, the effect of improving impregnation will become inadequate, and if content exceeds the said upper limit, conversely, impregnation may deteriorate and the moldability of a prepreg may be inferior. Moreover, it is more preferable that content of the silica particle of the said average particle diameter of 5-100 nm is 3-15 mass% of the whole filler.

The filler used in the present invention is not particularly limited to silica particles having an average particle diameter of 5 to 100 nm, but, for example, silicates such as talc, calcined clay, unbaked clay, mica, glass, titanium oxide, alumina, and average particle diameter are 100 nm. Oxides such as larger silica particles, carbonates such as calcium carbonate, magnesium carbonate, hydrotalcite, aluminum hydroxide, boehmite (AlO (OH), boehmite commonly referred to as "imitation" boehmite (i.e., Al ₂ O ₃ xH ₂ O, where x = 1 to 2)), metal hydroxides such as magnesium hydroxide and calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite, zinc borate, barium metaborate, aluminum borate and calcium borate And inorganic fillers such as borate salts such as sodium borate, aluminum nitride, boron nitride, silicon nitride, nitrides such as carbon nitride, and titanates such as strontium titanate and barium titanate. . The said inorganic filler may be used individually by 1 type, and may use two or more types together. Among these, magnesium hydroxide, aluminum hydroxide, boehmite, spherical silica particles having an average particle diameter of more than 100 nm, talc, calcined talc, and alumina are preferable, and spherical silica having a particularly good boehmite and an average particle diameter of more than 100 nm in terms of low thermal expansion and impregnation. Particles and spherical alumina are preferable.

Although it does not specifically limit as inorganic fillers other than the silica particle of the average particle diameter of 5-100 nm mentioned above (Hereinafter, it may be called "other inorganic filler."), The inorganic filler whose average particle diameter is monodisperse can also be used, and an average particle diameter This polydisperse inorganic filler can also be used. Moreover, you may use together one type or two types or more of inorganic fillers whose average particle diameter is monodispersion and / or polydispersion. In the present invention, the average particle diameter means monodispersion means that the standard deviation of the particle size is 10% or less, and polydispersion means that the standard deviation of the particle size is 10% or more.

Although the average particle diameter of the said other inorganic filler is not specifically limited, 0.1 micrometer-5.0 micrometers are preferable, and 0.1 micrometer-3.0 micrometers are especially preferable. Since the viscosity of a resin composition becomes it high that the particle size of another inorganic filler is less than the said lower limit, workability may be influenced at the time of prepreg preparation. Moreover, when it exceeds the said upper limit, the phenomenon, such as sedimentation of an inorganic filler, may arise in a resin composition. In addition, an average particle diameter can be measured using a laser diffraction / scattering particle size distribution measuring apparatus (general apparatuses, such as SALD-7000 by Shimadzu Corporation).

Moreover, when processing small diameter hole, narrow pitch process of a hole, and thin wire processing, it is preferable that the said other inorganic filler is granulated and cut. Especially, it is preferable that the granules cut | disconnected 45 micrometers or more, It is also preferable that the granules cut | disconnected 20 micrometers or more, It is especially preferable that the granules cut | disconnected 10 micrometers or more are especially preferable. In addition, "assembly cutting | disconnection" means that granulation of the size more than the particle diameter is excluded.

Moreover, it is preferable that the filler used for this invention contains organic fillers, such as rubber particles, in addition to the said inorganic filler. Preferred examples of the rubber particles that can be used in the present invention include core-shell rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrenebutadiene rubber particles, acrylic rubber particles, silicon particles and the like.

The core-shell rubber particles are rubber particles having a core layer and a shell layer, for example, a two-layer structure in which the shell layer of the outer layer is made of a glassy polymer, and the core layer of the inner layer is made of a rubbery polymer, or the shell layer of the outer layer is a glassy polymer. And a three-layer structure in which the intermediate layer is composed of a rubbery polymer and the core layer is composed of a glassy polymer. The glassy polymer layer is composed of, for example, a polymer of methyl methacrylate, and the like, and the rubbery polymer layer is composed of, for example, a butyl acrylate polymer (butyl rubber). Specific examples of the core-shell rubber particles include starpiroid AC3832 and AC3816N (trade name, manufactured by Gantz Chemical Co., Ltd.), and metabrene KW-4426 (trade name, manufactured by Mitsubishi Rayon Corporation). As a specific example of crosslinked acrylonitrile butadiene rubber (NBR) particle | grains, XER-91 (average particle diameter 0.5 micrometer, JSR Corporation make), etc. are mentioned.

Specific examples of the crosslinked styrene-butadiene rubber (SBR) particles include XSK-500 (average particle diameter of 0.5 µm, manufactured by JSR Corporation), and the like. Specific examples of the acrylic rubber particles include metabrene W300A (average particle diameter of 0.1 µm), W450A (average particle diameter of 0.2 µm) (manufactured by Mitsubishi Rayon Corporation), and the like.

The silicone particles are not particularly limited as long as they are rubber elastic fine particles formed of organopolysiloxane, and for example, the core part composed of fine particles made of silicone rubber (organopolysiloxane crosslinked elastomer) itself and silicon of a two-dimensional crosslinked main body is used. And core shell structural particles coated with silicon. As said silicon particle, KMP-605, KMP-600, KMP-597, KMP-594 (made by Shin-Etsu Chemical Co., Ltd.), training pillar E-500, training pillar E-600 (Toray Doukoning Co., Ltd.) Commercial items, such as (i), can be used.

Among the fillers used in the present invention, fillers other than silica particles having an average particle diameter of 5 to 100 nm are also preferably subjected to surface treatment in advance in order to increase aggregation prevention and dispersibility. A well-known silane coupling agent can be used for a surface treating agent, For example, an epoxy silane, an amino silane, a vinyl silane, an acryl silane, a mercapto silane, etc. are mentioned. Moreover, as for surface treatment, 50% or more of a specific surface area is preferable.

It is preferable that it is 50-85 mass% on the solid content basis of the whole resin composition, and, as for content of the filler in the resin composition used for this invention, it is especially preferable that it is 65-75 mass%. When filler content exceeds the said upper limit, the fluidity | liquidity of a resin composition is extremely bad, and workability at the time of prepreg manufacture is inferior. If it is less than the said lower limit, thermal expansion coefficient is high and the strength of an insulating layer may not be enough.

(Thermosetting resin)

Although it does not specifically limit as said thermosetting resin, Epoxy resin, cyanate resin, bismaleimide resin, a phenol resin, benzoxazine resin, vinyl benzyl ether resin, benzocyclobutene resin, etc. are used, Usually, thermosetting other than epoxy resin It is used by combining resin suitably.

Although it does not specifically limit as said epoxy resin, It is preferable that it does not contain a halogen atom substantially. Here, "substantially does not contain a halogen atom" means that the halogen derived from the halogen-based component used in the synthesis process of the epoxy resin is allowed to remain in the epoxy resin even after the halogen removal process. . Usually, it is preferable not to contain more than 30 ppm of halogen atoms in an epoxy resin.

Examples of the epoxy resins substantially free of halogen atoms include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol E type epoxy resins, bisphenol S type epoxy resins, and bisphenol Z type epoxy resins (4, 4). '-Cyclohexydienebisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4) -phenylenediisopropylidene) bisphenol type epoxy resin), bisphenol M type epoxy resin (4,4 Bisphenol-type epoxy resins such as'-(1,3-phenylenediisopropylidene) bisphenol-type epoxy resins), novolak-type epoxy resins such as phenol novolak-type epoxy resins, cresol novolak-type epoxy resins, and biphenyl-type epoxy resins Resin, xylylene type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl dimethylene type epoxy resin, trisphenol methane novolak type epoxy resin, 1,1,2,2- (tetraphenol) Ethane Aryl alkylene type epoxy resins, such as a lycidyl ether, a trifunctional or tetrafunctional glycidylamine, and a tetramethyl biphenyl type epoxy resin, a naphthalene skeleton modified epoxy resin, a methoxy naphthalene modified cresol novolak-type epoxy resin, and memeth Naphthalene type epoxy resins, such as a methoxy naphthalene dimethylene type | mold epoxy resin and a naphthylene ether type epoxy resin, anthracene type epoxy resin, a phenoxy type epoxy resin, a dicyclopentadiene type epoxy resin, norbornene type epoxy resin, and adamantane type epoxy resin And a fluorene type epoxy resin, a flame retardant epoxy resin obtained by halogenating the epoxy resin, and the like.

One kind of these epoxy resins may be used alone, two or more kinds of epoxy resins having different weight average molecular weights may be used in combination, and one or two or more kinds of epoxy resins and prepolymers of epoxy resins may be used in combination.

Especially among these epoxy resins, at least 1 sort (s) chosen from the group which consists of a biphenyl dimethylene type | mold epoxy resin, a novolak-type epoxy resin, a naphthalene-modified cresol novolak epoxy resin, and an anthracene type epoxy resin is preferable. By using these epoxy resins, the moisture absorption solder heat resistance and flame retardance of the obtained laminated board and printed wiring board can be improved.

Moreover, the heat resistance, the low thermal expansion property, and the low heat shrinkability of the obtained laminated board and printed wiring board can be improved by using a naphthylene ether type epoxy resin among these epoxy resins.

A naphthylene ether type epoxy resin can be represented by following General formula (1), for example.

(In formula, R <^1> represents a hydrogen atom or a methyl group, R <^2> represents a hydrogen atom, a C1-C4 alkyl group, an aralkyl group, a naphthalene group, or a glycidyl ether group containing naphthalene group each independently, o and m is an integer of 0-2, respectively, and either one of o or m is 1 or more.)

Although content of the said epoxy resin is not specifically limited, It is preferable to set it as 5 to 60 weight% on the solid content basis of the whole said resin composition. When content is less than the said lower limit, sclerosis | hardenability of a resin composition may fall, or the moisture resistance of the prepreg obtained using the said resin composition, or a printed wiring board may fall. Moreover, when the said upper limit is exceeded, the linear thermal expansion rate of a prepreg or a printed wiring board may become large, and heat resistance may fall. Content of the said epoxy resin becomes like this. Especially preferably, it is 10-50 weight% on the solid content basis of the whole resin composition.

Although the weight average molecular weight of the said epoxy resin is not specifically limited, 1.0 * 10 <^2> -2.0 * 10 <^4> is preferable. If a weight average molecular weight is less than the said lower limit, the tack property may generate | occur | produce on the surface of a prepreg, and if it exceeds the said upper limit, the soldering heat resistance of a prepreg may fall. By carrying out a weight average molecular weight in the said range, it can be set as the outstanding balance of these characteristics.

In this invention, the weight average molecular weight of the said epoxy resin can be specified by the weight molecular weight of polystyrene conversion, for example by measuring by gel permeation chromatography (GPC).

Although the said resin composition is not specifically limited, By containing a cyanate resin, a flame retardance can be improved, a thermal expansion coefficient can be made small, and the electrical characteristics (low dielectric constant, low dielectric loss tangent), etc. of a prepreg can be improved.

Although the said cyanate resin is not specifically limited, For example, it can obtain by making a cyanide halide compound, phenols, and naphthols react, and prepolymerizing by methods, such as a heating, as needed. Moreover, the commercial item prepared in this way can also be used.

Although it does not specifically limit as a kind of said cyanate resin, For example, bisphenol-types, such as novolak-type cyanate resin, bisphenol-A cyanate resin, bisphenol-E cyanate resin, and tetramethyl bisphenol F-cyanate resin, etc. Cyanate resin etc. are mentioned.

It is preferable that the said cyanate resin has two or more cyanate groups (-O-CN) in a molecule | numerator. For example, 2,2'-bis (4-cyanatophenyl) isopropylidene, 1,1'-bis (4-cyanatophenyl) ethane, bis (4-cyanato-3,5-dimethyl Phenyl) methane, 1,3-bis (4-cyanatophenyl-1- (1-methylethylidene)) benzene, dicyclopentadiene-type cyanatoester, phenol novolac-type cyanate ester, bis ( 4-cyanatophenyl) thioether, bis (4-cyanatophenyl) ether, 1,1,1-tris (4-cyanatophenyl) ethane, tris (4-cyanatophenyl) phosphite, Bis (4-cyanatophenyl) sulfone, 2,2-bis (4-cyanatophenyl) propane, 1,3-, 1,4-, 1,6-, 1,8-, 2,6- Or cyan obtained by the reaction of polyhydric phenols of 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonatophthalene, 4,4-dicyanatobiphenyl and phenol novolak type and cresol novolak type with cyanide halide Nate resin, obtained by reaction of naphthol aralkyl type polyhydric naphthol and cyanide halide Oh, there may be mentioned carbonate resins.

Among these, phenol novolac-type cyanate resin is excellent in flame retardancy and low thermal expansion property, and 2,2'-bis (4-cyanatophenyl) isopropylidene and dicyclopentadiene type cyanatoester control the crosslinking density. And excellent moisture resistance. In particular, a phenol novolak-type cyanate resin is preferable at the point of low thermal expansion. Moreover, you may use together 1 type or 2 or more types of other cyanate resin, and it is not specifically limited.

The cyanate resin may be used alone. Moreover, you may use together 2 or more types of cyanate resin from which a weight average molecular weight differs, or may use together the said cyanate resin and its prepolymer.

The said prepolymer is normally obtained by trimerizing the said cyanate resin by a heating reaction etc., for example, and is used suitably in order to adjust the moldability and fluidity of a resin composition.

Although the said prepolymer is not specifically limited, For example, when the prepolymer whose trimerization rate is 20-50 weight% is used, favorable moldability and fluidity can be expressed.

Although content of the said cyanate resin is not specifically limited, It is preferable that it is 5-60 weight% on the solid content basis of the whole resin composition, More preferably, it is 10-50 weight%. When content of cyanate resin exists in the said range, the heat resistance and flame retardance of a prepreg can be improved more effectively. When content of cyanate resin is less than the said minimum, the thermal expansion property of a prepreg may become large, and heat resistance may fall, and when exceeding the said upper limit, the strength of a prepreg may fall.

Although the weight average molecular weight of the said cyanate resin is not specifically limited, 5.0 * 10 <^2> -4.5 * 10 <^3> is preferable and 6.0 * 10 <^2> -3.0 * 10 <^3> is especially preferable. If a weight average molecular weight is less than the said lower limit, adhesiveness may arise in the surface of a prepreg, or mechanical strength may fall. Moreover, when a weight average molecular weight exceeds the said upper limit, hardening reaction of a resin composition may accelerate and adhesiveness with a conductor layer may deteriorate.

In the present invention, the weight average molecular weight of the cyanate resin can be determined by, for example, gel permeation chromatography (GPC) and specified by the weight molecular weight in terms of polystyrene.

Although the said resin composition is not specifically limited, Heat resistance can be improved by including bismaleimide resin.

Although it does not specifically limit as said bismaleimide resin, N, N '-(4,4'- diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4- maleimide phenyl) methane, 2 And bismaleimide resins such as 2-bis [4- (4-maleimide phenoxy) phenyl] propane. The said bismaleimide resin can also use together 1 type (s) or 2 or more types of other bismaleimide resin, and is not specifically limited. Moreover, you may use the said bismaleimide resin independently. Moreover, you may use together the bismaleimide resin from which a weight average molecular weight differs, or use the said bismaleimide resin and its prepolymer together.

Although content of the said bismaleimide resin is not specifically limited, It is preferable that it is 1 to 35 weight% on the basis of solid content of the whole resin composition, and 5-20 weight% is especially preferable.

(Hardener, hardening accelerator)

The resin composition used for this invention may use a hardening | curing agent together. It does not specifically limit as a hardening | curing agent, For example, when using an epoxy resin as said thermosetting resin, the phenolic hardening | curing agent, aliphatic amine, aromatic amine, dicyandiamide, dicarboxylic acid dihydrazide generally used as a hardening | curing agent of an epoxy resin A compound, an acid anhydride, etc. can be used.

Moreover, the hardening accelerator can be added to the resin composition used for this invention as needed. The curing accelerator is not particularly limited, and examples thereof include organometallic salts, tertiary amines, imidazoles, organic acids, and onium salt compounds. As a hardening accelerator, one type may be used independently including these derivatives, and two or more types may be used together including these derivatives.

(Coupling agent)

The said resin composition may contain a coupling agent further. A coupling agent is mix | blended in order to improve the wettability of the interface of a thermosetting resin and a filler. Thereby, resin and filler can be fixed uniformly with respect to a fiber woven fabric, and the heat resistance of a prepreg, especially the soldering heat resistance after moisture absorption can be improved.

Although the said coupling agent is not specifically limited, For example, an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a titanate coupling agent, a silicone oil type coupling agent, etc. are mentioned. Thereby, wettability with the interface of a filler can be made high, and the heat resistance of a prepreg can be improved more by it.

Although the addition amount of the said coupling agent is not specifically limited, 0.05-3 weight part is preferable with respect to 100 weight part of fillers, and 0.1-2 weight part is especially preferable. When content is less than the said lower limit, since a filler cannot fully be coat | covered, the effect of improving heat resistance may fall. Moreover, when content exceeds the said upper limit, reaction may be influenced and bending strength etc. may fall.

(etc)

Moreover, you may add additives other than the said components, such as an antifoamer, a leveling agent, a ultraviolet absorber, a foaming agent, antioxidant, a flame retardant, phosphorus system, a phosphazene, an ion trapping agent, to the said resin composition as needed.

The prepreg of this invention can be obtained by removing the said solvent, after hold | maintaining the varnish containing the above-mentioned thermosetting resin composition in a textile fabric. Although the method for preparing the varnish is not particularly limited, for example, a slurry obtained by dispersing a thermosetting resin and a filler in a solvent is prepared, and other components of the resin composition are added to the slurry, and the solvent is added to dissolve and mix. The method is preferred. As a result, the dispersibility of the filler can be improved, and silica particles having an average particle diameter of 5 to 100 nm contained in the filler can be easily picked up into the fiber woven fabric, and the impregnability of the resin composition in the fiber woven fabric can be improved.

In addition, in this invention, containing a thermosetting resin composition in a solvent means that the soluble resin contained in the said thermosetting resin composition is melt | dissolved in a solvent, and an insoluble filler etc. are disperse | distributed in a solvent.

Although it does not specifically limit as said solvent, The solvent which shows favorable solubility with respect to the said resin composition is preferable, For example, acetone, methyl ethyl ketone (MEK), cyclohexanone (ANON), methyl isobutyl ketone (MIBK), Cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Moreover, you may use a poor solvent in the range which does not adversely affect.

Although solid content (component except a solvent from a varnish) of the resin composition which the said varnish contains is not specifically limited, 30-80 weight% is preferable and 40-70 weight% is especially preferable. Thereby, the impregnation property with respect to the fiber woven fabric of a resin composition improves. Moreover, surface smoothness, thickness gap, etc. at the time of coating can be suppressed.

The method of impregnating the varnish into the fiber woven fabric includes, for example, a method of immersing the fiber woven fabric into the varnish, a method of applying by various coaters, a method of spraying by spray, and applying and drying the varnish to a substrate to form a resin sheet. The method of manufacturing and arrange | positioning the resin sheet so that a resin layer may contact a fiber woven fabric, etc. are mentioned. Among these, the method of immersing a fiber woven fabric in a varnish is preferable. Thereby, the impregnation property of the thermosetting resin composition with respect to a fiber woven fabric can be improved. Moreover, when immersing a fiber woven fabric in a varnish, a normal impregnation application | coating installation can be used. In addition, the prepreg which was semi-hardened can be obtained by drying the solvent of the said varnish, for example at 90-180 degreeC for 1 to 10 minutes.

The prepreg is composed of a fiber woven layer made of a fiber woven fabric and a resin layer made of a resin composition formed on both sides of the fiber woven layer. Although the thickness of the said fiber woven fabric layer is not specifically limited, It is preferable that it is 10-200 micrometers, More preferably, it is 10-140 micrometers, More preferably, it is 20-90 micrometers. Although the thickness (thickness only for one side only) of the said resin layer is not specifically limited, It is preferable that it is 0.5-20 micrometers, and it is especially preferable that it is 2-10 micrometers. By making the thickness of a fiber woven fabric layer and the thickness of a resin layer into the said range, adhesiveness and surface smoothness with a conductor layer become further more favorable.

Although the total thickness of the said prepreg is not specifically limited, It is preferable that it is 30-220 micrometers, and it is especially preferable that it is 40-165 micrometers. Thereby, the handleability of a prepreg is favorable and it can respond to thickness reduction.

In the prepreg, there are no voids having a length of 50 µm or more in the strands constituting the fiber woven fabric in the direction in which the fibers constituting the strands extend. Thereby, the insulation reliability of the printed wiring board which used the prepreg for the insulating layer can be improved. Furthermore, in the strand which comprises a fiber woven fabric, it is preferable that the space | gap which has a length of 20 micrometers or more, especially 10 micrometers or more exists in the direction which the fiber which comprises a strand extends.

Moreover, the water density of the space | gap whose diameter is 50 micrometers or more in the strand which comprises a fiber woven fabric in the said prepreg is 50 cm <^-3> or less. Also in this case, the insulation reliability of the printed wiring board which used the prepreg for the insulating layer can be improved. Moreover, it is preferable that the water density of the space | gap whose diameter is 50 micrometers or more in the strand which comprises a fiber woven fabric is 20 cm <^-3> or less, especially 10 cm <^-3> or less.

The length and water density of the voids in the strands described above are realized by appropriately adjusting the average particle diameter of the silica particles present in the strands, the bulk density of the fiber woven fabric, and the like.

2. Laminate

Next, a laminated board is demonstrated.

The laminate of the present invention is obtained by curing the prepreg according to the present invention. Moreover, it is preferable that the laminated board of this invention is provided by the conductor layer provided in the surface of at least one outer side of the prepreg which concerns on the said invention.

The said prepreg may be used by 1 sheet, and the laminated body laminated | stacked 2 or more sheets may be used. In the case of the laminated board which a conductor layer is provided (henceforth a "laminate board with a metal"), metal foil is laminated | stacked on the prepreg mentioned above, and it can obtain by heating and pressing. When using a single prepreg, the metal foil is laminated on both upper and lower surfaces or one side thereof, and when using a laminate in which two or more prepregs are laminated, the metal foil is stacked on the upper and lower sides or one side of the outermost layer of the laminate. Next, the laminated sheet with a metal can be obtained by heat-press-molding the thing which prepreg and metal foil were wrapped.

Examples of the metal foil include copper, copper alloys, aluminum, aluminum alloys, silver, silver alloys, gold, gold alloys, zinc, zinc alloys, nickel, nickel alloys, tin, tin alloys, iron, and iron alloys. Metal foil, such as an alloy, is mentioned. Moreover, you may form conductor layers, such as copper and copper alloy as mentioned above by plating.

Although the temperature to heat at the time of manufacture of a laminated plate with a metal is not specifically limited, 120-220 degreeC is preferable and 150-200 degreeC is especially preferable. Although the pressure to pressurize is not specifically limited, 0.5-5 MPa is preferable and 1-3 MPa is especially preferable. Moreover, you may perform postcure at the temperature of 150-300 degreeC with a high temperature tank etc. as needed.

Moreover, as another method of manufacturing the laminated sheet with a metal of this invention, the manufacturing method of the laminated sheet with a metal using the metal foil with a resin layer shown in FIG. 1 is mentioned. First, the metal foil 10 with a resin layer which coated the uniform resin layer 12 on the metal foil 11 with the coater is prepared. Subsequently, the metal foils 10 and 10 with the resin layer were disposed on both sides of the fiber woven fabric 20 with the resin layer 12 inward (FIG. 1 (a)), and heated in vacuum at 60 to 130 ° C. The laminate is impregnated with 0.1-5 MPa under pressure. Thereby, the prepreg 41 with metal foil is obtained (FIG. 1 (b)). Subsequently, the laminated sheet 51 with a metal can be obtained by directly heating and pressing the prepreg 41 with a metal foil (FIG. 1 (c)).

Moreover, as another method of manufacturing the laminated plate with metal of this invention, the manufacturing method of the laminated plate with metal using the polymer film sheet with a resin layer shown in FIG. 2 is also mentioned. First, the polymer film sheet 30 with a resin layer which coated the uniform resin layer 32 with the coater on the polymer film sheet 31 is prepared. Subsequently, the polymer film sheets 30 and 30 with the resin layer are disposed on both sides of the fiber woven fabric 20 with the resin layer 32 inward (FIG. 2 (a)). The laminate is impregnated at 130 ° C. with a pressure of 0.1 to 5 MPa. Thereby, the prepreg 42 with a polymer film sheet can be obtained (FIG. 2 (b)). Next, after peeling the polymer film sheet 31 of at least one surface of the prepreg 42 with a polymer film sheet (peel both sides in FIG.2 (c)), the metal foil on the surface which peeled the polymer film sheet 31 (11) is arrange | positioned (FIG. 2 (d)), and heat press molding. Thereby, the laminated plate 52 with a metal can be obtained (FIG. 2 (e)). In addition, when peeling a polymer film sheet of both surfaces, you may laminate | stack two or more sheets like the prepreg mentioned above. When laminating | stacking two or more prepregs, the laminated sheet with a metal can be obtained by arrange | positioning and heating and molding metal foil or a polymer film sheet in the upper and lower surfaces or one side of the outermost prepreg laminated | stacked. The laminated sheet with a metal obtained by such a manufacturing method has high thickness precision, uniform thickness, and excellent surface smoothness. Moreover, since the laminated board with a metal with a small shaping | molding distortion can be obtained, the printed wiring board and semiconductor device produced using the laminated board with a metal obtained by the said manufacturing method have a small warpage, and a curvature gap is also small. Moreover, a printed wiring board and a semiconductor device can be manufactured with a good yield.

Although the temperature is not specifically limited as conditions for the said hot press molding, 120-250 degreeC is preferable and 150-220 degreeC is especially preferable. Although the pressure to pressurize is not specifically limited, 0.1-5 Mpa is preferable and 0.5-3 Mpa is especially preferable. Moreover, you may perform post-cure at the temperature of 150-300 degreeC with a high temperature tank etc. as needed.

Although the laminated board with metal, such as FIGS. 1-2, is not specifically limited, For example, it is manufactured using the apparatus which manufactures the metal foil with a resin layer, and the apparatus which manufactures a laminated board with metal.

In the apparatus for producing the metal foil with the resin layer, the metal foil can be supplied by continuously unwinding it, for example, by using a sheet having a long length in the form of a roll or the like. The resin varnish is continuously supplied on the metal foil by a predetermined amount by the supply device of the resin. As a resin varnish, the coating liquid which melt | dissolved and disperse | distributed the resin composition of this invention is used. The coating amount of the resin varnish can be controlled by the clearance between the comma roll and the backup roll of the comma roll. The metal foil coated with a predetermined amount of resin varnish transfers the inside of the transverse conveyance type hot air drying apparatus, substantially removes the organic solvent contained in the resin varnish, and removes the resin layer. It can be set as attached metal foil. Although the metal foil with a resin layer can be wound as it is, a protective film is piled up on the side in which the resin layer was formed by the lamination roll, and the metal foil with a resin layer with which the said protective film was laminated is wound up, and the metal foil with insulation resin layer of a roll form is obtained. When using the manufacturing methods, such as FIGS. 1-2, since the control of uniform resin amount and the in-plane thickness precision are superior to the conventional manufacturing method which impregnates a varnish, the bending gap of the semiconductor device which mounts a semiconductor element is small. , Product yield is improved.

Moreover, when the laminated plate with a metal is obtained by such a manufacturing method, it is necessary to consider the impregnation of the resin composition with respect to a fiber woven fabric. Since the filler is improved in impregnation with respect to the fibrous substrate, in particular, by using silica particles having an average particle diameter of 5 to 100 nm, the flow of the resin composition in the laminate with a metal at the time of heat press molding is suppressed and the nonuniform movement of the molten resin Since this is suppressed, the unevenness | corrugation on the stripe of the surface of a laminated plate with metal can be prevented, and it can be set as uniform thickness.

3. Printed wiring board

Next, the printed wiring of this invention is demonstrated.

The printed wiring board of this invention uses said prepreg and / or said laminated board for an inner layer circuit board.

Or the printed wiring board of this invention uses said prepreg for the insulating layer on an inner layer circuit.

Moreover, in the case of the printed wiring board which used the prepreg of this invention or the laminated board of this invention for an inner-layer circuit board, the layer which hardened | cured the prepreg in an inner-layer circuit board is an insulating layer.

In the present invention, a printed wiring board is formed by forming a conductor circuit layer such as a metal foil on an insulating layer, and forming a conductor circuit layer, and any one of a single-sided printed wiring board (one layer board), a double-sided printed wiring board (two layer board) and a multilayer printed wiring board (multilayer board) May be used. A multilayer printed wiring board is a printed wiring board laminated | stacked in three or more layers by the plating through-hole method, a buildup method, etc., and can be obtained by laminating | stacking an insulating layer on an inner layer circuit board, and heat-molding. As the inner layer circuit board, for example, one formed by using the laminate of the present invention and / or the prepreg of the present invention can be used. As an inner layer circuit board which uses the laminated board of this invention, the conductor circuit of a predetermined pattern was formed in the laminated board of this invention which does not have a metal foil, for example by the semiadditive method etc., and the said conductor circuit part blackened, What formed the conductor circuit of a predetermined pattern on the metal foil of the laminated plate with a metal of this invention, and blackened the said conductor circuit part can be used suitably.

Moreover, as an inner circuit board which uses the prepreg of this invention, electric / electronic components, such as a capacitor | condenser, a resistor, and a chip | tip, are mounted on the insulating support body which consists of cured resin, etc., and the prepreg of this invention is laminated | stacked on it. The thing which blacked the said conductor circuit part by forming the conductor circuit of a predetermined pattern by the semiadditive method etc. on the board | substrate with a component obtained by heat press hardening can also be used.

Moreover, in this invention, the prepreg of this invention is further laminated | stacked on the inner circuit board which consists of such a laminated board of this invention, and / or the prepreg of this invention, and the conventionally well-known inner layer circuit board, and it heat-cured-cured What was made may be made into an inner layer circuit board. The prepreg of the present invention can be used as the insulating layer on the inner layer circuit. In addition, when using the prepreg of this invention as an insulating layer on the said inner layer circuit, the said inner layer circuit board does not need to be made using the prepreg or laminated board of this invention.

Hereinafter, as a representative example of the printed wiring board of the present invention, multilayer printed wiring in the case of using the laminated board with a metal of the present invention as an inner layer circuit board and using the prepreg of the present invention as an insulating layer will be described.

An inner circuit board is formed by forming a conductor circuit of a predetermined pattern on one side or both sides of the laminate with a metal, and blackening the conductor circuit portion. The formation method of the said conductor circuit is not specifically limited, It can carry out by well-known methods, such as a subtractive method, an additive method, a semiadditive method. In addition, through-holes are formed in the inner circuit board by drilling, laser processing, or the like, and electrical connection on both sides can be made by plating or the like. Since the said inner layer circuit board consists of the laminated board with a metal of this invention, especially through laser processing, the through hole excellent in the precision, such as a hole diameter and a shape, can be formed. The laser may use an excimer laser, a UV laser, a carbon dioxide laser, or the like.

Next, the said prepreg is piled up on this inner layer circuit board, and it heat-press-moldes and heat-cure, and an insulating layer is formed. Specifically, the prepreg and the inner circuit board are stacked, vacuum heated and press molded using a vacuum pressurized laminator apparatus or the like, and then the insulating layer is heat-cured by a hot air drying apparatus or the like. Although it does not specifically limit as conditions to heat press-molding here, For example, it can carry out at the temperature of 60-160 degreeC, and a pressure of 0.2-3 MPa. Moreover, it does not specifically limit as conditions to heat-harden, For example, it can carry out between temperature 140-240 degreeC and time 30-120 minutes.

Next, a laser is irradiated to the laminated insulating layer, and a opening part (empty hole) is formed. The laser may be the same as the laser used for forming the through hole. Since the said insulating layer consists of the prepreg of this invention, a hole part excellent in the precision, such as a hole diameter and a shape, can be formed by laser processing.

It is preferable to perform the process which removes the resin residue (smear) etc. after laser irradiation with oxidizing agents, such as a permanganate, a dichromate, etc., ie, a desmear process. If the desmear treatment is insufficient and the desmearability is not sufficiently secured, there is a possibility that the conduction of the upper conductor circuit layer and the lower conductor circuit layer may not be sufficiently secured due to the smear even if the metal plating treatment is performed in the openings. . Moreover, since the surface of the smooth insulating layer can be matched simultaneously by performing a desmear process, when the conductor layer is formed in the insulating layer surface by metal plating process, it is excellent in the adhesiveness of an insulating layer surface and a conductor layer. In addition, you may form a conductor layer on the surface of an insulating layer before formation of the aperture part by laser irradiation.

Next, a metal plating process is performed on the opening part and the insulating layer surface, and a conductor layer is formed. The surface of the insulating layer is further subjected to conductor circuit formation by the above-described known method or the like. In addition, the upper layer conductor circuit layer and the lower layer conductor circuit layer can be electrically conductive by forming a conductor layer by applying a metal plating treatment to the openings.

Moreover, although an insulating layer may be laminated | stacked and conductor circuit formation may be performed as mentioned above, in a multilayer printed wiring board, a soldering resist film is formed in outermost layer after conductor circuit formation. Although the formation method of a soldering resist film is not specifically limited, For example, the method of laminating | stacking (laminating) a dry film type soldering resist and forming it by exposure and image development, or the method of forming what printed the liquid resist by exposure and image development is carried out. Is made by When using the obtained multilayer printed wiring board for a semiconductor device, the connection electrode part for mounting a semiconductor element is provided. The connecting electrode portion can be appropriately coated with a metal film such as gold plating, nickel plating and solder plating.

4. Semiconductor device

Next, the semiconductor device of the present invention will be described.

A semiconductor element having solder bumps is mounted on the printed wiring board obtained above, and the connection with the printed wiring board is achieved through the solder bumps. Then, a sealing resin is filled between the printed wiring board and the semiconductor element to form a semiconductor device. It is preferable that a solder bump is comprised from the alloy which consists of tin, lead, silver, copper, bismuth, etc.

Connect the semiconductor element and the printed wiring board using a flip chip bonder or the like, and after aligning the solder bumps of the semiconductor electrode with the connection electrode portion on the printed wiring board, the IR reflow apparatus, the hot plate, and other heating devices are replaced. Use to heat the solder bumps above the melting point and connect them by fusion bonding the printed wiring board and the solder bumps. In addition, in order to improve connection reliability, a relatively low melting point metal layer, such as solder paste, may be formed in advance on the electrode portion for connection on the printed wiring board. Prior to this joining step, the connection reliability may be improved by applying flux to the surface layer of the electrode portion for connection on the solder bumps and / or the printed wiring board.

Example

Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples, but the present invention is not limited thereto.

The fiber woven fabric used by the Example and the comparative example is the woven fabric which the glass fiber prescribed | regulated to JISR3413 was woven into the woven fabric, and is the following glass fiber woven fabrics A-L.

A: T glass, E1101 / 0 using a glass fiber yarn, the number of Merc per 25mm of the warp and 44.5 hoengsa dog, 42, the flat carding process · 130㎛ thickness, basis weight of 155g / m ²

B: 46.5 pieces, 44 pieces, insulated / flattened thickness 95 µm, basis weight 121g / m ² , with E glass and glass fiber yarn of DE1501 / 0 per 25mm of warp and cross yarns

C: T glass, E2251 / 0 using a glass fiber yarn, the number of Merc per 25mm of warp and hoengsa 65, 64, the flat carding process, a thickness 95㎛, basis weight 121g / m ²

D: D glass, 65 pieces, 64 pieces, insulated and flattened thickness of 95m, basis weight 121g / m ² per 25mm of warp and cross thread using glass fiber yarn of E2251 / 0

E: T glass, D4501 / 0 using a glass fiber yarn, the number of Merc per 25mm of warp and hoengsa 59, 59, the flat carding process, a thickness 46㎛, basis weight 53g / m ²

F: T glass, BC15001 / 0 using a glass fiber yarn, the number of Merc per 25mm of warp and hoengsa 90, 90, the flat carding process, a thickness 20㎛, basis weight 24g / m ²

G: T glass, C12001 / 0 using a glass fiber yarn, the number of Merc per 25mm of warp and hoengsa 74, 77, the flat carding process, a thickness 25㎛, basis weight 31g / m ²

H: 44.5 pieces, 42 pieces of perforated and 25 mm inclined and cross yarns using T glass and glass fiber yarn of E1101 / 0, 115 micrometers of open and flattened thickness, basis weight 155 g / m ²

I: T glass, E1101 / 0 using a glass fiber yarn, the number of Merc per 25mm of warp and hoengsa 43, 40, the flat carding process, a thickness 145㎛, basis weight 150g / m ²

J: 59 pieces, 54 pieces of permeation and flattening per 25mm of the warp and cross yarns using T glass and glass fiber yarn of E2251 / 0, 97 µm thick, open and flat, 100 g / m ²

K: 60 pieces, 47 pieces, 50 micrometers of thickness that opened and flattened the insulated and flat yarns per 25mm using T glass and D4501 / 0 glass fiber yarn, basis weight 48g / m ²

L: T glass, C12001 / 0 using a glass fiber yarn, the number of Merc per 25mm of warp and hoengsa 68, 72, · opening 27㎛ flat processing thickness, basis weight 25g / m ²

The varnish used by the Example and the comparative example is manufactured by containing and mixing a resin composition in a solvent by the following varnish manufacture examples 1-7.

(Varnish production example 1)

6 parts by weight of epoxy resin (HP-5000 manufactured by DIC Corporation), 12 parts by weight of phenol novolac-type cyanate resin (PT30 manufactured by Lonza Corporation) and 6 parts by weight of phenolic curing agent (MEH-7851-4L manufactured by Meiwa Chemical) 10 parts by weight of silica particles (NSS-5N manufactured by Tokuyama Co., Ltd., 70 nm average particle diameter), 65 parts by weight of spherical silica (SO-31R manufactured by Admatex Co., Ltd., 1.0 μm average particle size) and epoxy silane (Shin-Etsu Chemical Co., Ltd.) 1.0 weight part of KBM-403E) was contained and mixed in methyl ethyl ketone, and it stirred using the high speed stirrer, and obtained the varnish whose epoxy resin composition is 70 weight% based on solid content. Moreover, when the whole filler contained in the resin composition mixed and mixed with varnish was 100 mass%, the silica particle contained in the said filler was 13 mass%, and spherical silica was 87 mass%.

(Varnish production example 2)

9 parts by weight of biphenyl aralkyl type epoxy resin (NC-3000 manufactured by Nippon Kayaku Co., Ltd.), 17 parts by weight of bismaleimide resin (BMI-70 manufactured by Keika Chemical Co., Ltd.), 4,4'-diaminodiphenylmethane 3 parts by weight, 10 parts by weight of silica particles (NSS-5N manufactured by Tokuyama Co., Ltd., average particle diameter: 70 nm), 60 parts by weight of boehmite (BMB manufactured by Kawaii Co., Ltd., average particle diameter: 0.5 μm), epoxy silane (KBM manufactured by Shin-Etsu Chemical Co., Ltd.) -403E) 1.0 part by weight was contained and mixed in dimethylformamide. Subsequently, the mixture was stirred using a high speed stirrer and adjusted to 70% by weight of a nonvolatile content to prepare a resin varnish. Moreover, when the whole filler contained in the resin composition mixed and mixed with varnish was 100 mass%, the silica particle contained in the said filler was 14 mass%, and boehmite was 86 mass%.

(Varnish production example 3)

20 parts by weight of biphenyl aralkyl type epoxy resin (NC-3000FH manufactured by Nippon Chemical Co., Ltd.), 5 parts by weight of naphthalene type epoxy resin (HP4032D manufactured by DIC Corporation), cyanate resin (derivatives of Tohto Chemical Co., Ltd. SN485, naphthol 17 parts by weight, 7 parts by weight of bismaleimide resin (BMI-70 manufactured by Kei-Akasei Kogyo Co., Ltd.), silica particles (NSS-5N manufactured by Tokuyama Co., Ltd., average particle diameter: 70 nm), and spherical silica (admatex) 35.5 weight part of SO-31R by the company, 1.0 micrometer of average particle diameters, 7.5 weight part of silicon particles (Shin-Etsu Chemical Co., Ltd. KMP600, 5 micrometers of average particle diameters), 0.01 weight of zinc octylate, epoxy silane (KBM by Shin-Etsu Chemical Co., Ltd.) -403E) 0.5 weight was contained and mixed in methyl ethyl ketone. Subsequently, the mixture was stirred using a high speed stirrer and adjusted to 70% by weight of a nonvolatile content to prepare a resin varnish. Moreover, when the whole filler contained in the resin composition mixed and mixed with varnish was 100 mass%, the silica particle contained in the said filler was 14 mass%, spherical silica was 71 mass%, and the silicon particle was 15 mass%.

(Varnish production example 4)

18.5 parts by weight of biphenyl aralkyl type epoxy resin (NC-3000 manufactured by Nippon Kayaku Co., Ltd.), 34.9 parts by weight of bismaleimide resin (BMI-70, manufactured by Keika Chemical Co., Ltd.), 4,4'-diaminodiphenylmethane 6.1 parts by weight, 5 parts by weight of silica particles (NSS-5N manufactured by Tokuyama Co., Ltd., average particle diameter: 70 nm), 35 parts by weight of boehmite (BMB manufactured by Kawaii Co., Ltd., average particle diameter: 0.5 μm), epoxy silane (KBM manufactured by Shin-Etsu Chemical Co., Ltd.) -403E) 0.5 weight part was contained and mixed in dimethylformamide. Subsequently, the mixture was stirred using a high speed stirrer and adjusted to 70% by weight of a nonvolatile content to prepare a resin varnish. In addition, when the whole filler contained in the varnish containing-mixed resin was 100 mass%, the silica particle contained in the said filler was 12.5 mass%, and boehmite was 87.5 mass%.

(Varnish production example 5)

2.80 parts by weight of biphenyl aralkyl type epoxy resin (NC-3000 manufactured by Nippon Kayaku Co., Ltd.), 5.27 parts by weight of bismaleimide resin (BMI-70, manufactured by Keika Chemical Co., Ltd.), 4,4'-diaminodiphenylmethane 0.93 parts by weight, 10 parts by weight of silica particles (NSS-5N manufactured by Tokuyama Co., Ltd., average particle diameter: 70 nm), 80 parts by weight of boehmite (BMB manufactured by Kawaii Corporation, average particle diameter of 0.5 μm), epoxy silane (KBM manufactured by Shin-Etsu Chemical Co., Ltd.) -403E) 1.0 part by weight was contained and mixed in dimethylformamide. Subsequently, the mixture was stirred using a high speed stirrer and adjusted to 70% by weight of a nonvolatile content to prepare a resin varnish. Moreover, when the whole filler contained in the resin composition mixed and mixed with varnish was 100 mass%, the silica particle contained in the said filler was 11 mass%, and boehmite was 89 mass%.

(Varnish production example 6)

6 parts by weight of epoxy resin (HP-5000 manufactured by DIC Corporation), 12 parts by weight of phenol novolac-type cyanate resin (PT30 manufactured by Lonza Corporation) and 6 parts by weight of phenolic curing agent (MEH-7851-4L manufactured by Meiwa Chemical) 30 parts by weight of silica particles (NSS-5N manufactured by Tokuyama Co., Ltd., average particle diameter: 70 nm), 45 parts by weight of spherical silica (SO-31R manufactured by Admatex, 1.0 μm), epoxy silane (Shin-Etsu Chemical Co., Ltd.) 1.0 weight part of KBM-403E) was contained and mixed in methyl ethyl ketone, and it stirred using the high speed stirrer, and the epoxy resin composition obtained 70 weight% of varnish on the basis of solid content. Moreover, when the whole filler contained in the resin composition mixed and mixed with varnish was 100 mass%, the silica particle contained in the said filler was 40 mass%, and spherical silica was 60 mass%.

(Varnish production example 7)

6 parts by weight of epoxy resin (NC-3000 manufactured by Nippon Chemical Co., Ltd.), 12 parts by weight of phenol novolac-type cyanate resin (PT30 manufactured by Lonza), and 6 parts by weight of phenol-based curing agent (MEH-7851-4L manufactured by Meiwa Chemical) 75 parts by weight of spherical silica (SO-31R manufactured by Admatex, 1.0 μm in average particle size) and 1.0 part by weight of epoxy silane (KBM-403E manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed and mixed in methyl ethyl ketone, followed by high speed stirring. It stirred using the apparatus and the epoxy resin composition obtained the varnish of 70 weight% on a solid content basis. Moreover, when the whole filler contained in the resin composition contained and mixed in the varnish was 100 mass%, the silica particle contained in the said filler was 0 mass%, and spherical silica was 100 mass%.

The composition of the resin composition used for varnish manufacture examples 1-7 is shown in Table 1. In addition, the compounding quantity of each component is shown by weight part.

Using the said glass fiber woven fabric and the said varnish, the prepreg, the laminated board with a metal, the printed wiring board (inner layer circuit board), the multilayer printed wiring board, and the semiconductor device were produced.

&Lt; Example 1 &gt;

(1) Preparation of prepreg

The varnish obtained in the manufacture example 1 was apply | coated flexibly on the polyethylene terephthalate base material (hereinafter PET base material) of thickness 38micrometer, the solvent was volatilized and dried at the temperature of 140 degreeC for 10 minutes, and the thickness of the resin layer was set to 30 micrometers. . The base material with the resin layer was disposed on both surfaces of the glass cloth A so that the resin layer was in contact with the glass cloth, and was placed in a vacuum pressurized laminator (MLVP-500 manufactured by Miki Manufacturing Co., Ltd.) under a condition of 1 minute at a pressure of 0.5 MPa and a temperature of 140 ° C. It heated and pressurized and impregnated the resin composition. This obtained the prepreg (resin layer (one side): 10 micrometers, fiber woven fabric layer: 130 micrometers) of thickness 150micrometer which has a PET base material on both surfaces.

(2) Manufacture of Laminates with Metal

2 micrometers copper foil with a carrier (Microsine MT18Ex-2 by Mitsui Metal Co., Ltd.) was piled on both surfaces of the said prepreg, and it heat-molded for 2 hours at the pressure of 3 Mpa and the temperature of 220 degreeC. This obtained the laminated board with a metal which has copper foil on both surfaces of the 150-micrometer-thick insulating layer which prepreg hardens | cures.

(3) Preparation of prepreg for multilayer printed wiring board insulation layer

The varnish obtained in Production Example 1 was impregnated into a glass woven fabric (thickness 16 µm, manufactured by Unichika Co., Ltd. E glass woven fabric, E02Z, basis weight 17.5 g / m ² ), dried in a heating furnace at 180 ° C. for 2 minutes, and resin in a prepreg. The composition obtained the prepreg (40 micrometers in thickness) which is about 78 weight% based on solid content. Further, the glass woven fabric had a bulk density of 1.09 g / cm ³ , an air permeability of 41 cc / cm ² / sec, and a flatness (thickness: width) of 1:16. The glass woven fabric was made of glass fibers having a Young's modulus of 93 GPa and a plate-like tensile strength of 48 GPa and a long-woven tensile strength of 90 N / 25 mm.

(4) Production of printed wiring boards (inner layer circuit boards)

Carrier foil is peeled from the said laminated board with metal, and it uses aperture carbon laser (ML605GTX3-5100U2 by Mitsubishi Electric Corporation) with aperture Φ1.4mm, beam diameter about 120 micrometers, energy 7-9mJ, number of shots 6 On the condition of, a through-hole of Φ 100 µm was formed. Subsequently, the laminated sheet with metal was immersed in a swelling liquid at 70 ° C. (manufactured by Arttec Japan, Swelling Deep Secure P) for 5 minutes, and further subjected to an aqueous solution of potassium permanganate at 80 ° C. (manufactured by Arttec Japan, Inc.). After immersion in compact CP) for 10 minutes, it neutralized and performed the roughening process. Next, the upper and lower copper foils were challenged by electroless plating (Kamimura Industries Co., Ltd., through-cupper PEA process).

Subsequently, an ultraviolet photosensitive dry film (manufactured by Asahi Kasei Co., Ltd., Sanport UFG-255) having a thickness of 25 µm was bonded to the surface of the electroless plating layer by a hot roll laminator. Next, the position of the glass mask (made by the topic company) in which the pattern with the minimum line width / line between 20/20 micrometers was drawn was matched. Then, after exposing with the exposure apparatus (Onosoki EV-0800) using the said glass mask, it developed by the sodium-carbonate aqueous solution and formed the resist mask. Next, the electroless plated layer as a power feeding layer for electrolytic copper plating was performed electrode (Okuno Pharmaceutical the 81-HL) to 3A / dm ^2, 25 minutes. This formed the pattern of the copper wiring which is about 20 micrometers in thickness. Next, the said resist mask was peeled off with the monoethanolamine solution (R-100 by Mitsubishi Gas Chemical Corporation) using a peeler. And unnecessary copper foil and electroless plating layer other than the pattern shape which is a power supply layer were removed by flash etching (pure solution of SAC-702M and SAC-701R35 by Ebara Computer Co., Ltd.), and the pattern of L / S = 20 / 20micrometer. Formed.

Subsequently, the roughening process of the conductor circuit (Mech Hbond CZ-8100) was performed. The said roughening process was performed by spray-spraying on condition of 35 degreeC of liquid temperature, and 0.15 MP of spray pressure, and roughening about 3 micrometers of roughness on the same surface. Subsequently, the surface treatment of conductor circuits (manufactured by Meck H. Bond CL-8300) was performed. In the said surface treatment, it immersed on the conditions of 25 degreeC of liquid temperature, and 20 second immersion time, and performed antirust process on the same surface. Thus, the printed wiring board (inner layer circuit board) was produced.

(5) Manufacture of multilayer printed wiring board

Next, the printed wiring board obtained above is used as an inner layer circuit board, and the said prepreg for multilayer printed wiring board insulating layers and 2 micrometers copper foil (microsin MT18Ex-2 by Mitsui Metal Co., Ltd.) with a carrier are piled up on both surfaces, and laminated | stacked. It laminated | stacked using the vacuum lamination apparatus, it heat-hardened for temperature 200 degreeC, pressure 3MPa, and time 120 minutes, and obtained the multilayer laminated body. Next, an outer layer circuit is formed in the same manner as in the above (4) manufacturing method of a printed wiring board (inner layer circuit board), and finally a solder resist (PSR4000 / AUS308, manufactured by Solar Ink, Inc.) is formed on the circuit surface to form a multilayer printed wiring board. Got it.

The said multilayer printed wiring board gave ENEPIG process to the connection electrode part corresponded to the solder bump array of a semiconductor element. ENEPIG treatment includes [1] cleaner treatment, [2] soft etching treatment, [3] pickling treatment, [4] pre-dip treatment, [5] palladium catalysis, [6] electroless nickel plating treatment, [7] electroless It carried out by the process of palladium plating process and [8] an electroless gold plating process.

(6) Manufacturing of semiconductor devices

The semiconductor device mounts a semiconductor device (TEG chip, size 10mm x 10mm, thickness 0.1mm) having solder bumps by heat compression bonding with a flip chip bonder on a printed wiring board subjected to ENEPIG treatment, and then in an IR reflow furnace. After melt-bonding a solder bump, it obtained by filling liquid sealing resin (CRP-4152S by Sumitomo Bak Cleat Co., Ltd.), and hardening liquid sealing resin. In addition, the liquid sealing resin was hardened on the conditions of the temperature of 150 degreeC, and 120 minutes. In addition, the solder bump of the said semiconductor element used what was formed by the process of Sn / Pb composition. Finally, the semiconductor device was obtained by reorganization into a router having a size of 14 mm x 14 mm.

<Examples 2-3 and Comparative Examples 1-6>

Using the varnish obtained by the manufacture example of the fiber woven fabric and varnish shown in Table 4, the prepreg and the laminated board with metal which have copper foil on both surfaces of the insulating layer of 150 micrometers in thickness similar to Example 1, a printed wiring board (inner-layer circuit board) ), A multilayer printed wiring board and a semiconductor device.

<Examples 4-6 and Comparative Example 7>

Except having made the thickness of the resin layer of the base material with a resin layer at the time of prepreg manufacture as it described in Table 5, it carried out similarly to Example 1 using the varnish obtained by the manufacture example of the fiber woven fabric and varnish shown in Table 5 The prepreg, the laminated board with metal which has copper foil on both surfaces of the insulating layer of thickness 100micrometer, the printed wiring board (inner layer circuit board), the multilayer printed wiring board, and the semiconductor device were obtained.

In addition, through-hole formation of a printed wiring board uses a carbon dioxide laser (ML605GTX3-5100U2, manufactured by Mitsubishi Electric Corporation), under the conditions of aperture Φ1.1 mm, beam diameter of about 110 μm, energy 7 to 9 mJ, and the number of shots 6. A through-hole having a diameter of 100 µm was formed.

<Example 7, 8 and Comparative Example 8>

Example 7 and Comparative Example 8 were made using the varnish obtained by the manufacture example of the fiber woven fabric and varnish shown in Table 6 except having made the thickness of the resin layer of the base material with a resin layer at the time of prepreg preparation as described in Table 6. In the same manner as in Example 1, a prepreg, a laminate with a metal having a copper foil on both surfaces of an insulating layer having a thickness of 60 µm, a printed wiring board (inner layer circuit board), a multilayer printed wiring board, and a semiconductor device were obtained.

Example 8 used Example 1 using the varnish obtained by the manufacture example of the fiber woven fabric and varnish shown in Table 6 except having made the thickness of the resin layer of the base material with a resin layer at the time of prepreg manufacture as described in Table 6. In the same manner as the prepreg (30 μm in total thickness) and two prepregs of 30 μm, the laminated plate with a metal having copper foil on both surfaces of an insulating layer having a thickness of 60 μm formed by curing, an inner layer circuit board, and a multilayer printed wiring board And a semiconductor device.

In addition, through-hole formation of a printed wiring board uses a carbon dioxide laser (ML605GTX3-5100U2, manufactured by Mitsubishi Electric Corporation), under the conditions of aperture Φ1.1 mm, beam diameter of about 110 μm, energy 6 to 8 mJ, and the number of shots 6. And through-holes having a diameter of 100 µm were formed.

<Example 9 and Comparative Example 9>

Except having made the thickness of the resin layer of the base material with a resin layer at the time of prepreg manufacture as it showed in Table 7, it carried out similarly to Example 1 using the varnish obtained by the manufacture example of the fiber woven fabric and varnish shown in Table 7. The leg, the laminated board with metal which has copper foil on both surfaces of the insulating layer of 40 micrometers in thickness, the printed wiring board (inner layer circuit board), the multilayer printed wiring board, and the semiconductor device were obtained.

In addition, through-hole formation of a printed wiring board uses a carbon dioxide laser (ML605GTX3-5100U2, manufactured by Mitsubishi Electric Corporation), under the conditions of aperture Φ1.1 mm, beam diameter of about 110 μm, energy 6 to 8 mJ, and the number of shots 6. And through-holes having a diameter of 100 µm were formed.

The following evaluation was performed about the prepreg obtained by the Example and the comparative example, the laminated board with a metal, the printed wiring board (inner layer circuit board), and a semiconductor device. Evaluation items are shown together with contents. Moreover, the obtained evaluation result is shown to Tables 4-7.

In addition, since the measurement result of the PKG curvature mentioned later depends on the thickness of the insulating layer of the laminated plate with metal, the evaluation result of the Example and comparative example whose thickness of the insulating layer of the laminated plate with metal is 150 micrometers is shown in Table 4, and with metal The evaluation result of the Example and comparative example whose thickness of the insulating layer of a laminated board is 100 micrometers is shown in Table 5, The evaluation result of the Example and comparative example whose thickness of the insulating layer of a laminated plate with metal is 60 micrometers is shown in Table 6, and with metal Table 7 shows the evaluation results of Examples and Comparative Examples in which the thickness of the insulating layer of the laminate was 40 μm.

In addition, in Tables 4-7, the filler amount (mass%) in a resin composition shows the filler amount when the whole resin composition is 100 mass%, and the composition (mass)% of the filler made the whole filler 100 mass%. The ratio of each component at time is shown.

<Evaluation method>

(1) Impregnation of Resin Composition

After curing the prepreg obtained in the above Examples and Comparative Examples for 1 hour at a temperature of 170 ° C., the cross section (for the range of 300 mm in the cross section in the width direction) was observed by SEM (scanning electron microscope) to void the inside of the fiber. Was evaluated. The voids are observed as white granular spots on the fiber cross section, on the image.

The respective codes are as follows.

(Circle): When resin composition impregnates all well and there is no void inside a fiber

×: when there is a void inside the fiber

(2) formability

After etching the copper foil of the laminated sheet with metal obtained in the above Examples and Comparative Examples, the range of 500 mm x 500 mm was observed by SEM (scanning electron microscope) to determine the insulation layer (resin layer on the surface of the fiber woven layer). The presence or absence of voids on the surface was evaluated. The voids are observed as white granular spots on the image.

The respective codes are as follows.

○: no void

×: void

(3) moisture absorption soldering heat resistance

Using a sample obtained by cutting a 50 mm × 50 mm square of the laminated sheet with a metal obtained in the above Examples and Comparative Examples, all copper foils other than half of one side of the sample were etched away according to JIS C-6481, and a pressure cooker ) After 2 hours of treatment at 121 ° C. and 2 atmospheres with a tester (manufactured by Espe Co.), it was immersed in a soldering bath at 260 ° C. for 30 seconds, and the presence or absence of abnormality in appearance change was visually observed.

The respective codes are as follows.

○: no abnormality

×: there is expansion, peeling

(4) Coefficient of Thermal Expansion (CTE) (ppm / K)

The coefficient of linear thermal expansion (CTE) is made by using a TMA (thermomechanical analysis) device (manufactured by TA Instruments Co., Ltd., Q400), and fabricating a test piece of 4 mm x 20 mm to obtain a temperature range of 30 to 300 ° C, 10 ° C / min, and a load of 5 g. CTE in 50-100 degreeC of the 2nd cycle was measured. In addition, the sample used what removed the copper foil of the laminated sheet with a metal obtained by each Example and the comparative example.

(5) laser processability

Using the printed wiring board (inner layer circuit board) obtained by the said Example and the comparative example, the cloth protrusion amount of the through-through hole after carbonic acid laser processing, and the roundness of the hole diameter were measured. The cloth protrusion amount and roundness were measured using a color 3D laser microscope (manufactured by Keyence, apparatus name VK-9710), and the cloth protrusion amount was measured just above the hole on the laser incident side to measure the protrusion length from the hole wall surface. The roundness was measured by observing directly above the hole on the laser incident side, measuring the long and short diameters of the maximum hole diameters, and calculating the long diameter and short diameter. In addition, the sample used the printed wiring board (inner-layer circuit board) obtained by the said Example and a comparative example, observed the board | substrate immediately after the hole processing of diameter 100 micrometers on the carbon dioxide laser conditions shown in following Table 2, and showed the average value of ten through holes. I did.

Device: Mitsubishi Electric Corporation, ML605GTX3-5100U2

Pulse length: 10μsec / 1 shot + 97μsec / 2 ~ 6 shot

The respective codes are as follows.

(Circle): When cloth protrusion amount is less than 10 micrometers, or roundness is 0.85 or more

(Triangle | delta): When cloth protrusion amount is 10 micrometers or more, or roundness is less than 0.85.

X: When cloth protrusion amount was 10 micrometers or more, or roundness was less than 0.85

(6) Insulation reliability of through-hole

The insulation reliability between through-holes was evaluated using the printed wiring board (inner layer circuit board) obtained by the said Example and the comparative example.

Using the 0.1 mm part of the through-hole wall surface of a printed wiring board, it evaluated by continuous measurement on the conditions of the applied voltage 10V and temperature of 130 degreeC, and 85% of humidity. In addition, the measurement was performed using the high acceleration life test apparatus (ESP Co., Ltd. EHS-211 (M), AMI ion migration system), and it finished when the insulation resistance value became less than 10 <^8> .

The respective codes are as follows.

(Double-circle): It exceeded 200 hours.

(Circle): 100 or more and 200 or less.

(Triangle | delta): It was 50 hours or more and less than 100 hours.

X: It was less than 50 hours.

(7) PKG bending

The semiconductor device (14 mm x 14 mm) obtained in Examples and Comparative Examples was placed in a sample chamber of a temperature-variable laser three-dimensional measuring instrument (Model LS220-MT100MT50 manufactured by Hitachi Technology & Service Co., Ltd.) with the semiconductor element face down. The warpage at room temperature (25 ° C) and 260 ° C of the semiconductor device was measured. The measurement of the warp measured the displacement of the height direction, and made the value with the largest displacement difference the deflection amount. In addition, the measurement range was 13 mm x 13 mm size.

Each code | symbol is as Table 3 below. In addition, since the measurement of PKG curvature depends on the thickness of the insulating layer of the laminated plate with metal, it determined as shown in Table 3 for every thickness of the insulating layer of the laminated plate with metal.

The photograph of the cross section of the prepreg obtained in Example 1 was shown in FIG. 3, and the photograph of the cross section of the prepreg obtained in the comparative example 4 was shown in FIG. 4 as a representative example of the observation result of the impregnation property of said (1) resin composition.

As can be seen from FIG. 4, in Comparative Example 4, voids were observed in the fiber woven fabric because of poor impregnation of the resin composition. On the other hand, as shown in FIG. 3, in Example 1, since the impregnation property of the resin composition was favorable, there was no void in a fiber woven fabric.

In Example 1, it is thought that the impregnability of a resin composition improved by the nanosized silica particle sticking in a strand. On the other hand, in the comparative example 4, since the silica particle of the nanosize is not contained, it turns out that the impregnation property of the resin composition could not be aimed at.

As a representative example of the moldability observation result of the said (2) laminated sheet with metal, the photograph of the surface which etched the copper foil of the laminated sheet with metal obtained in Example 1 in whole is shown in FIG. 5, and the copper foil of the laminated sheet with metal obtained by the comparative example 6 is shown The photograph of the surface etched by the front surface is shown in FIG. 6, and the SEM photograph of the enlarged view of the void (a white granular point on an image) observed in FIG. 6 is shown in FIG. 7, and the enlarged view of the cross section of the void observed in FIG. The SEM photograph of the is shown in FIG. As can be seen from FIGS. 6, 7 and 8, in Comparative Example 6, voids were observed on the surface of the laminate with the metal on the entire surface. On the other hand, as shown in FIG. 5, in Example 1, there was no void in the surface etched all over.

9-12 is a SEM photograph of sectional drawing which shows a part of strand which comprises the fiber woven fabric of the prepreg obtained in Example 1. FIG. 9 has shown the cross section parallel to the extending direction of a strand. 10-12 has shown the cross section perpendicular | vertical to the extending | stretching direction of a strand.

As shown to FIGS. 9-12, it turns out that a silica particle exists in strand in the prepreg obtained in Example 1.

In Examples 1-9 shown to Tables 4-7, favorable prepreg impregnation property was obtained. Moreover, it turns out that all the other various characteristics can obtain a favorable result. It is thought that this is due to the preparation of the prepreg under the condition that the silica particles enter the strand constituting the fiber woven fabric.

In addition, various factors, such as the average particle diameter of a silica particle, content of the silica particle in a filler, content of the filler in a resin composition, and the bulk density of a fiber woven fabric, are mentioned as a factor which controls that a silica particle in a strand enters, for example. Can be.

As can be seen from Tables 4-7, in Examples 1-9, the resin composition contained in a varnish contains 50-85 mass% of fillers in the whole said resin composition, and the silica particle whose average particle diameter is 5-100 nm in the said filler is used. It contained 1-20 mass%, and the bulk density of the fiber woven fabric was 1.05-1.30 g / cm <^3> . In this case, the evaluation result was excellent in all the said evaluation items. In other words, the prepreg according to this embodiment is excellent in impregnation of the resin composition to the fiber woven fabric, low thermal expansion properties, excellent laser workability when used as an insulating layer of a printed wiring board, and the hole formed by the laser is the precision of the hole diameter and shape It turned out that the hole can suppress the protrusion of the fiber and can be formed. Furthermore, it can be said that the prepreg concerning this Example is excellent in moisture absorption solder heat resistance, high heat resistance, excellent moldability, and excellent surface smoothness, and also excellent adhesiveness with a conductor layer. Moreover, since the PKG curvature in the semiconductor device of this invention is small, it turns out that the prepreg which concerns on a present Example is low thermal expansion and is high rigidity.

Good prepreg impregnation was also obtained in Comparative Example 1.

However, in Comparative Example 1, good results were not obtained in CTE and package warpage. It is considered that this is because the content of the filler is low, so that only the resin component of the resin composition is gathered into the strand, whereby the silica particles are prevented from entering the strand. Thereby, it is thought that the filling material cannot be hardly filled, the CTE of the prepreg increases, and package warpage has occurred.

In Comparative Example 6, good results could not be obtained. Since this cannot impregnate a sufficient amount of the resin composition due to the low bulk density, it is considered that the silica particles contained in the resin composition are suppressed from entering into the strands. Moreover, since the bulk density of a fiber woven fabric is small, it becomes a thick fiber base material, and the thickness of the resin layer of the surface layer of a prepreg becomes thin. For this reason, although CTE is favorable because of inferior moldability and moisture absorption solder heat resistance, it is thought that PKG curvature arose.

In Comparative Examples 4 and 7 to 9, good results were not obtained with respect to the impregnation of the prepreg. In Comparative Examples 4 and 7 to 9, no nano-sized silica particles were contained in the resin composition constituting the prepreg. For this reason, it is thought that a silica particle did not get into a strand and the impregnation property of the resin composition was not able to be aimed at. In addition, good results could not be obtained for various other properties such as CTE and package warpage.

In the comparative example 7, laser workability is inferior because the bulk density of a fiber woven fabric is small, and insulation reliability of a through-hole is inferior because of poor impregnation. Moreover, since the relatively thick fiber woven fabric was used, the thickness of the resin layer of the prepreg became thin, inferior in moldability and moisture absorption solder heat resistance, and PKG curvature arose.

In Comparative Examples 8 and 9, the thickness of the insulating layer of the laminate with metal is relatively thin, so that the moldability, the moisture absorption solder heat resistance, and the insulation reliability of the through-through hole are excellent. However, since the bulk density of the fiber woven fabric was small, good results could not be obtained in laser workability.

Also in Comparative Examples 2, 3 and 5, good results could not be obtained with respect to the impregnation of the prepreg. In addition, good results could not be obtained for other various properties. In the comparative example 2, since the content of a filler is too large, the fluidity | liquidity of the silica particle in a resin composition is not acquired, and it is thought that it is suppressed that a silica particle enters in a resultant strand. In Comparative Example 3, since the content of the nano-sized silica particles is large, it is considered that the nano-sized silica particles aggregate to suppress the silica particles from entering into the resultant strands. In the comparative example 5, since the bulk density of a fiber woven fabric is large, it is thought that it is suppressed that a silica particle enters into a strand.

In the comparative example 5, since the bulk density of a fiber woven fabric was too large, the impregnation property of the resin composition was inferior, and the moisture absorption solder heat resistance was inferior, and also the laser workability and the insulation reliability of a through-through hole were inferior.

In the comparative example 6, since the bulk density of a fiber woven fabric was small, the laser workability and the insulation reliability of through-through hole were inferior. Moreover, since the bulk density of a fiber woven fabric is small, it becomes a thick fiber base material, and the thickness of the resin layer of the surface layer of a prepreg becomes thin. For this reason, PKG curvature generate | occur | produced because of inferior moldability and moisture absorption solder heat resistance.

This application claims the priority based on Japanese Patent Application No. 2011-012166 for which it applied on January 24, 2011, and inserts all the indications here.

Claims (18)

As a prepreg formed by impregnating a resin composition in the fiber fabric comprised by strands,
The bulk density of the fiber fabric is 1.05 ~ 1.30g / cm ³ ,
The resin composition comprises at least a thermosetting resin and a filler,
The filler is contained in a proportion of 50 to 85% by weight relative to the solid content of the resin composition, and also contains silica particles having an average particle diameter of 5 to 100nm in a ratio of 1 to 20% by weight relative to the filler,
The prepreg in which the said silica particle exists in the said strand. The method according to claim 1,
The prepreg in which the space | gap which has a length of 50 micrometers or more does not exist in the said strand in the direction which the fiber which comprises the said strand extends. The method according to claim 1,
The prepreg whose water density of the space | gap whose diameter in a strand is 50 micrometers or more is 50 cm <^-3> or less. The method according to claim 1,
Prepreg with a total thickness of 30 to 220 µm. The method according to claim 1,
The strand prepreg composed of a glass fiber containing at least SiO ₂ of 50 to 100 mass%, Al ₂ O ₃ 0 to 30 weight%, CaO in a proportion of 0 to 30% by weight. The method according to claim 5,
The said glass fiber is the prepreg which uses at least 1 sort (s) of glass chosen from the group which consists of T glass, S glass, D glass, E glass, NE glass, and quartz glass. The method according to claim 5,
The said glass fiber is the prepreg whose Young's modulus when it is plate shape is 50-100 GPa, the tensile strength when it is plate shape is 25 GPa or more, and the tensile strength of the longitudinal direction when it is made into a fiber woven fabric is 30 N / 25 mm or more. The method according to claim 5,
The air permeability of the fiber woven fabric is 1 ~ 80 cc / cm ² / sec prepreg. The method according to claim 1,
The said silica particle is the prepreg which surface-treats by functional group containing silanes or alkylsilazane. The laminated board obtained by hardening | curing the prepreg of Claim 1. The method of claim 10,
The laminated board with which the conductor layer is provided in the at least one outer side surface of the said prepreg. The printed wiring board which uses the prepreg of Claim 1, or the laminated board of Claim 10 for an inner layer circuit board. The method of claim 12,
The printed wiring board in which the prepreg of Claim 1 is provided as an insulating layer on the said inner-layer circuit board. The semiconductor device which mounts a semiconductor element in the printed wiring board of Claim 12. delete delete delete delete

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